WO2015076399A1

WO2015076399A1 - Glycolurils having functional group and use thereof

Info

Publication number: WO2015076399A1
Application number: PCT/JP2014/081009
Authority: WO
Inventors: 岳熊野; 琢磨武田; 昌三三浦; 隆志柏原; 昇溝部
Original assignee: 四国化成工業株式会社
Priority date: 2013-11-25
Filing date: 2014-11-25
Publication date: 2015-05-28

Abstract

Provided are glycolurils represented by general formula (Z). (Z) (In the formula, group Z is a carboxyalkyl group, glycidyl group, or allyl group, R¹ and R² are each independently a hydrogen atom, lower alkyl group, or phenyl group, R³, R⁴, and R⁵ are each independently a hydrogen atom or the same group as group Z, provided that when group Z is a carboxyalkyl group, R³, R⁴, and R⁵ are a carboxyalkyl group the same as group Z and when group Z is an allyl group, R⁵ is a hydrogen atom.) Also provided are various resin compositions comprising the glycolurils, for example, a polyester resin composition, epoxy resin composition, or silicone resin composition.

Description

Glycolurils with functional groups and their use

The present invention relates to glycolurils having a functional group and use thereof. In particular, the present invention has at least one carboxyalkyl group, glycidyl group, or allyl group in the molecule as a functional group, and glycolurils useful as components of various resin compositions depending on the functional group, Furthermore, it is related with various useful resin compositions containing them as utilization of such glycolurils.

Glycolurils are heterocyclic compounds having four urea nitrogens in the ring structure, and are used for various applications and production of new functional compounds by utilizing the reactivity of the urea nitrogens. Yes.

On the other hand, a functional group rich in reactivity, for example, a compound having a plurality of allyl groups in the molecule, for example, triallyl isocyanurate, is well known as a crosslinking agent for synthetic resins and synthetic rubbers. Tetraallyl glycolurils having four allyl groups in the molecule that function as a crosslinking agent for resins and synthetic rubbers are also known.

However, for example, compounds in which all hydrogen atoms on four nitrogen atoms of glycolurils are substituted with carboxyalkyl groups are expected to function as crosslinking agents for epoxy resins, etc., but are known so far. Absent.
Further, a compound having a plurality of glycidyl groups in the molecule as a functional group, for example, triglycidyl isocyanurate having three glycidyl groups in the molecule is well known as a crosslinking agent for epoxy resins.

However, a compound in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group has not been known so far.

A compound in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group is useful as an intermediate for the synthesis of an oxygen-containing compound, and a glycoluril having one epoxy group in the molecule. Are useful as reactive diluents in epoxy resins, for example, and glycolurils having two or more epoxy groups in the molecule are expected to be useful as crosslinking agents for epoxy resins, for example. The

As described above, tetraallyl glycolurils are already known, but glycolurils having one allyl group in the molecule are useful as such, for example, as synthetic intermediates, and Although allyl glycolurils having 2 or 3 allyl groups in the molecule are expected to be useful as crosslinking agents for synthetic resins and synthetic rubbers, they have not been known so far.

Therefore, the basic invention according to the present invention relates to novel glycolurils having a carboxyalkyl group, a glycidyl group or an allyl group as a functional group. Further, the present invention includes some already known glycolurils. The present invention relates to various useful resin compositions using glycolurils having a carboxyalkyl group, a glycidyl group or an allyl group as a functional group.

That is, the present invention comprises the above basic invention and the first, second and third inventions which are resin compositions using glycolurils each having a carboxyalkyl group, a glycidyl group and an allyl group as functional groups. The background art of the first, second and third inventions will be described below.

First Invention In particular, the first invention according to the present invention relates to the following two inventions.
(1) Novel tetrakis (carboxyalkyl) glycolurils and their use, in particular, epoxy resin compositions containing the above tetrakis (carboxyalkyl) glycolurils as crosslinking agents

(2) Polyester resin composition for powder coatings comprising a polyester resin obtained by polycondensation reaction of the above tetrakis (carboxyalkyl) glycolurils and glycols. Advantages of non-polluting paint with no generation, thick coating at one time, use immediately after coating, relatively low cost, and recovery In recent years, there has been a rapid increase in demand for paints for protective decoration of members such as home appliances, building materials and automobile parts.

As the powder coating, epoxy resin, acrylic resin, and polyester resin are mainly used. Among them, polyester resin powder coating has a balanced coating performance. It is.

In order to obtain a powder coating having excellent weather resistance, it is necessary to improve the weather resistance of the polyester resin as a main component. Usually, co-use of isophthalic acid as a carboxylic acid component and neopentyl glycol as a glycol component is required. A polyester resin having a high polymerization rate is used.

Since isophthalic acid has a different absorption range with respect to the wavelength range of solar energy, and neopentyl glycol does not have hydrogen bonded to the carbon at the β-position, polyesters with more of these components are less susceptible to photodegradation. It is known that the weather resistance is good.

Isocyanate-based curing agents with hydroxyl groups at the main ends used in polyester resin powder coatings have a structure that shows no activity below a certain temperature by blocking highly reactive isocyanate groups with blocking agents. However, the block agent is dissociated at the time of baking, so that the baking furnace is contaminated.

In addition, although the triglycidyl isocyanurate-based curing agent does not contain a blocking agent, it is not preferable to use it because of its mutagenicity.

In recent years, hydroxyalkylamide curing agents have attracted attention as curing agents that can replace triglycidyl isocyanurate curing agents. A powder coating using a hydroxyalkylamide-based curing agent can be baked at a low temperature, does not generate volatiles during baking, and can be a clean coating with no environmental burden.

However, powder coatings using a hydroxyalkylamide-based curing agent have the disadvantage that the smoothness of the coating film and the adhesion to the object to be coated, particularly the adhesion after water and moisture resistance, are poor.

In order to solve such a problem, a powder paint obtained from a polyester resin comprising an aromatic dicarboxylic acid and an aliphatic diol having a specific viscosity and acid value has been proposed (see Patent Document 1). Although this powder coating is excellent in the smoothness of the coating film and the adhesion to the object to be coated, satisfactory weather resistance is not expressed.

In addition, a powder coating mainly composed of a resin obtained by depolymerizing a polyester resin composed of isophthalic acid and neopentyl glycol with isophthalic acid or the like has been proposed (see Patent Document 2). However, this powder coating is excellent in weather resistance, low-temperature curability, coating film smoothness, and adhesion to a material, but the coating film smoothness is still not sufficient.

Second invention The second invention according to the present invention is a novel glycidyl glycoluril in which a hydrogen atom on at least one nitrogen atom of a glycoluril is substituted with a glycidyl group and use thereof, particularly an epoxy containing the same. The present invention relates to a resin composition.

That is, the second invention according to the present invention relates to the following four inventions.
(1) Novel glycidyl glycolurils and resin compositions containing the same Glycolurils having a glycidyl group as a functional group have not been known so far, but are expected to be useful due to the reactivity of the glycidyl group. Is done.

(2) Epoxy resin composition for sealing an optical semiconductor element In recent years, as a thermosetting resin composition used for sealing an optical semiconductor element such as a light emitting element or a light receiving sensor, transparency of the cured body is required. Therefore, in general, an epoxy resin composition obtained by using an epoxy resin such as a bisphenol A type epoxy resin and a curing agent such as an acid anhydride is widely used.

However, recently, the brightness of light-emitting elements has increased, and the use of light-receiving sensors as in-vehicle applications and Blu-ray pickups has become widespread. Therefore, thermosetting resin compositions have higher heat resistance or light resistance than before. There is a demand for a transparent sealing material having a property.

Therefore, in the thermosetting resin composition, as a technique for improving heat resistance or light resistance, a technique for increasing the glass transition temperature (Tg) of the cured product using a polyfunctional epoxy resin or an alicyclic epoxy is used. A method of suppressing light deterioration due to light absorption using a resin has been proposed (see Patent Document 3).

As such an epoxy resin, for example, triglycidyl isocyanurate is used. However, since the cured body of the thermosetting resin composition using triglycidyl isocyanurate is hard and brittle, there arises a problem that cracks occur in the cured body due to thermal contraction when the optical semiconductor element is sealed with resin. . In addition, since triglycidyl isocyanurate has high crystallinity, a liquid thermosetting resin composition using the triglycidyl isocyanurate has problems such as an increase in viscosity due to crystallization. There was a problem that time could not be obtained.

(3) Thermosetting resin composition containing phenolic compound The thermosetting resin composition represented by the epoxy resin composition is excellent in workability and has excellent electrical properties, heat resistance and adhesiveness. Due to moisture resistance (water resistance), etc., it is widely used in the fields of electric / electronic parts, structural materials, adhesives, paints, and the like.

However, in recent years, with the advancement of technology in the electric and electronic fields, the resin used as a material has been improved in purity, moisture resistance, adhesiveness, dielectric properties, and low resistance for high filler filling. There is a need for further improvements in various properties such as viscosity increase and increased reactivity to shorten the molding cycle.

Also, in aerospace materials, leisure / sports equipment applications, etc., lightweight materials with excellent mechanical properties are required as structural materials.

In particular, in the field of semiconductor encapsulation and substrates (substrates themselves and their peripheral materials), electronic devices are becoming smaller, lighter, and more multifunctional, and as a result, higher integration of LSIs and chip components is progressing. The form is rapidly changing to a higher pin count and smaller size. For this reason, in order to improve the mounting density of electronic components, development of fine wiring has been advanced for printed wiring boards.

There is a built-up method as a printed wiring board manufacturing method meeting these requirements, and it is becoming mainstream as a method suitable for weight reduction, miniaturization, and miniaturization.

Also, due to the growing environmental awareness, there is an active movement to regulate materials that may generate harmful substances during combustion, including electronic parts. Bromine compounds have been used in conventional printed wiring boards to make them flame retardant. However, since there is a possibility of generating harmful substances during combustion, it is expected that this bromine compound will not be usable in the near future. Is done.

¡Lead-free solder that does not contain lead is also being put into practical use as a solder generally used for connecting electronic components to a printed wiring board. Since this lead-free solder has a use temperature of about 20 to 30 ° C. higher than that of conventional eutectic solder, the material is required to have higher heat resistance than ever before.

In addition, a low dielectric constant layer is formed on the surface of a recent silicon chip for high-speed computation or the like, and the formation of this low dielectric constant layer makes the silicon chip very brittle. Conventional printed wiring boards have a large difference in thermal expansion coefficient from silicon chips, and in order to ensure connection reliability when silicon chips are mounted, the thermal expansion coefficient of printed wiring boards is comparable to the thermal expansion coefficient of silicon chips. It is demanded to reduce it to a minimum.

In order to reduce the thermal expansion coefficient of a printed wiring board, generally, a method has been adopted in which a large amount of an inorganic filler having a low thermal expansion coefficient is filled to reduce the thermal expansion coefficient of the entire insulating layer (see, for example, Patent Document 4). . However, such a method tends to cause many problems such as a decrease in fluidity and a decrease in insulation reliability.

Therefore, attempts have been made to achieve low thermal expansion by selecting a resin or improving the resin. For example, as an example of an epoxy resin having an aromatic ring, a low thermal expansion pressure molding resin composition using an epoxy resin having a bifunctional naphthalene skeleton or a biphenyl skeleton has been proposed (see Patent Document 5). ) And 80 to 92.5% by volume of filler.

In addition, conventionally, a method for reducing the thermal expansion coefficient of a resin composition for a wiring board is generally a method of increasing the crosslinking density, increasing the glass transition temperature (Tg), and reducing the thermal expansion coefficient (Patent Document 6). And 7). However, in order to increase the crosslink density, it is necessary to shorten the molecular chain between the functional groups. However, it is difficult to shorten the molecular chain beyond a certain point in terms of reactivity and resin strength.

Furthermore, introduction of an imide skeleton, which is considered to be useful for heat resistance and low thermal expansion, has been attempted. For example, a thermosetting resin composition for build-up using an aromatic diamine having an imide group and an epoxy resin is proposed. (See Patent Document 8). However, when a low molecular weight polyimide compound is used as a curing agent for an epoxy resin, most of them are not different from the characteristics of the epoxy resin in many cases.

(4) Alkali-developable photocurable / thermosetting resin composition Generally, a printed wiring board used in an electrical product has a solder resist film formed as a permanent protective film on a substrate having a circuit of a conductor layer. Yes. This solder resist film prevents solder from adhering to unnecessary parts in the soldering process for bonding (mounting) electrical / electronic components to printed wiring boards, avoiding short circuits and conductors. It is what protects the layer.

Therefore, the solder resist film is required to have properties such as adhesion to the substrate and the conductor layer, chemical resistance, and insulation. As a resin composition from which a solder resist film satisfying these characteristics can be obtained, a resin composition that can be developed with an alkaline aqueous solution is known (see Patent Document 9). However, the solder resist film obtained by curing this composition has insufficient flexibility and has a problem that cracks occur during cutting and thermal shock tests. Note that the cracks in the solder resist film not only serve to protect the insulation, but also cause circuit disconnection.

Also, resin compositions for flexible printed wiring boards have been proposed (see Patent Documents 10, 11 and 12). However, the solder resist film obtained by curing these compositions has not yet exhibited sufficient flexibility. In addition, when trying to improve flexibility, problems such as a decrease in soldering heat resistance have occurred, and no one having sufficient performance has been proposed.

Thus, there is a demand for a resin composition capable of obtaining a solder resist film having excellent flexibility and thermal shock resistance while maintaining the basic characteristics required for the solder resist film.

Third Invention The third invention according to the present invention relates to the following six inventions.
(1) Novel allylglycolurils Reactive compounds having a plurality of allyl groups in the molecule, such as triallyl isocyanurate, are well known as crosslinking agents for synthetic resins and synthetic rubbers. Further, tetraallylglycolurils having four allyl groups in a molecule that functions as a crosslinking agent for synthetic resins and synthetic rubbers are also known (see Patent Document 13).

However, glycolurils having one allyl group in the molecule are useful as such as, for example, synthetic intermediates, and glycolurils having two or three allyl groups in the molecule are also useful. Although it is expected to be useful as a crosslinking agent for synthetic resins and synthetic rubbers, it has not been known so far.

(2) Olefin-based resin composition Olefin-based resins have excellent electrical insulation and solvent resistance, and include radiation crosslinking, electron beam crosslinking, peroxide crosslinking, sulfur crosslinking, and silane crosslinking with silane compounds. By appropriately adopting various crosslinking means, it is possible to control various physical properties of the olefin resin, and it is widely used in various fields including electric and electronic materials.

As described above, glycolurils are heterocyclic compounds having four urea nitrogens in the ring structure, and use intermediates of various applications and functional compounds by utilizing the reactivity of urea nitrogens. Is used.

Among these, glycolurils having an allyl group rich in reactivity in the molecule are expected to be useful as a crosslinking agent for olefinic resins due to the active allyl group.

(3) Curable composition with excellent adhesiveness The demand for reliability in the external environment such as light and heat in the field of electronic materials and optical materials is increasing year by year. In this field, thermosetting resins have been used for a long time. In particular, epoxy resins have been widely used because of their versatility and high adhesion to various substrates. As peripheral materials such as luminance light emitting diodes and power semiconductors, they are insufficient from the viewpoint of long-term heat resistance and light resistance. As a material satisfying such heat resistance and light resistance, glass has been known for a long time, but there is a problem that workability and adhesion to a substrate are poor.

In order to solve these problems, organic-inorganic hybrid resins that have better heat and light resistance than organic polymer materials such as epoxy resins, and better workability and adhesion than inorganic polymers such as glass, are widely used. Among them, thermosetting resins using a hydrosilylation reaction that is an addition reaction of a carbon-carbon double bond and a hydrosilyl group have been proposed (see, for example, Patent Documents 14, 15, and 16). Has excellent heat resistance, light resistance and adhesion.

However, from the viewpoint of optical transparency, none of them is sufficient, so that it has been difficult to apply it to optical material applications such as light emitting diodes and display devices.

In contrast, in a system having an isocyanuric acid skeleton as an organic component (see, for example, Patent Document 17), a composition that provides a thermosetting resin having high transparency while maintaining the above characteristics has been proposed. The glass transition point is high. For example, when it is applied on a substrate, the occurrence of warpage due to the high thermal stress and the low adhesiveness have been problems.

In order to solve such a problem, a composition containing a compound having an epoxy group such as a glycidyl group as a component has been proposed (see, for example, Patent Document 18), but an epoxy group is introduced to develop adhesiveness. Therefore, there is a trade-off problem that heat resistance and light resistance deteriorate.

Against this background, development of a thermosetting resin that suppresses warping and provides excellent adhesion by reducing thermal stress while maintaining excellent heat resistance, light resistance, and transparency has been eagerly desired. .

(4) Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril In order to encapsulate a semiconductor device with a resin, a transfer mold using a mold, potting with a liquid encapsulating resin, Screen printing and the like are performed. In recent years, with the miniaturization of semiconductor elements, there has been a demand for downsizing and thinning of electronic devices, and it has become necessary to resin seal a thin package having a thickness of 500 μm or less and a stack of silicon dies.

On the other hand, various uses of isocyanurate compounds, which are substances similar to glycolurils, have been proposed in connection with the present invention.

For example, as a composition using an isocyanurate ring-containing polymer and an isocyanurate ring-containing terminal hydrogen polysiloxane polymer, an epoxy of polysiloxane obtained by addition reaction of diallyl monoglycidyl isocyanurate to an Si—H group-containing polysiloxane. Group-opening polymer-containing composition (see Patent Document 19), the above-described isocyanurate ring-containing polysiloxane and Si—H group-containing polysiloxane polymer-containing composition (see Patent Document 20), triallyl isocyanurate and Si— Addition-curable composition with H group-containing polysiloxane (see Patent Document 21), polysiloxane containing isocyanurate ring and Si—H group, alkenyl group-containing cured product, and addition-curable composition (Patent Documents 22, 23) And 24) are known.

However, since the above-mentioned isocyanurate ring-containing polymer composition contains a siloxane bond in the main component, it is flexible but poorly compatible with the crosslinking agent. Further, since the position of the alkenyl group is uncertain, it is difficult to cure by addition reaction, and the characteristics (rapid curing reaction) of hydrosilylation (addition reaction) cannot be utilized. In addition, the isocyanuric acid-containing polymer composition has a problem that it has a high crosslinking density, is rigid and lacks flexibility.

Under these circumstances, a cured product obtained by addition reaction between an isocyanurate ring-containing polysiloxane and an Si—H group-containing polysiloxane, which has excellent flexibility, curing characteristics, compatibility, and water vapor permeability resistance. Has not yet been obtained.

(5) Electron beam curable resin composition Since LED elements are power-saving and have a long life, they have been widely used in recent years as light sources to replace incandescent bulbs and the like. In general, when an LED element is used as a light source, a plurality of LED elements are installed on a metal substrate, and a reflector is disposed around the LED element, thereby reflecting light and improving illuminance.

However, in the case of the apparatus using the reflector as described above, there is a problem that the reflectivity is lowered due to the deterioration of the reflector due to heat generation during light emission, and as a result, the luminance is lowered.

Therefore, in order to cope with this problem, an electron beam curable resin composition using triallyl isocyanurate as a cross-linking agent for polyolefin resin has been proposed, and if such a resin composition is used, deterioration of the reflector device has been proposed. (See Patent Document 25). However, since triallyl isocyanurate used in the resin composition has high volatility, there has been a problem that a crosslinking agent is reduced at the time of thermoforming in producing a cured product.

(6) Silicone resin composition Conventionally, it has been proposed to use an epoxy resin as a resin in a composition for sealing an optical semiconductor (for example, see Patent Document 26). However, the sealing body obtained from the composition containing an epoxy resin has a problem such as yellowing due to heat generated from the white LED element.

A room temperature-curable organopolysiloxane containing an organopolysiloxane having two silanol groups, a silane compound having two or more hydrolyzable groups bonded to a silicon atom in one molecule, and an organic zirconium compound. Siloxane compositions have been proposed (see Patent Documents 27 and 28). Furthermore, it has been proposed to mix and heat a condensation catalyst to diorganopolysiloxane having two silanol groups and silane having three or more alkoxy groups (see Patent Documents 29 and 30).

However, in the case of silicone resin, gas permeability is higher than epoxy resin and air easily passes through, so the silver plating of the optical semiconductor package is easily discolored over time due to hydrogen sulfide in the air. There was a problem that decreased. Moreover, in the case of silicone resin, it is generally performed to harden the resin in order to improve the sulfidation resistance. However, in that case, there is a problem of shrinkage due to curing, peeling from the LED package, and wire breakage. .

JP 2003-119256 A JP 2006-37015 A JP-A-2-222165 JP 2004-182851 A Japanese Patent Laid-Open No. 5-148543 JP 2000-243864 A JP 2000-114727 A JP 2000-17148 A JP-A-1-141904 JP-A-7-207211 JP-A-8-274445 Japanese Patent Laid-Open No. 9-5997 Japanese Patent Application Laid-Open No. 11-171887 JP-A-3-277645 Japanese Patent Laid-Open No. 7-3030 JP 9-302095 A International Publication No. 02/053648 Pamphlet Japanese Patent No. 4216512 JP 2008-143594 A JP 2008-150506 A JP-A-9-291214 Japanese Patent No. 4073223 JP 2006-291044 A JP 2007-9041 A JP 2013-166926 A Japanese Patent Laid-Open No. 10-228249 Japanese Patent Laid-Open No. 2001-200161 Japanese Patent Laid-Open No. 2-196860 JP 2007-224089 A JP 2006-206700 A

An object of the present invention is to provide a novel glycoluril having a functional group and various resin compositions containing the same as a basic invention. Furthermore, the present invention has an object to provide the following first, second, and third inventions in particular in view of the above-described state of the art.

1st invention The 1st invention by this invention,
(1) Novel tetrakis (carboxyalkyl) glycolurils and their use, in particular, epoxy resin compositions using tetrakis (carboxyalkyl) glycolurils,
(2) It aims at providing the polyester resin composition for powder coatings which gives the powder coating material which was excellent in the weather resistance of the coating film, smoothness, and low-temperature curability.

2nd invention The 2nd invention by this invention is:
(1) Novel glycidyl glycolurils and their use, in particular, various resin compositions containing the same,
(2) An object is to provide an epoxy resin composition for sealing an optical semiconductor element.

The inventors of the present invention have made extensive studies in order to obtain a sealing material for optical semiconductor elements that is liquid, has a long working life, and is excellent in heat resistance and light resistance. Then, paying attention to the epoxy resin component itself, and as a result of repeated research centering on the improvement of the properties of triglycidyl isocyanurate used in the past, the cured product obtained when using allyl glycoluril which is a liquid epoxy resin Discovered that heat resistance and light resistance were improved without impairing high transparency, and reached the epoxy resin composition for sealing an optical semiconductor element according to the present invention.

(3) Furthermore, an object of this invention is to provide the thermosetting resin composition containing a phenol compound.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that the intended purpose can be achieved by using glycidyl glycoluril as an epoxy compound (resin). It came to complete.

That is, the object of the present invention is to provide insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, and adhesives. Another object of the present invention is to provide a thermosetting resin composition that is useful for paints and the like and provides a cured product that is not only excellent in flame retardancy but also excellent in heat resistance and toughness.

(4) Another object of the present invention is to provide an alkali development type photocurable / thermosetting resin composition.

That is, as a result of intensive research on the above-mentioned problems, the present inventors achieved the intended purpose by using a photocurable thermosetting resin composition containing glycidyl glycoluril as an epoxy compound. As a result, the present invention has been completed.

Thus, the present invention provides a photocurable / thermosetting resin composition capable of obtaining a cured film having excellent flexibility and thermal shock resistance without impairing properties such as solder heat resistance, heat deterioration resistance, and acid resistance. And it aims at providing the printed wiring board which formed the soldering resist film (cured film) using these.

3rd invention The 3rd invention by this invention is:
(1) It is an object of the present invention to provide novel allyl glycolurils and various useful resin compositions using them.

(2) Olefin resin composition It aims at providing the olefin resin composition suitable as a raw material of the olefin resin which has a crosslinked structure.

(3) Curable composition with excellent adhesion The present invention uses tetraallylglycoluril as an essential component as an organic compound having an alkenyl group, so that the heat and light resistance of the cured product can be reduced without impairing heat resistance and light resistance. An object of the present invention is to provide a curable composition that reduces stress and exhibits excellent adhesiveness.

(4) Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril The present inventors have identified both specific resin components as a resin component comprising a main agent (base polymer) and a curing agent (crosslinking agent). A thermosetting resin composition using a terminal allylic glycoluril ring-blocked organopolysiloxane polymer (base polymer) and a glycoluril ring-containing terminal hydrogen polysiloxane polymer (crosslinking agent) in combination with a curing accelerator, When a semiconductor device is sealed, it has superior water resistance and gas permeability compared to conventional silicone compounds, and even when sealed, warpage is reduced and slight tack is generated on the surface of the cured product. Therefore, the present invention was found to be very versatile and completed the present invention.

That is, the present invention relates to a thermosetting resin composition that can provide a semiconductor device that has almost no warpage and is excellent in heat resistance and moisture resistance even when a semiconductor element is sealed. An object of the present invention is to provide a semiconductor device sealed with a resin composition.

(5) Electron beam curable resin composition The present invention is suitable for molding a reflector, and an object thereof is to provide an electron beam curable resin composition from which a cured product having excellent heat resistance can be obtained.

(6) Silicone resin composition An object of this invention is to provide the silicone resin composition from which the cured | curing material excellent in sulfidation resistance and transparency is obtained.

According to the present invention, as a basic invention, the general formula (Z)

(In the formula, group Z represents a carboxyalkyl group, a glycidyl group or an allyl group; R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group; and R ³ , R ⁴ and R ⁵ represent each Independently represents a hydrogen atom or the same group as group Z. However, when group Z is a carboxyalkyl group, R ³ , R ⁴ and R ⁵ represent the same carboxyalkyl group as group Z, and group Z is an allyl group. In this case, R ⁵ represents a hydrogen atom.)
Novel glycolurils having a functional group represented by the formula: are provided.

Furthermore, according to the present invention, the following first, second and third inventions are provided based on the novel glycolurils having the functional group.

First Invention (1) Novel Tetrakis (carboxyalkyl) glycoluril Carboxyl Glycoluril and Epoxy Resin Composition Containing The Same According to the present invention, the general formula (A)

(In the formula, n represents 0 or 1, and R ¹ and R ² each independently represent a hydrogen atom or a lower alkyl group.)
1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the formula:

According to the present invention, there is also provided a crosslinking agent for an epoxy resin as the use of the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril, and further, the crosslinking agent for an epoxy resin and an amine An epoxy resin composition comprising a curing agent is provided.

1,3,4,6-Tetrakis (carboxyalkyl) glycolurils according to the present invention are novel compounds in which all hydrogen atoms on four nitrogen atoms in a molecule are substituted with carboxylalkyl groups, ie molecules Glycolurils having 4 carboxyl groups in them.

Since such 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention are tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, conventional bifunctional or trifunctional Therefore, it is possible to obtain an epoxy resin cured product having a higher crosslinking density than that when a functional crosslinking agent is used, and thus, for example, an epoxy resin cured product superior in hardness, heat resistance, moisture resistance, and the like. It is useful as a crosslinking agent or solder flux activator.

(2) Polyester resin composition The polyester resin composition for powder coatings according to the present invention comprises:
(A) a polyester resin obtained by a polycondensation reaction between 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) and a glycol;
(B) contains a β-hydroxyalkylamide curing agent.

Such a resin composition for powder coating can be a powder coating excellent in the weather resistance and smoothness of the coating film and low-temperature curability.

Second invention (1) Novel glycidyl glycoluril and epoxy resin composition containing the same According to the present invention, general formula (B)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a glycidyl group.)
The glycidyl glycoluril represented by these is provided.

Further, according to the present invention, as the utilization of the glycidyl glycoluril, there is provided an epoxy resin crosslinking agent, and further an epoxy resin composition containing the epoxy resin crosslinking agent.

The glycidyl glycoluril according to the present invention is a novel compound in which at least one hydrogen atom of hydrogen atoms bonded to four nitrogen atoms of the glycoluril is substituted with a glycidyl group.

Accordingly, such compounds are useful as intermediates for the synthesis of novel oxygen-containing compounds, and those having one glycidyl group in the molecule can be used, for example, as reactive diluents for epoxy resins. Useful. Moreover, what has two or more glycidyl groups in a molecule | numerator is useful as a crosslinking agent for epoxy resins, for example.

In particular, since 1,3,4,6-tetraglycidyl glycoluril in which all hydrogen atoms on nitrogen atoms are substituted with glycidyl groups is tetrafunctional, for example, when used as a crosslinking agent for epoxy resins, A cured epoxy resin having a higher crosslinking density than when a conventional bifunctional or trifunctional crosslinking agent is used, and therefore, an epoxy resin cured product superior in hardness, heat resistance, and the like can be obtained. .

(2) Epoxy resin composition for sealing an optical semiconductor element The epoxy resin composition for sealing an optical semiconductor element according to the present invention comprises (1) an epoxy resin, and at least one component in the (1) epoxy resin is the above-mentioned These are glycidyl glycolurils represented by the general formula (B).

Furthermore, the epoxy resin composition for sealing an optical semiconductor element according to the present invention is preferably at least selected from a glass filler, a curing agent, a curing accelerator, a curing catalyst, a polyester resin, an organosiloxane, rubber particles, and an additive. It contains one component.

In the epoxy resin composition for sealing an optical semiconductor element according to the present invention, the glycidyl glycoluril has at least one glycidyl group (epoxy group) in the molecule and exhibits liquid properties at room temperature. When the resin composition is stored, the formation of crystalline substances is suppressed. As a result, a sufficient pot life can be obtained for resin sealing, as well as a high glass transition temperature (Tg), high strength, good transparency, and light resistance. Can be maintained.

Therefore, by using the epoxy resin composition for sealing an optical semiconductor element according to the present invention, an improvement in production workability is realized, the optical semiconductor device has high light transmittance, and is excellent in heat resistance and light resistance. Is obtained. Thus, a highly reliable optical semiconductor device is obtained by sealing an optical semiconductor element with the resin composition according to the present invention.

Furthermore, since the epoxy resin composition according to the present invention is liquid at the time of handling, it is excellent in handling properties at the time of sealing work. Accordingly, the epoxy resin composition according to the present invention can be preferably used as a resin composition for optical semiconductor encapsulation.

Moreover, the epoxy resin composition according to the present invention includes, for example, an adhesive, an electrical insulating material, a laminate, a coating, an ink, a paint, a sea lantern, a resist candy, a composite material, a transparent substrate, a transparent sheet, a transparent film, and an optical element , Optical lenses, optical members, stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memories, and the like.

(3) Thermosetting resin composition containing a phenol compound The thermosetting resin composition according to the present invention contains glycidyl glycoluril represented by the general formula (B) and a phenol resin as components.

Since the thermosetting resin composition according to the present invention provides a cured product having excellent flame retardancy, heat resistance and toughness, insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.) and laminated boards (printed wiring) Plate, build-up substrate, etc.) and various composite materials including CFRP, adhesives, paints and the like.

(4) Alkali development type photocurable / thermosetting resin composition The alkali development type photocurable / thermosetting resin composition according to the present invention comprises:
(A) Glycidyl glycoluril represented by the general formula (B),
(B) A photosensitive prepolymer having two or more unsaturated double bonds in one molecule and (c) a photopolymerization initiator.

Furthermore, the alkali-developable photocurable / thermosetting resin composition according to the present invention preferably contains an epoxy compound or an epoxy resin excluding the glycidyl glycoluril represented by the general formula (B).

The alkali development type photocurable / thermosetting resin composition according to the present invention preferably contains a diluent, a polybutadiene compound and a polyurethane compound.

The photocurable / thermosetting resin composition according to the present invention has both flexibility and thermal shock resistance without impairing the basic characteristics required for solder resist coating such as solder heat resistance and heat degradation resistance. Therefore, it can be suitably used in the formation of a solder resist film for printed wiring boards for various applications.

Moreover, the photocurable / thermosetting resin composition according to the present invention is superior in the flexibility of the cured film as compared with known photosensitive resin compositions used for flexible printed wiring boards, and is suitable for BGA or CSP. Compared to known photosensitive resin compositions used for printed wiring boards, the cured film has excellent thermal shock resistance.

Third invention (1) Novel allyl glycolurils The novel allyl glycolurils according to the present invention are:
General formula (C0)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or an allyl group.)
It is represented by

The allyl glycolurils according to the present invention are novel compounds in which 1 to 3 of nitrogen atoms of glycolurils are substituted with allyl groups.

Among such allyl glycolurils according to the present invention, glycolurils having one allyl group in the molecule are useful as such, for example, as synthetic intermediates, and two or Glycolurils having three allyl groups are expected to be useful as crosslinking agents for synthetic resins and synthetic rubbers.

(2) Olefin Resin Composition The olefin resin composition according to the present invention is represented by the general formula (C)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.)
Allyl glycolurils represented by the formula (I) and olefin polymers.

Various molded products such as films, sheets and cases (containers) obtained by crosslinking the olefin resin composition according to the present invention to obtain a crosslinked product (resin) and molding the product have excellent transparency. Furthermore, it has excellent resolution, electrical insulation, heat resistance, low moisture absorption, hydrolysis resistance, weather resistance, adhesion, mechanical properties such as elasticity, and the like.

(3) Curable composition excellent in adhesiveness The curable composition according to the present invention is:
(A) an organic compound having an alkenyl group,
(B) A curable composition comprising a compound having at least three or more hydrosilyl groups in one molecule and (C) a hydrosilylation catalyst,
As said (A) component, general formula (C1)

(In the formula, X represents a hydrogen atom, an alkyl group or an aryl group.)
The tetraallylglycoluril represented by these is an essential component.

The curable composition according to the present invention effectively reduces thermal stress while maintaining excellent heat resistance and light resistance, and provides a cured product having excellent adhesion and low warpage.

(4) Thermosetting resin composition for semiconductor encapsulation containing organopolysiloxane-modified allyl glycoluril The thermosetting resin composition according to the present invention comprises:
(A) General formula (C3) as alkenyl group-containing organopolysiloxane

(In the formula, each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, and p is an integer of 1 to 30.)
An organopolysiloxane polymer represented by:
(B) As organohydrogenpolysiloxane, general formula (C4)

(In the formula, each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, m is an integer of 0 to 5, and each siloxane repeating unit in the formula is bonded randomly. May be.)
A glycoluril ring-containing organohydrogenpolysiloxane polymer represented by:
(C) A curing accelerator is included.

The thermosetting resin composition according to the present invention preferably further comprises (D) an inorganic filler.

Further, the thermosetting resin composition according to the present invention has 0.8 to 4.0 moles of Si—H groups in the component (B) with respect to 1 mole of allyl groups in the component (A).

The thermosetting resin composition according to the present invention gives a semiconductor device having almost no warping and excellent heat resistance and moisture resistance even when a semiconductor element is sealed.

(5) Electron beam curable resin composition The electron beam curable resin composition by this invention contains polyolefin resin and a crosslinking agent, and the said crosslinking agent is general formula (C5).

(In the formula, m is an integer of 0 to 16.)
Or general formula <C6>

(In the formula, n is an integer of 0 or 1.)
It is an isocyanurate compound represented by these.

Furthermore, the electron beam curable resin composition according to the present invention contains a polyolefin resin and a crosslinking agent, and the crosslinking agent is an allyl glycoluril represented by the general formula (C).

The electron beam curable resin composition according to the present invention is suitable for molding a reflector and gives a cured product having excellent heat resistance.

(6) Silicone resin composition The silicone resin composition according to the present invention comprises:
(A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
(D) component: including allyl glycoluril represented by the general formula (C),
The component (D) comprises 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B).

The silicone resin composition according to the present invention preferably contains substantially no silicon compound having a silanol group.

In the silicone resin composition according to the present invention, the alkenyl group is preferably a vinyl group or a (meth) acryloyl group.

Furthermore, the silicone resin composition according to the present invention is particularly suitable as a resin composition for sealing an optical semiconductor element.

The silicone resin composition according to the present invention gives a cured product having excellent sulfidation resistance and transparency.

It is an IR spectrum of 1,3,4,6-tetrakis (carboxymethyl) glycoluril. It is an IR spectrum of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril. It is an IR spectrum of 1,3,4,6-tetrakis (2-carboxyethyl) glycoluril. It is an IR spectrum of 1,3-diallylglycoluril. It is an IR spectrum of 1,3-diglycidyl glycoluril. It is an IR spectrum of 1,3,4,6-tetraglycidyl glycoluril. It is an IR spectrum of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. It is IR spectrum of 1-allyl glycoluril. It is an IR spectrum of 1,3-diallylglycoluril. It is IR spectrum of 1,3,4-triallylglycoluril.

Hereinafter, the basic invention according to the present invention, the first, second and third inventions will be described in detail.

Basic Invention The basic invention according to the present invention is represented by the general formula (Z)

(In the formula, group Z represents a carboxyalkyl group, a glycidyl group or an allyl group; R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group; and R ³ , R ⁴ and R ⁵ represent each Independently represents a hydrogen atom or the same group as group Z. However, when group Z is a carboxyalkyl group, R ³ , R ⁴ and R ⁵ represent the same carboxyalkyl group as group Z, and group Z is an allyl group. In this case, R ⁵ represents a hydrogen atom.)
It is glycoluril represented by these.

That is, the glycolurils according to the present invention are 1,3,4,6-tetrakis <carboxyalkyl> glycolurils when the group Z is a carboxylalkyl group in the above general formula <Z>, and the group Z is When it is a glycidyl group, it is mono, di, tri and tetraglycidyl glycolurils, and when the group Z is an allyl group, it is mono, di and triallyl glycolurils.

Hereinafter, 1,3,4,6-tetrakis <carboxyalkyl> glycoluril and a resin composition using the same are the first invention, glycidyl glycoluril and a resin composition using the same are the second invention, The allyl glycoluril and a resin composition using the allyl glycoluril will be described in detail below as the third invention.

First invention (1) Novel 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and epoxy resin composition containing the same 1,3,4,6-tetrakis (carboxyalkyl) glycol according to the present invention Urils are represented by the general formula (A)

(In the formula, n represents 0 or 1, and R ¹ and R ² each independently represent a hydrogen atom or a lower alkyl group.)
It is represented by

In the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A), when R ¹ or R ² is a lower alkyl group, the lower alkyl group is usually carbon. The number of atoms is 1 to 5, preferably 1 to 3, and most preferably 1. Therefore, the most preferred lower alkyl group is a methyl group.

Accordingly, preferred specific examples of 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention include, for example,
1,3,4,6-tetrakis (carboxylmethyl) glycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) glycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a, 6a-dimethylglycoluril,
Examples include 1,3,4,6-tetrakis (2-carboxylethyl) -3a, 6a-dimethylglycoluril.

Among the 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention, those in which n is 0, that is, the following general formula (A1)

(In the formula, R ¹ and R ² are the same as described above.)
1,3,4,6-tetrakis (carboxymethyl) glycoluril represented by the general formula (a)

(In the formula, R ¹ and R ² are the same as described above.)
The dicarbonyl compound represented by general formula (b) in the presence of an acid in an appropriate solvent as necessary.

(In the formula, R ³ represents a lower alkyl group.)
It can obtain by making it react with the urea derivative (b) represented by these.
The ester group (—CO ₂ R ³ ) in the urea derivative (b) is an ester group that is hydrolyzed during the reaction, and the group R ³ is preferably an alkyl group having 1 to 3 carbon atoms. And more preferably a methyl group or an ethyl group. Therefore, as the urea derivative (b), for example, N, N′-carbonylbis (glycinemethyl) and N, N′-carbonylbis (glycineethyl) are preferably used.

The urea derivative (b) is used in a proportion of 2 to 10 mole parts, preferably in a ratio of 2 to 4 mole parts, with respect to 1 mole part of the dicarbonyl compound (a).

As the dicarbonyl compound (a), for example, glyoxal, 2-oxopropanal, diacetyl and the like are used.

Examples of the acid used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. These acids are usually used in a proportion of 0.05 to 10 mol parts, preferably 0.1 to 1.0 mol parts, relative to 1 mol part of the dicarbonyl compound (a).

In the reaction of the dicarbonyl compound (a) and the urea derivative (b), the solvent is not particularly limited as long as it does not inhibit the reaction. For example, water, methanol, ethanol , Alcohols such as isopropyl alcohol, aliphatic hydrocarbons such as hexane and heptane, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, benzene, toluene and xylene Aromatic hydrocarbons, methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol di Ethers such as til ether, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, amides such as hexamethylphosphorotriamide, dimethyl sulfoxide Such sulfoxides can be mentioned. These solvents are used alone or in combination of two or more, and an appropriate amount is used.

The reaction of the dicarbonyl compound (a) and the urea derivative (b) is usually performed at a temperature in the range of −10 to 150 ° C., preferably at a temperature in the range of 0 ° C. to 100 ° C. In addition, although depending on the reaction temperature, the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

After completion of the reaction of the dicarbonyl compound (a) and the urea derivative (b), the desired 1,3,4,6-tetrakis (carboxymethyl) is obtained from the obtained reaction mixture by an operation such as extraction. ) Glycolurils can be obtained. If necessary, the desired 1,3,4,6-tetrakis (carboxymethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.

Among the 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention, those in which n is 1, that is, the following general formula (A2)

(In the formula, R ¹ and R ² are the same as described above.)
1,3,4,6-tetrakis (2-carboxyethyl) glycoluril represented by the general formula (c)

(In the formula, R ¹ and R ² are the same as described above.)
Is reacted with acrylonitrile in the presence of a base, preferably in an appropriate solvent, to give a general formula (d)

(In the formula, R ¹ and R ² are the same as described above.)
Step 1, to obtain 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril represented by the following formula, then, the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is obtained Preferably, it can be obtained by passing through a second step of hydrolysis in the presence of an acid in an appropriate solvent.

In the first step, that is, in the reaction of glycolurils (c) and acrylonitrile, acrylonitrile is usually in a ratio of 4.0 to 20.0 mole parts per mole of glycolurils (c). Preferably, it is used in a proportion of 4.0 to 8.0 mole parts.

Examples of the base in the first step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert. An inorganic base such as butoxide or an organic base such as triethylamine, diisopropylethylamine, DBU (1,8-diazabicyclo [5.4.0] unde-7-cene) is used. These bases are usually used in a proportion of 0.01 to 5.0 mol parts, preferably in a proportion of 0.01 to 1.0 mol parts, relative to 1 mol part of the glycolurils (c). It is done.

In the first step, when the solvent is used, it is not particularly limited as long as it does not inhibit the reaction. For example, the dicarbonyl compound (a) and the urea derivative (b) The same solvent as that used in the reaction can be used.

The reaction temperature and reaction time in the first step are also the same as the reaction temperature and reaction time in the reaction of the dicarbonyl compound (a) and the urea derivative (b).

In the synthesis of 1,3,4,6-tetrakis (carboxyethyl) glycoluril by the first and second steps described above, after completion of the first step, excess acrylonitrile and solvent are removed from the resulting reaction mixture. In the second step, the resulting residue may be hydrolyzed as it is, or the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is reacted with the reaction mixture. May be separated by appropriate means and subjected to hydrolysis in the second step.

Examples of the acid used in the second step, that is, hydrolysis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid. Can do. These acids are usually in a ratio of 0.1 to 20.0 mol parts, preferably 1.0 to 1 mol parts of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril. Used in a proportion of ~ 3.0 mol parts.

The solvent used in the second step is not particularly limited as long as the reaction is not inhibited. For example, the same solvent as used in the reaction of the dicarbonyl compound (a) and the urea derivative (b) is used. A solvent can be used.

The hydrolysis reaction of the 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril is usually carried out at a temperature in the range of 0 to 150 ° C., preferably in the range of room temperature to 100 ° C. At a temperature of The reaction time is usually in the range of 1 to 36 hours, preferably in the range of 1 to 16 hours, although depending on the reaction temperature.

Thus, after completion of the hydrolysis reaction of the 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril, the target 1 is obtained from the resulting reaction mixture by an operation such as extraction. , 3,4,6-tetrakis (2-carboxyethyl) glycoluril can be obtained. If necessary, the desired 1,3,4,6-tetrakis (2-carboxyethyl) glycoluril can be further purified by washing with a solvent such as water or activated carbon treatment.

The 1,3,4,6-tetrakis (carboxyalkyl) glycolurils according to the present invention have four carboxyl groups in the molecule, as described above, and thus, for example, as crosslinkers for epoxy resins Useful.

The epoxy resin composition according to the present invention contains 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) as a crosslinking agent, and further contains a curing agent comprising amines. Including.

According to the present invention, an epoxy resin composition containing 1,3,4,6-tetrakis (carboxyalkyl) glycoluril as a crosslinking agent and a curing agent comprising an amine is conventionally known. In comparison with the above, a cured epoxy resin having a higher crosslink density, and therefore, an cured epoxy resin superior in hardness, heat resistance, moisture resistance, etc., for example, is provided.

In the present invention, the above-mentioned epoxy resin means an epoxy compound having two or more epoxy groups per molecule on average. Therefore, as is well known, as such an epoxy resin, for example, bisphenol A is used. Polyglycidyl ethers obtained by reacting polychlorophenols such as bisphenol F, bisphenol AD, catechol and resorcinol, polyhydric alcohols such as glycerin and polyethylene glycol and epichlorohydrin, p-hydroxybenzoic acid, β-hydroxynaphthoic acid Glycidyl ether esters obtained by reacting such a hydroxycarboxylic acid with epichlorohydrin, polyglycidyl esters obtained by reacting a polycarboxylic acid such as phthalic acid and terephthalic acid with epichlorohydrin, and epoxide Phenolic novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, urethane-modified epoxy resin, etc., but in the present invention, the epoxy resin is limited to the above examples is not.

As known in the art, the curing agent comprising amines in the epoxy resin composition according to the present invention has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule, and a primary amino group, What is necessary is just to have at least one amino group selected from a secondary amino group and a tertiary amino group in the molecule. Examples of the curing agent comprising such amines include aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diaminodicyclohexylmethane. Aromatic amines such as 4,4'-diaminodiphenylmethane, 2-methylaniline, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, Examples thereof include nitrogen-containing heterocyclic compounds such as piperidine and piperazine. However, in this invention, the hardening | curing agent which consists of amines is not limited to the said illustration.

Furthermore, the epoxy resin composition according to the present invention may contain various additives such as a filler, a diluent, a solvent, a pigment, a flexibility imparting agent, a coupling agent, and an antioxidant as necessary. Good.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not particularly limited to these examples.

In the following, N, N′-carbonylbis (glycine methyl) was synthesized according to the method described in Synlett, Vol. 7, pages 1104 to 1106 (2010).

Further, 40% aqueous glyoxal solution, glycoluril and acrylonitrile were all manufactured by Tokyo Chemical Industry Co., Ltd., and DBU was manufactured by Wako Pure Chemical Industries, Ltd.

Example 1
(Synthesis of 1,3,4,6-tetrakis (carboxylmethyl) glycoluril)
A 100 mL flask equipped with a thermometer was charged with 2.04 g (10.0 mmol) of N, N′-carbonylbis (glycine methyl), 726 mg (5.0 mmol) of 40% aqueous glyoxal solution, 10 mL of acetic acid and 49 mg (0.5 mmol) of sulfuric acid. I put it in.

The resulting mixture was stirred at 110 ° C. overnight, cooled to room temperature, 50 mL of acetone was added, the precipitated crystals were filtered off, dried, and dried with 1,3,4,6-tetrakis (carboxylmethyl) glycol. 1.26 g of uril was obtained as white crystals. Yield 67%.

The obtained 1,3,4,6-tetrakis (carboxylmethyl) glycoluril had a melting point of 223 ° -239 ° C. The IR spectrum is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (d6-DMSO) was as follows.

12.8 (br, 4H), 5.52 (s, 2H), 4.05 (d, 4H), 3.85 (d, 4H)

Example 2
(Synthesis of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril)
A 200 mL autoclave vessel equipped with a thermometer was charged with 13.54 g (95.3 mmol) of glycoluril, 35.38 g (666.8 mmol) of acrylonitrile, 0.58 g (3.8 mmol) of DBU and 54 mL of water.

The resulting mixture was stirred at 120 ° C. for 5 hours and then cooled to room temperature. The precipitated crystals were separated by filtration and recrystallized from a mixed solvent of 50 mL of acetone / 10 mL of water to obtain 20.75 g of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril as white crystals. Yield 61%.

The melting point of the obtained 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril was 139 to 141 ° C. The IR spectrum is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (d6-DMSO) was as follows.

5.50 (s, 2H), 3.64-3.71 (m, 4H), 3.44-3.51 (m, 4H), 2.79 (t, 8H)

(Synthesis of 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril)
A 100 mL flask equipped with a thermometer was charged with 10.00 g (28.2 mmol) of 1,3,4,6-tetrakis (2-cyanoethyl) glycoluril and 20 mL of concentrated hydrochloric acid.

The resulting mixture was stirred at 110 ° C. for 2 hours, then concentrated under reduced pressure, and 40 mL of acetone was added to the resulting concentrate. The insoluble material was removed by filtration, and the filtrate was stirred for 1 hour under ice cooling. The precipitated crystals were separated by filtration and dried to obtain 4.62 g of 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril as white crystals. Yield 38%.

The melting point of the obtained 1,3,4,6-tetrakis (2-carboxylethyl) glycoluril was 115 to 121 ° C. The IR spectrum is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (D ₂ O) was as follows.

3.99 (s, 2H), 3.88 (t, 2H), 3.66 (t, 2H), 3.57 (t, 2H), 3.27 (t, 2H), 2.64 (t , 2H), 2.58 (t, 4H), 2.05 (t, 2H)

(2) Polyester resin composition The polyester resin composition according to the present invention comprises:
(A) a polyester resin obtained by a polycondensation reaction between 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) and a glycol;
(B) A β-hydroxyalkylamide-based curing agent.

In the present invention, 1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the general formula (A) is used as a carboxylic acid as a raw material for the polyester resin.

Specific examples of the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril include the following:
1,3,4,6-tetrakis (carboxylmethyl) glycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) glycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (2-carboxylethyl) -3a-methylglycoluril,
1,3,4,6-tetrakis (carboxylmethyl) -3a, 6a-dimethylglycoluril,
Examples include 1,3,4,6-tetrakis (2-carboxylethyl) -3a, 6a-dimethylglycoluril.

In the present invention, as long as the effects of the present invention are not impaired, isophthalic acid, terephthalic acid, 5-sodium sulfoisophthalic acid may be used as carboxylic acids separately from 1,3,4,6-tetrakis (carboxyalkyl) glycoluril. Aromatic dicarboxylic acids such as acid, phthalic anhydride, naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and dodecanedioic acid, trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid, Further, ester-forming derivatives of these acids may be used in combination with oxycarboxylic acids such as 4-hydroxybenzoic acid and ε-caprolactone.

In the present invention, the glycols include neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, aliphatic diols such as 1,4-butanediol and 1,6-hexanediol, 1,4-cyclohexanedimethanol, And aromatic glycols such as alicyclic glycols such as 1,4-cyclohexanediol, trivalent or higher alcohols such as trimethylolpropane, pentaerythritol and glycerin, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol S, and the like. It is done.

In the present invention, the ratio of the total amount (total amount) of 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and glycols needs to be 80 to 100 mol% with respect to all components. When the total ratio is less than 80 mol%, the weather resistance of the coating film is insufficient.

The acid value of the polyester resin of the present invention is preferably 20 to 50 mgKOH / g, more preferably 25 to 40 mgKOH / g.

If the acid value of the polyester resin is less than 20 mgKOH / g, the molecular weight of the resin becomes too high and the fluidity is lowered, so that the smoothness of the coating film is lowered and the adhesion to the material is deteriorated. . On the other hand, when the acid value exceeds 50 mgKOH / g, when blended as a raw material of a coating, the curing reaction with the curing agent is excessively increased, so that the smoothness of the coating film is deteriorated and the adhesion with the material is decreased. Absent.

The polyester resin of the present invention preferably has a melt viscosity at 160 ° C. of 100 to 800 dPa · s, and more preferably 150 to 700 dPa · s. If the melt viscosity at 160 ° C. of the polyester resin is less than 100 dPa · s, the melt viscosity becomes too low and the coating film is sagged. When melt viscosity exceeds 800 dPa * s, the smoothness of a coating film will fall and adhesiveness with a raw material will be impaired.

The polyester resin of the present invention uses the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and glycols (including their ester-forming derivatives) as raw materials, and has a temperature of 200 to 280 ° C. by a conventional method. After the esterification or transesterification reaction is performed at a temperature, the polycondensation reaction is performed at a temperature of 200 to 300 ° C., preferably 230 to 290 ° C. under a reduced pressure of 5 hPa or less.

Further, if necessary, 1,3,4,6-tetrakis (carboxyalkyl) glycoluril and / or aromatic tricarboxylic acid is added, and at a reaction temperature of 230 to 290 ° C., preferably 250 to 280 ° C., A depolymerization step may be added for a reaction time of 2 to 5 hours, preferably 2.5 to 4 hours.

When the depolymerization temperature is less than 230 ° C., the depolymerizer does not react sufficiently, resulting in a polymer having a high degree of polymerization and poor smoothness. On the other hand, when the depolymerization temperature exceeds 290 ° C., the thermal decomposition of the polymer proceeds. Even at a predetermined temperature, when the depolymerization time is less than 2 hours, the depolymerization agent does not react at all, so that the smoothness of the coating film is lowered and the adhesion with the material is deteriorated. When the depolymerization time exceeds 5 hours, the thermal history becomes long, so that the thermal decomposition of the polymer proceeds. In the esterification, transesterification reaction and polycondensation reaction, a known reaction catalyst can be used.

For the resin composition for powder coatings of the present invention, the performance of the coating film is further improved by blending the polyester resin of the present invention with a hydroxyalkylamide curing agent.

The type of the curing agent is not particularly limited, and examples thereof include “PrimidXL-552” manufactured by EMS. The amount of the curing agent is preferably 0.7 to 1.2 times equivalent, more preferably 0.9 to 1 times equivalent to the acid value of the polyester resin.

The resin composition for powder coatings of the present invention can be mixed with a known leveling agent and other additives, for example, a mixture of pigments such as titanium dioxide, precipitated barium sulfate, carbon black, etc. Can be prepared by melting and kneading at 70 to 140 ° C.

The resin composition for powder coatings of the present invention is applied to an object to be coated, and is usually baked at a temperature of 150 to 190 ° C. for 15 to 25 minutes to form a coating film excellent in smoothness and adhesion to the material. give.

According to the polyester resin of the present invention, since the acid value is low, the curing reaction is relatively slow, and the melt viscosity is low. Therefore, when used as a raw material for powder coating, it has excellent smoothness, and further 1,3,4 , 6-Tetrakis (carboxyalkyl) glycoluril and glycols have a high copolymerization ratio, so that a coating film having excellent weather resistance can be obtained.

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, the properties and coating film performances of polyester resins and resin compositions for powder coatings were measured and evaluated according to the following methods.

(1) Acid value 0.5 g of polyester resin is dissolved in 50 ml of a mixed solvent of dioxane / distilled water = 10/1 (weight ratio), heated to reflux, and then 0.1 × 10 ³ mol / m ³ of potassium hydroxide methanol. Determined by titration with solution.

(2) Melt Viscosity Viscosity was determined by measuring with a Brookfield melt viscometer (VISCOMETERDV-1 manufactured by Brookfield) at a sample amount of 15 g and a temperature of 150 ° C.

(3) Smoothness The smoothness of the coating film was visually determined according to the following criteria.
○: The coating film has few irregularities and the smoothness is good. ×: The coating film has large irregularities.

(4) Adhesiveness According to JISK5400, the coated plate was immersed in boiling water for 2 hours and then air-dried at room temperature for 24 hours. Subsequently, the coating film was cut into a grid pattern with a cutter knife, a peel test was performed with an adhesive tape, and visually judged according to the following criteria.
○: No peeling of the coating film is observed.
X: Peeling of a coating film is recognized partially or entirely.

(5) Accelerated weather resistance According to SK5400, using a WEL-6-XS-HC-B-EC type sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the gloss retention (%) of the coating film when irradiated for 500 hours Asked. A case where the gloss retention was 80% or more was regarded as acceptable.

Example 1
1,3,4,6-tetrakis (2-carboxyethyl) glycoluril 53.5 mol parts and neopentyl glycol 47.6 mol parts were charged into an esterification reaction vessel, pressure 0.3 MPaG, temperature 260 ° C. for 4 hours. An esterification reaction was performed.

After the obtained esterified product was transferred to a polycondensation reaction tank, 4.0 × 10 ⁻⁴ mol / carboxylic acid component of antimony trioxide and tetrabutyl titanate 0.1 × 10 ⁻⁴ mol / carboxylic acid component 1 mol was added, the pressure was reduced to 0.5 hPa, and a polycondensation reaction was performed at 280 ° C. for 4 hours to obtain a polyester resin having the characteristics shown in Table 1.

A mixture of the obtained polyester resin and a hydroxyalkylamide curing agent ("PrimidXL-552" manufactured by EMS) mixed with a butyl polyacrylate leveling agent ("Acronal 4F" manufactured by BASF), benzoin and rutile type dioxide. Titanium pigment (“Taipek CR-90” manufactured by Ishihara Sangyo Co., Ltd.) was added in the amount (part by mass) shown in Table 1 and dry blended with a Henschel mixer (“FM10B type” manufactured by Mitsui Miike Seisakusho). The product was melt-kneaded at 100 ° C. using a “PR-46 type” manufactured by the company, cooled, pulverized, and classified with a 140 mesh (106 μm) wire mesh to obtain a resin composition for powder coating.

The obtained resin composition for powder coating was electrostatically coated on a zinc phosphate-treated steel sheet so as to have a film thickness of 50 to 60 μm, and baked at 160 ° C. for 20 minutes. The results of evaluating the performance of the coating film are shown in Table 1.

Examples 2 and 3, Comparative Examples 1 and 2
In the same manner as in Example 1, polyester resins and powder coating resin compositions described in Table 1 were prepared, and their characteristics and coating film performance were measured and evaluated.

The results of measurement and evaluation obtained were as shown in Table 1.

Second invention (1) Novel glycidyl glycoluril and epoxy resin composition containing the same New glycidyl glycoluril according to the present invention is represented by the general formula (B)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a glycidyl group.)
It is represented by

That is, the glycidyl glycoluril according to the present invention has the general formula (Ba)

(In the formula, R ¹ and R ² are the same as described above.)
Monoglycidyl glycoluril represented by the general formula (Bb)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidyl glycoluril represented by the general formula (Bc)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidylglycoluril represented by the general formula (Bd)

(In the formula, R ¹ and R ² are the same as described above.)
Diglycidyl glycoluril represented by the general formula (Be)

(In the formula, R ¹ and R ² are the same as described above.)
And triglycidyl glycoluril represented by the general formula (Bf)

(In the formula, R ¹ and R ² are the same as described above.)
It is tetraglycidyl glycoluril represented by these.

In the glycidyl glycolurils represented by the above general formulas (B) and (Ba) to (Bf), when R ¹ or R ² is a lower alkyl group, the lower alkyl group usually has 1 to 5, preferably 1 to 3, most preferably 1, and therefore the most preferred lower alkyl group is a methyl group.

Accordingly, preferred specific examples of glycidyl glycolurils according to the present invention include, for example,
1-glycidyl glycoluril,
1,3-diglycidyl glycoluril,
1,4-diglycidyl glycoluril,
1,6-diglycidyl glycoluril,
1,3,4-triglycidyl glycoluril,
1,3,4,6-tetraglycidylglycoluril,
1-glycidyl-3a-methylglycoluril,
1-glycidyl-6a-methyl-glycoluril,
1,3-diglycidyl-3a-methylglycoluril,
1,4-diglycidyl-3a-methylglycoluril,
1,6-diglycidyl-3a-methylglycoluril,
1,3,4-triglycidyl-3a-methylglycoluril,
1,3,4-triglycidyl-6a-methylglycoluril,
1,3,4,6-tetraglycidyl-3a-methylglycoluril,
1-glycidyl-3a, 6a-dimethylglycoluril,
1,3-diglycidyl-3a, 6a-dimethylglycoluril,
1,4-diglycidyl-3a, 6a-dimethylglycoluril,
1,6-diglycidyl-3a, 6a-dimethylglycoluril,
1,3,4-triglycidyl-3a, 6a-dimethylglycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril,
1-glycidyl-3a, 6a-diphenylglycoluril,
1,3-diglycidyl-3a, 6a-diphenylglycoluril,
1,4-diglycidyl-3a, 6a-diphenylglycoluril,
1,6-diglycidyl-3a, 6a-diphenylglycoluril,
1,3,4-triglycidyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetraglycidyl-3a, 6a-diphenylglycoluril and the like.

The glycidyl glycoluril represented by the general formula (B) according to the present invention is represented by the general formula (a)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a glycidyl group.)
It can be obtained by oxidizing and epoxidizing the carbon-carbon double bond of the allyl glycoluril by allowing an oxidant to act on the allylglycoluril represented by formula (1).

Generally, a method of oxidizing a carbon-carbon double bond and epoxidizing is already well known, and in the present invention, such a method can be used. Examples of such a method include a method using a peracid such as an oxone reagent, peracetic acid, and metachloroperbenzoic acid, and a method using hydrogen peroxide using sodium tungstate as a catalyst.

When peracid is used as the oxidizing agent, the peracid is preferably used at a ratio of 1.0 to 5.0 equivalents relative to the allyl group of allyl glycoluril.

When used, the reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, water, alcohols such as methanol, ethanol and isopropyl alcohol, aliphatics such as hexane and heptane are used. Hydrocarbons, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, chloro Halogenated hydrocarbons such as trifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, formamide, N, N-dimethyl Formamide, N, N- dimethylacetamide, amides such as N- methyl-2-pyrrolidone, N- methylpyrrolidinone, hexamethylphosphoric triamide, may be mentioned sulfoxides such as dimethyl sulfoxide and the like. These reaction solvents are used alone or in combination of two or more, and an appropriate amount is used.

The reaction temperature when oxidizing allyl glycoluril using the peracid is usually in the range of −10 to 150 ° C., and preferably in the range of 0 ° C. to 100 ° C. In addition, although depending on the reaction temperature, the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

After completion of the reaction, the target glycidyl glycoluril can be obtained by extraction from the obtained reaction mixture, or crystallization from an appropriate solvent and filtration.

When allyl glycoluril is oxidized with hydrogen peroxide using sodium tungstate as a catalyst, hydrogen peroxide is in a ratio of 1.0 to 5.0 equivalents relative to the allyl group of allyl glycoluril. Used in Further, sodium tungstate is preferably used in a proportion of 0.001 to 0.5 equivalents relative to the allyl group of allyl glycoluril.

The reaction solvent is not particularly limited as long as it does not inhibit the reaction. For example, the same reaction solvent as in the above-described oxidation reaction using a peracid can be used.

The reaction temperature is usually in the range of −10 to 150 ° C., preferably in the range of 0 ° C. to 100 ° C., as in the above-described oxidation reaction using peracid, and the reaction time is also the reaction temperature. However, it is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

After completion of the reaction, in the same manner as in the case of the oxidation reaction with peracid described above, the objective is obtained by extracting from the obtained reaction mixture, or crystallizing from an appropriate solvent and filtering. Glycidyl glycoluril can be obtained.

The glycidyl glycoluril thus obtained can be purified as necessary by washing with a solvent such as water, activated carbon treatment, silica gel chromatography, and the like.

Among the glycidyl glycolurils according to the present invention, those having one glycidyl group in the molecule are useful, for example, as an intermediate for synthesizing oxygen-containing compounds and as a diluent for epoxy resins. Of the glycidyl glycolurils according to the present invention, those having two or more glycidyl groups in the molecule are useful as, for example, a crosslinking agent for epoxy resins.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, alicyclic epoxy resin, 3 ′, 4′- Cycloaliphatic epoxy resins such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, nitrogen-containing cyclic epoxies such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monoglycidyl isocyanurate and hydantoin type epoxy resins Resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, dicyclo ring In addition to epoxy resins, naphthalene-type epoxy resins, halogenated epoxy resins, etc., epoxy-modified organopolysiloxane compounds by hydrosilylation addition reaction of organic compounds having carbon-carbon double bonds and glycidyl groups with silicon compounds having SiH groups (for example, And epoxy-modified organopolysiloxane compounds disclosed in JP-A-2004-99751 and JP-A-2006-282898.

The glycidyl glycoluril according to the present invention can be made into an epoxy resin composition by blending it with the above-described epoxy resin together with a curing agent and, if necessary, a curing accelerator.

In such an epoxy resin composition according to the present invention, the glycidyl glycoluril according to the present invention is usually used at a ratio of 0.1 to 150 parts by mass, preferably 10 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin. Used at a rate of 100 parts by weight.

Examples of the curing agent include compounds having phenolic hydroxyl groups, acid anhydrides, amines, mercaptan compounds such as mercaptopropionic acid esters and epoxy resin-terminated mercapto compounds, triphenylphosphine, diphenylnaphthylphosphine, diphenylethylphosphine, and the like. Examples thereof include organic phosphine compounds, aromatic phosphonium salts, aromatic diazonium salts, aromatic iodonium salts, and aromatic selenium salts.

Examples of the compound having a phenolic hydroxyl group include bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, and phenol. Examples thereof include novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and resorcinol.

Examples of the acid anhydride include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic acid anhydride , Hymic acid anhydride, methylnadic acid anhydride, methyldicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride And methylnorbornane-2,3-dicarboxylic acid.

Further, examples of the amines include diethylenediamine, triethylenetetramine, hexamethylenediamine, dimer acid-modified ethylenediamine, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenol ether, 1,8-diazabicyclo. Examples include [5.4.0] -7-undecene and the like, and imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

In the epoxy resin composition according to the present invention, the curing agent is usually used in a proportion of 10 to 300 parts by mass, preferably 100 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin.

Examples of the curing accelerator include 1,8-diazabicyclo [5.4.0] -7-undecene, diethylenetriamine, triethylenetetramine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl). Amine compounds such as phenol, imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Organic phosphine compounds such as tetrabutylphosphonium bromide, phosphonium compounds such as tetrabutylphosphonium diethyl phosphorodithioate, tetrapheny Tetraphenylboron salts such as phosphonium tetraphenylborate, 2-methyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate, aliphatic acid metals such as lead acetate, tin octylate and cobalt hexanoate A salt etc. can be mentioned. It is already known that some of these curing accelerators can also be used as the above-described curing agent.

In the epoxy resin composition according to the present invention, the curing accelerator is usually used in a proportion of 0.01 to 2.0 parts by weight, preferably 0.1 to 0.5 parts, per 100 parts by weight of the epoxy resin. Used in the ratio of parts by mass.

In addition, the epoxy resin composition according to the present invention may be filled with an inorganic material such as amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, as necessary. In addition to the materials, various polymers such as phenol resin and unsaturated polyester can be included.

The epoxy resin composition according to the present invention can contain various additives in addition to the above. Examples of such additives include aliphatic polyols such as ethylene glycol and propylene glycol, carbon dioxide generation inhibitors such as aliphatic or aromatic carboxylic acid compounds and phenol compounds, flexibility imparting agents such as polyalkylene glycol, and oxidation. Inhibitors, plasticizers, lubricants, silane-based coupling agents, inorganic filler surface treatment agents, flame retardants, antistatic agents, coloring agents, antistatic agents, leveling agents, ion trapping agents, sliding property improving agents , Various rubber, organic polymer beads, glass beads, impact modifiers such as inorganic fillers such as glass fibers, thixotropic agents, surfactants, surface tension reducing agents, antifoaming agents, anti-settling agents, light diffusion Agents, ultraviolet absorbers, antioxidants, release agents, fluorescent agents, conductive fillers and the like.

Such epoxy resin compositions include paints for printed wiring boards and electronic components, sealing materials, adhesives, resist inks, etc., as well as coating materials for woodwork, optical fibers, plastics, and cans. The use as is expected.

Reference example 1
(Synthesis of 1,3-diallylglycoluril)
A 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to this mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. Subsequently, the reaction mixture was concentrated under reduced pressure. To the resulting concentrate, 7.00 g (50.0 mmol) of diallylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C. overnight. The reaction mixture is then cooled to room temperature and then 50 mL of acetone is added to separate the viscous oil from the reaction mixture, which is dried to give 1,3-diallylglycoluril as a white viscous oil. It was. Yield 39%.

The IR spectrum of the resulting 1,3-diallylglycoluril is shown in FIG. Further, its ¹ H-NMR spectrum (d6-DMSO) δ value: 7.52 (s, 2H), 5.69-5.84 (m, 2H), 5.08-5.23 (m, 6H) , 3.92 ^ 3.97 (m, 2H), 3.52 (dd, 2H)

Reference example 2
(Synthesis of 1,3,4,6-tetraallylglycoluril)
The compound was synthesized according to the method described in JP-A-11-171887.

Glycoluril (14.2 g, 100 mmol), sodium hydroxide (16.0 g, 400 mmol) and dimethyl sulfoxide (140 mL) were mixed, heated and stirred at 40 ° C. for 1 hour, and then allyl chloride (34.4 g, 400 mmol) was added at the same temperature for 20 minutes. It was dripped over. After completion of the dropwise addition, the mixture was further heated and stirred at 40 ° C. for 2 hours to complete the reaction.

The obtained reaction mixture was dried under reduced pressure. The obtained dried product was subjected to liquid separation extraction with 400 mL of ethyl acetate and 400 mL of water. The ethyl acetate layer was washed with 100 mL of water and then with 100 mL of saturated brine, and then dried over anhydrous sodium sulfate. Ethyl acetate was distilled off under reduced pressure, and 1,3,4,6-tetraallylglycoluril 27. 4 g was obtained as a colorless oil. Yield 90%.

Reference example 3
(Synthesis of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril)
3a, 6a-dimethylglycoluril (17.0 g, 100 mmol), sodium hydroxide (16.0 g, 400 mmol) and dimethyl sulfoxide (150 mL) were mixed and heated and stirred at 40 ° C. for 1 hour, and then 34.4 g of allyl chloride ( 400 mmol) was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was further heated and stirred at 40 ° C. for 2 hours to complete the reaction. Thereafter, the same post-treatment as in Reference Example 2 was carried out to obtain 26.1 g of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril as crystals. Yield 79%.

Example 1
(Synthesis of 1,3-diglycidyl glycoluril)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 1.11 g (5.0 mmol) of 1,3-diallylglycoluril and 10 mL of dichloromethane, and 2.92 g of metachloroperbenzoic acid (purity 65%) under ice cooling. 11.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.

After adding 20 mL of 10% aqueous sodium sulfite solution to the obtained reaction mixture, the mixture was mixed with 20 mL of chloroform, shaken and allowed to stand, and the resulting organic layer was extracted and separated.

The extraction with chloroform was further performed twice, and the obtained extracts were combined and dried over sodium sulfate, and then the volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 10/1 (volume ratio)) to obtain 1.80 g of 1,3-diglycidylglycoluril as a white viscous oil. Yield 98%.

The IR spectrum of the obtained 1,3-diglycidyl glycoluril is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

7.36 (br, 2H), 5.12-5.37 (m, 8H), 4.77-4.82 (m, 2H), 4.54-4.57 (m, 2H)

Example 2
(Synthesis of 1,3,4,6-tetraglycidyl glycoluril)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 1.51 g (5.0 mmol) of 1,3,4,6-tetraallylglycoluril and 10 mL of dichloromethane, and this was cooled to ice with metachloroperbenzoic acid (purity 65 %) 5.84 g (22.0 mmol) was added, and the mixture was warmed to room temperature and stirred overnight.

20 mL of 10% sodium sulfite aqueous solution was added to the obtained reaction mixture, mixed with 20 mL of chloroform, shaken and allowed to stand, and the resulting organic layer was extracted and separated.

The extraction with chloroform was further performed twice, and the obtained extracts were combined and dried over sodium sulfate, and then the volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 40/1 (volume ratio)) to obtain 1.80 g of 1,3,4,6-tetraglycidylglycoluril as a colorless oil. It was. Yield 98%.

The IR spectrum of the obtained 1,3,4,6-tetraglycidylglycoluril is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

5.37-5.69 (m, 2H), 4.23-4.27 (m, 1H), 4.03-4.06 (m, 1H), 3.61-3.81 (m, 3H) ), 3.45-3.46 (m, 1H), 3.01-3.23 (m, 6H), 2.78-2.84 (m, 4H), 2.59-2.63 (m , 4H)

Example 3
(Synthesis of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril)
A 100 mL flask equipped with a thermometer and a stirrer was charged with 1.51 g (5.0 mmol) of 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril and 10 mL of dichloromethane. After adding acid (purity 65%) 5.84g (22.0mmol), it heated up to room temperature and stirred all night.

This extraction operation with chloroform was further performed twice, and the obtained extracts were combined and dried over sodium sulfate, and then volatile components were distilled off. The residue thus obtained was purified by silica gel chromatography (chloroform / methanol = 40/1 (volume ratio)) to obtain 1.81 g of 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. Was obtained as a colorless liquid. Yield 92%.

FIG. 7 shows the IR spectrum of the obtained 1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril. Further, the δ value in the ¹ H-NMR spectrum (CDCl ₃ ) was as follows.

3.40-4.37 (m, 8H), 3.03-3.18 (m, 3H), 2.78-2.85 (m, 3H), 2.55-2.62 (m, 3H) ), 2.55-2.62 (m, 3H), 1.45-1.70 (m, 9H)

Example 4
As shown in Table 2, hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Co., Ltd., abbreviated as YX8000 in Table 1) is used as a curing agent in 80 parts by mass of 4-methylhexahydrophthalic anhydride / hexahydro. 120 parts by weight of phthalic anhydride (mixture of 70/30 by weight, Rikacid MH-700 manufactured by Shin Nippon Chemical Co., Ltd., abbreviated as MH-700 in Table 1), tetra-n-butylphosphonium as a curing accelerator -O, o-diethyl phosphorodithionate (Hishicolin PX-4ET manufactured by Nippon Chemical Industry Co., Ltd., abbreviated as PX-4ET in Table 1) 0.5 parts by mass and 1,3,4,4 as a crosslinking agent 20 parts by mass of 6-tetraglycidyl glycoluril (abbreviated as TG-G in Table 1) was blended and kneaded to prepare an epoxy resin composition.

This epoxy resin composition was heated at a temperature of 120 ° C. for 6 hours to obtain a cured product. About this hardened | cured material, the glass transition point (Tg), the bending elastic modulus, and the bending strength were measured, and the result shown in Table 2 was obtained. Tg was measured by DSC according to JISK7121. The flexural modulus and flexural strength were measured according to JISK7203.

Comparative Example 1
As shown in Table 2, 100 parts by mass of hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Corporation) as a curing agent, 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride (70/30 mixture, new 80 parts by mass of Nippon Rika Co., Ltd. (Licacid MH-700) and tetra-n-butylphosphonium-o, o-diethylphosphorodithionate (Hishicolin PX-4ET, Nippon Chemical Industry Co., Ltd.) as a curing accelerator 5 parts by mass was blended and kneaded to prepare an epoxy resin composition.

In the same manner as in Example 4, this epoxy resin composition was heated to obtain a cured product, and the glass transition point (Tg), bending elastic modulus and bending strength of this cured product were measured, and the results shown in Table 2 were obtained. Got.

Comparative Example 2
In Example 4, instead of 20 parts by mass of the crosslinking agent 1,3,4,6-tetraglycidylglycoluril, triglycidyl isocyanuric acid (triglycidyl isocyanurate manufactured by Tokyo Chemical Industry Co., Ltd., in Table 2, TG-ICA) An epoxy resin composition was prepared in the same manner as in Example 4 except that 20 parts by mass was used.

As is apparent from the results shown in Table 2, the epoxy resin composition containing glycidyl glycoluril according to the present invention as a crosslinking agent is a cured product of an epoxy resin composition not containing a crosslinking agent (Comparative Example 1) or a crosslinking agent. As compared with the cured epoxy resin composition containing triglycidyl isocyanuric acid (Comparative Example 2), it has excellent heat resistance and excellent mechanical strength.

(2) Epoxy resin composition for optical semiconductor element encapsulation The epoxy resin composition for optical semiconductor element encapsulation according to the present invention comprises an epoxy resin (1), and at least one component in the epoxy resin is represented by the above general formula ( It is a glycidyl glycoluril represented by B).

The epoxy resin composition for sealing an optical semiconductor element according to the present invention (hereinafter sometimes simply referred to as a resin composition) contains the following component epoxy resin (1) as an essential component, and further includes the following components ( It may contain at least one selected from 2) to component (9).

Component (1): Epoxy Resin The epoxy resin of component (1) is a component that forms the main component of the resin composition of the present invention. It is essential that the component (1) contains the glycidyl glycoluril represented by the general formula (B). Specific examples of the glycidyl glycoluril represented by the chemical formula (B) include, for example,
1-glycidyl glycoluril,
1,3-diglycidyl glycoluril,
1,4-diglycidyl glycoluril,
1,6-diglycidyl glycoluril,
1,3,4-triglycidyl glycoluril,
1,3,4,6-tetraglycidylglycoluril,
1-glycidyl-3a-methyl-glycoluril,
1,3-diglycidyl-3a-methyl-glycoluril,
1,4-diglycidyl-3a-methyl-glycoluril,
1,6-diglycidyl-3a-methyl-glycoluril,
1,3,4-triglycidyl-3a-methyl-glycoluril,
1,3,4,6-tetraglycidyl-3a-methyl-glycoluril,
1-glycidyl-3a, 6a-dimethyl-glycoluril,
1,3-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,4-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,6-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,3,4-triglycidyl-3a, 6a-dimethyl-glycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-dimethyl-glycoluril,
1-glycidyl-3a, 6a-diphenyl-glycoluril,
1,3-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,4-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,6-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,3,4-triglycidyl-3a, 6a-diphenyl-glycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-diphenyl-glycoluril and the like.

The glycidyl glycoluril represented by the general formula (B) may be used alone or in combination with one or more other epoxy resins. The other epoxy resin is preferably liquid at room temperature, but even if it is solid at room temperature, it may be diluted with another liquid epoxy resin or diluent to be used in a liquid state. it can.

Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin such as phenol novolac type epoxy resin and cresol novolak type epoxy resin, nitrogen-containing ring such as isocyanurate type epoxy resin and hydantoin type epoxy resin Epoxy resin, cycloaliphatic epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic epoxy resin, glycidyl ether type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, which is the mainstream of low water absorption rate cured body type, A dicyclo ring type epoxy resin, a naphthalene type epoxy resin, etc. are mentioned.

The epoxy resin may be modified in advance by adding a compound that reacts with an epoxy group such as alcohol or acid anhydride.

More specifically, the isocyanurate type epoxy resin includes 1,3,5-triglycidyl isocyanurate, 1-allyl-3,5-diglycidyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate, and the like. Is mentioned.

In addition, as the alicyclic epoxy resin, more specifically, a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring represented by the following general formula (1) And a compound in which an epoxy group is directly bonded to the alicyclic ring represented by the following general formula (2) by a single bond.

(Wherein R ⁶ represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, and an ester bond. , A carbonate group, an amide group, a group in which a plurality of these are linked, and the like.)

(In the formula, n is an integer of 1 to 30, p is an integer of 1 to 10, and R ′ is a group obtained by removing p —OH from a p-valent alcohol.)

Representative examples of the alicyclic epoxy compound represented by the general formula (1) include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate.

Typical examples of the alicyclic epoxy compound represented by the general formula (2) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, and the like. Is mentioned.

The content of the glycidyl glycoluril represented by the general formula (B) with respect to 100% by weight of the total amount of the epoxy group-containing compounds contained in the resin composition of the present invention is not particularly limited, but is 0.1 to 100% by weight. Is preferred.

Component (2): Glass filler As the glass filler of component (2), a known glass filler can be used, and is not particularly limited. For example, glass beads, glass flakes, glass powder, milled glass, glass fiber, A glass fiber cloth (for example, a glass cloth, a glass nonwoven fabric, etc.) etc. are mentioned. Of these, glass beads, glass flakes, and glass powder are preferred from the viewpoints of easily increasing the filling rate and improving moisture absorption reflow resistance and thermal shock resistance.

Although it does not specifically limit as a kind of glass which comprises a glass filler, For example, T glass, E glass, C glass, A glass, S glass, L glass, D glass, NE glass, quartz glass, low dielectric constant glass, Examples thereof include high dielectric constant glass. Among these, E glass, T glass, and NE glass are preferable because they have few ionic impurities and are excellent in heat resistance and electrical insulation. In the resin composition of the present invention, one type of glass filler can be used alone, and two or more types of sentences can be used in combination.

The refractive index of the sodium D line (light having a wavelength of 589.29 nm) of the glass filler is not particularly limited, but is preferably 1.40 to 2.10. When the refractive index is out of this range, the transparency of the cured product tends to be remarkably lowered. In addition, the refractive index of the sodium D line | wire of a glass filler can be measured using an Abbe refractometer (measurement temperature: 25 degreeC), for example.

When glass beads or glass powder is used as the glass filler, the average particle diameter thereof is not particularly limited, but is preferably 0.5 to 200 μm. The average particle size of the glass filler is expressed by calculating the average value of the particle size of the glass filler (glass beads, glass filler, etc.) using, for example, a laser diffraction / scattering particle size distribution measuring device. Can do.

When a glass fiber cloth such as glass cloth is used as the glass filler, the method of weaving these filament knots is not particularly limited, and examples thereof include plain weave, Nanako weave, satin weave and twill weave. The thickness of the glass fiber cloth (including the glass nonwoven fabric) is not particularly limited, but is preferably 20 to 200 μm. A glass fiber cloth (including a glass nonwoven fabric) can be used alone, or a plurality of glass fiber cloths can be used.

The glass filler may have been surface-treated with a known surface treatment agent. Examples of such a surface treatment agent include silane coupling agents such as γ-aminopropyl pyrethoxysilane and γ-glycidoxypillylethoxysilane, surfactants, inorganic acids, and the like.

The content (blending amount) of the glass filler is not particularly limited, but is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.

Component (3): Curing Agent The resin composition of the present invention may further contain a curing agent of component (3). A hardening | curing agent is a compound which has a function which hardens the compound which has an epoxy group, and can use a well-known hardening | curing agent as a hardening | curing agent for epoxy resins.

The curing agent is preferably a liquid acid anhydride at room temperature, and examples thereof include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, and methylendomethylenetetrahydrophthalic anhydride. Also, for example, solid acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylcyclohexene dicarboxylic acid anhydride are dissolved in a liquid acid anhydride at room temperature to form a liquid. By using this mixture, it can be preferably used as a curing agent in the practice of the present invention.

In addition, a hardening | curing agent can be used individually by 1 type or in combination of 2 or more types. As described above, as a curing agent, from the viewpoint of heat resistance, light resistance, and crack resistance of a cured product, an anhydride of a saturated monocyclic hydrocarbon dicarboxylic acid (a ring having a substituent such as an alkyl group bonded thereto) Including).

Further, in the present invention, as the curing agent, trade names “Licacid MH-700” (manufactured by Shin Nippon Rika Co., Ltd.), “Rikacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.), Commercial products such as “5500” (manufactured by Hitachi Chemical Co., Ltd.) can also be used.

The content (blending amount) of the curing agent is not particularly limited, but is preferably 10 to 200 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.

Component (4): Curing Accelerator The resin composition of the present invention may further contain a component (4) curing accelerator. The curing accelerator is a compound having a function of accelerating the curing rate when the compound having an epoxy group is cured by the curing agent.

As the curing accelerator, a known curing accelerator can be used. For example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) or a salt thereof (for example, phenol salt, octylate) , P-toluenesulfonate, formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (for example, phenol salt, octylate, p-卜 ruene sulfonate, formate, tetraphenylborate salt); tertiary amines such as benzyldimethylamine, 2,4,6-４， ris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl Imidazole such as -4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate ester, triphenylphosphine Phosphines such as emissions; Te Bok La tetraphenylphosphonium te us (p- tolyl) phosphonium compounds of borate, organic metal salts such as zinc octylate and tin octylate; metal chelate and the like. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

The content (blending amount) of the curing accelerator is not particularly limited, but is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the resin composition of the present invention.

Component (5): Curing catalyst The resin composition of the present invention may further contain a curing catalyst of component (5). The curing catalyst is a compound having a function of initiating a curing reaction of a compound having an epoxy group and / or accelerating the curing reaction. Although it does not specifically limit as a curing catalyst, Cationic catalyst (cationic polymerization initiator) which generate | occur | produces a cationic seed | species by giving ultraviolet irradiation or heat processing, and starts superposition | polymerization is mentioned. In addition, a curing catalyst can be used individually by 1 type or in combination of 2 or more types.

Examples of the cation catalyst that generates cation species by ultraviolet irradiation include hexafluoroantimonate salt, pentafluorohydroxyantimonate salt, hexafluorophosphate salt, and hexafluoroarsenate salt.

Examples of the cation catalyst that generates cation species by heat treatment include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, and allene-ion complexes. Further, a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketone and a silanol such as triphenylsilanol, or a chelate of a metal such as aluminum or titanium and acetoacetic acid or diketone It may be a compound of a compound and a phenol such as bisphenol S.

The content (blending amount) of the curing catalyst is not particularly limited, but is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total amount of the compound having an epoxy group contained in the curable epoxy resin composition. By using the curing catalyst within the above range, a cured product having excellent heat resistance, light resistance and transparency can be obtained.

Component (6): Polyester Resin The resin composition of the present invention preferably further contains a polyester resin of component (6). By containing a polyester resin, the heat resistance and light resistance of the cured product are improved, and the light intensity of the optical semiconductor device tends to be suppressed. The alicyclic polyester resin is a polyester resin having at least an alicyclic structure (aliphatic ring structure). In particular, from the viewpoint of improving the heat resistance and light resistance of the cured product, the alicyclic polyester resin is preferably an alicyclic polyester resin having an alicyclic ring (alicyclic structure) in the main chain.

The alicyclic structure in the alicyclic polyester resin is not particularly limited, and examples thereof include a monocyclic hydrocarbon structure and a bridged ring hydrocarbon structure (for example, a bicyclic hydrocarbon). Of these, a saturated monocyclic hydrocarbon structure and a saturated bridged ring hydrocarbon structure in which the alicyclic skeleton (carbon-carbon bond) is entirely composed of carbon-carbon single bonds are particularly preferable. In addition, the alicyclic structure in the alicyclic polyester resin may be introduced into only one of the structural unit derived from dicarboxylic acid or the structural unit derived from diol, or both may be introduced, and particularly limited. Not.

The alicyclic polyester resin has a structural unit derived from a monomer component having an alicyclic structure. Examples of the monomer having an alicyclic structure include diols and dicarboxylic acids having a known alicyclic structure, and are not particularly limited. For example, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedi-strong rubonic acid, 4-methyl-1,2-cyclohexanedi-strong rubonic acid, hymic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-deca Dicarboxylic acids having an alicyclic structure such as hydronaphthalenedicarboxylic acid, 2,7-decahydronaphthalenedicarboxylic acid (including derivatives such as acid anhydrides), etc .; 1,2-cyclopentanediol, 1,3-cyclopentane Diol, 1,2-cyclopentanedimethanol, 1,3-cyclopentanedimethanol, bis (hydro 5-membered ring diol such as (cimethyl) 卜 cyclo [5.2.1.0] decane, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 6-membered ring diols such as 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2-bis- (4-hydroxycyclohexyl) propane, and diols having an alicyclic structure such as hydrogenated bisphenol A (these) And derivatives thereof)).

The alicyclic polyester resin may have a structural unit derived from a monomer component having no alicyclic structure. Examples of the monomer having no alicyclic structure include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid (including derivatives such as acid anhydrides); adipic acid, sebacic acid, azelaic acid, Aliphatic dicarboxylic acids such as succinic acid, fumaric acid and maleic acid (including derivatives such as acid anhydrides); ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3- Butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 3-methyl-1,5-pentanediol, 2-methyl 1,3-propanediol, 2,2-diethyl-1,3-propanediol, - butyl-2-ethyl-1,3-propanediol xylylene glycol, ethylene oxide adduct of bisphenol A, diol propylene oxide adduct of bisphenol A (. Including derivatives thereof) and the like. A monomer having an appropriate substituent (for example, an alkyl group, an alkoxy group, or a halogen atom) bonded to the dicarboxylic acid or diol having no alicyclic structure is also included in the monomer having no alicyclic structure.

The ratio of the monomer unit having an alicyclic ring to the total monomer units (total monomer components) (100 mol%) constituting the alicyclic polyester resin is not particularly limited, but is preferably 10 mol% or more.

Component (7): Organosiloxane Compound The resin composition of the present invention preferably further contains an organosiloxane compound of component (7). The organosiloxane compound is not particularly limited as long as it can be melt-mixed with the epoxy resin, and various polyorganosiloxanes, that is, solids without solvent or liquids at room temperature are used. be able to. Thus, the polyorganosiloxane used in the present invention only needs to be capable of being uniformly dispersed in the cured product of the resin composition.

Examples of such polyorganosiloxane include those in which a siloxane unit as a constituent component is represented by the following general formula (3). This has a hydroxyl group or an alkoxy group bonded to at least one silicon atom in one molecule, and 10 mol% or more of the monovalent hydrocarbon group (R ⁷ ) bonded to the silicon atom is substituted or unsubstituted. It becomes an aromatic hydrocarbon group.

(Wherein R ⁷ is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 18 carbon atoms, and may be the same or different. R ⁸ is a hydrogen atom or 1 carbon atom. And may be the same or different, and m and l each represents an integer of 0 to 3.)

In the general formula (3), among the R ⁷ which is a substituted or unsubstituted saturated monovalent hydrocarbon group having 1 to 18 carbon atoms, the unsubstituted saturated monovalent hydrocarbon group specifically includes methyl Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group A linear or branched alkyl group such as a decyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a dicyclopentyl group or a decahydronaphthyl group, and an aromatic group such as a phenyl group or a naphthyl group. Group, tetrahydronaphthyl group, tolyl group, ethylphenyl group and other aryl groups, benzyl group, phenylethyl group, phenyl Examples include aralkyl groups such as a pill group and a methylbenzyl group.

On the other hand, in R ⁷ of the general formula (3), as the substituted saturated monovalent hydrocarbon group, specifically, a part or all of the hydrogen atoms in the hydrocarbon group are halogen atoms, cyano groups, amino And those substituted by an epoxy group, specifically, chloromethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, chlorophenyl group, dibromophenyl And substituted hydrocarbon groups such as a group, a difluorophenyl group, a β-cyanoethyl group, a γ-cyanopropyl group, and a β-cyanopropyl group.

In addition, (OR ⁸ ) in the general formula (3) is a hydroxyl group or an alkoxy group, and as R ⁸ when (OR ⁸ ) is an alkoxy group, specifically, the above-mentioned R ⁷ is exemplified. An alkyl group having 1 to 6 carbon atoms. More specifically, examples of R ⁸ include a methyl group, an ethyl group, and an isopropyl group. These groups may be the same or different in the same siloxane unit or between siloxane units.

Further, the polyorganosiloxane has a hydroxyl group or alkoxy group bonded to at least one silicon atom in one molecule, that is, at least one of the siloxane units constituting the silicone resin, (OR ⁸ ) of the general formula (3). It preferably has a group.

That is, when it does not have a hydroxyl group or an alkoxy group, the affinity with the epoxy resin becomes insufficient, and the mechanism is not clear, but these hydroxyl groups or alkoxy groups are somehow in the curing reaction of the epoxy resin. Although it is thought that it acts, it is difficult to obtain sufficient physical properties of the cured product formed by the resin composition obtained. In the polyorganosiloxane, the amount of hydroxyl groups or alkoxy groups bonded to silicon atoms is preferably set in the range of 0.1 to 15% by weight in terms of OH groups.

In the resin composition of the present invention, as the organosiloxane, a siloxane derivative having an epoxy group in the molecule can be used. By including a siloxane derivative having an epoxy group in the molecule, the heat resistance and light resistance of the cured product can be improved to a higher level.

The siloxane skeleton (Si-0-Si skeleton) in the siloxane derivative having two or more epoxy groups in the molecule is not particularly limited. For example, a cyclic siloxane skeleton; a linear silicone, a cage type or a ladder type Examples include polysiloxane skeletons such as polysilsesquioxane. Among these, as the siloxane skeleton, a cyclic siloxane skeleton and a linear silicone skeleton are preferable from the viewpoint of improving the heat resistance and light resistance of the cured product and suppressing the decrease in luminous intensity.

That is, the siloxane derivative having two or more epoxy groups in the molecule is preferably a cyclic siloxane having two or more epoxy groups in the molecule or a linear silicone having two or more epoxy groups in the molecule. In addition, the siloxane derivative which has 2 or more epoxy groups in a molecule | numerator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the siloxane derivative having two or more epoxy groups in the molecule include 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2. , 4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,2,4 , 6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -6,8-dipropyl-2,4 , 6,8-tetramethyl-cyclotetrasiloxane, 4,8-di [2- (3- {oxabicyclo [4.1.0] heptyl}) ethyl] -2,6-dipropyl-2,4,6 , 8-tetramethyl-cyclotetrasiloxane, 2,4,8-poly [2- (3 {Oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8- 卜 [2- (3- {oxabicyclo [3- 4.1.0] heptyl}) ethyl] -6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8-tetra [2- (3- { Oxabicyclo [4.1.0] heptyl}) ethyl] -2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having two or more epoxy groups in the molecule, and the like.

Examples of the siloxane derivative having two or more epoxy groups in the molecule include alicyclic epoxy group-containing silicone resins described in JP-A-2008-248169, and single molecules described in JP-A-2008-19422. An organopolysilsesquioxane resin or the like having at least two epoxy functional groups therein can also be employed.

The content (blending amount) of the siloxane derivative having two or more epoxy groups in the molecule is not particularly limited, but is 1 with respect to 100% by weight of the total amount of the compounds having epoxy groups contained in the resin composition of the present invention. ~ 100% by weight is preferred.

Component (8): Rubber Particles The resin composition of the present invention may further contain a rubber particle of component (8). Examples of the rubber particles include rubber particles such as particulate NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl group NBR (CTBN), metal-free NBR, and particulate SBR (styrene-butadiene rubber).

The rubber particles are preferably rubber particles having a multilayer structure (core-shell structure) comprising a core portion having rubber elasticity and at least one shell layer covering the core portion.

The rubber particles are particularly composed of a polymer (polymer) having (meth) acrylic acid ester as an essential monomer component, and hydroxyl groups and functional groups capable of reacting with a compound having an epoxy group such as an epoxy resin on the surface. Rubber particles having a carboxyl group (one or both of a hydroxyl group and a carboxyl group) are preferred.

When there is no hydroxyl group and / or carboxyl group on the surface of the rubber particles, the cured product becomes clouded by a thermal shock such as a thermal cycle, and the transparency is lowered.

The polymer constituting the core part having rubber elasticity in the rubber particles is not particularly limited, but (meth) acrylic acid steal such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. It is preferable to use an essential monomer component.

Polymers constituting the core portion having rubber elasticity include, for example, aromatic vinyls such as styrene and α-methylstyrene, nitriles such as acrylonitrile and methacrylonitrile, conjugated dienes such as butadiene and isoprene, ethylene, and propylene. , Isobutene and the like may be included as a monomer component.

Especially, the polymer which comprises the core part which has rubber elasticity combines the 1 type (s) or 2 or more types selected from the group which consists of aromatic vinyl, a nitrile, and a conjugated diene with a (meth) acrylic acid ester as a monomer component. It is preferable to include. That is, as the polymer constituting the core portion, for example, (meth) acrylic acid ester / aromatic vinyl, (meth) acrylic acid ester / conjugated diene and other binary copolymers; (meth) acrylic acid ester / aromatic Examples thereof include terpolymers such as vinyl / conjugated dienes. The polymer constituting the core portion may contain silicone such as polydimethylsiloxane and polyphenylmethylsiloxane, polyurethane, and the like.

The polymer constituting the core portion is composed of other monomer components such as divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, diallyl phthalate, butylene glycol diacrylate, etc. The monomer (one molecule) may contain a reactive crosslinking monomer having two or more reactive functional groups.

The core part of the rubber particle is a core part composed of a (meth) acrylate / aromatic vinyl binary copolymer (especially butyl acrylate / styrene). It is preferable in that the rate can be easily adjusted.

The core part of the rubber particles can be manufactured by a commonly used method, for example, by a method of polymerizing the above monomer by an emulsion polymerization method. In the emulsion polymerization method, the whole amount of the monomer may be charged all at once and may be polymerized, or after polymerizing a part of the monomer, the remainder may be added continuously or intermittently to polymerize. A polymerization method using seed particles may be used.

The polymer constituting the shell layer of rubber particles is preferably a polymer different from the polymer constituting the core portion. As described above, the shell layer preferably has a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with an epoxy group-containing compound such as an epoxy resin. Thereby, in particular, the adhesiveness can be improved at the interface with the epoxy resin, and excellent crack resistance is exhibited for a cured product obtained by curing the resin composition including the rubber particles having the shell layer. be able to. Moreover, the fall of the glass transition temperature of hardened | cured material can also be prevented.

The polymer constituting the shell layer preferably contains (meth) acrylic acid ester such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate as an essential monomer component.

For example, when butyl acrylate is used as the (meth) acrylic acid ester in the core part, as a monomer component of the polymer constituting the shell layer, (meth) acrylic acid esters other than butyl acrylate (for example, (meth) acrylic acid Methyl, ethyl (meth) acrylate, butyl methacrylate, etc.) are preferably used.

Examples of monomer components that may be contained other than (meth) acrylic acid esters include aromatic vinyl such as styrene and α-methylstyrene, and nitriles such as acrylonitrile and methacrylonitrile.

In the rubber particles, it is preferable that the monomer component constituting the shell layer includes the (meth) acrylic acid ester alone or in combination of two or more, and particularly includes at least aromatic vinyl. It is preferable in that the refractive index of rubber particles can be easily adjusted.

In addition, the polymer constituting the shell layer may be a hydroxyl group-containing monomer (for example, a monomer component) to form a hydroxyl group and / or a carboxyl group as a functional group capable of reacting with a compound having an epoxy group such as an epoxy resin. Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate) and carboxyl group-containing monomers (for example, α, s-unsaturated acids such as (meth) acrylic acid, α such as maleic anhydride) , Β-unsaturated acid anhydride, etc.).

It is preferable that the polymer constituting the shell layer in the rubber particles contains, as a monomer component, one or more selected from the monomers together with (meth) acrylic acid ester. That is, the shell layer is formed of, for example, ternary co-polymer such as (meth) acrylic acid ester / aromatic vinyl / hydroxyalkyl (meth) acrylate, (meth) acrylic acid ester / aromatic vinyl / α, β-unsaturated acid, etc. A shell layer composed of coalescence or the like is preferable.

The polymer constituting the shell layer is divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, in addition to the above-mentioned monomers, in the same manner as the core part as other monomer components. One monomer (one molecule) such as diallyl phthalate or butylene glycol diacrylate may contain a reactive crosslinking monomer having two or more reactive functional groups.

Rubber particles (rubber particles having a core-shell structure) can be obtained by covering the core portion with a shell layer. Examples of the method of coating the core part with the shell layer include, for example, a method of coating the surface of the core part having rubber elasticity obtained by the above method by applying a copolymer constituting the shell layer, and the above method And a method of graph-polymerization using the core portion having rubber elasticity obtained by the above as a trunk component and each component constituting the shell layer as a branch component.

The average particle diameter of the rubber particles is not particularly limited, but is preferably 10 to 500 nm. The refractive index of the rubber particles is, for example, cast into rubber molds and compression molded at 210 ° C. and 4 MPa to obtain a flat plate having a thickness of 1 mm. From the obtained flat plate, a test of 20 mm in length × 6 mm in width is performed. A multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) is used with the prism and the test piece in close contact using monobromonaphthalene as an intermediate solution. It can be obtained by measuring the refractive index at 20 ° C. and sodium D line.

For the refractive index of the cured product of the resin composition of the present invention, for example, a test piece having a length of 20 mm × width of 6 mm × thickness of 1 mm is cut out from a cured product obtained by the heat curing method described in the section of the optical semiconductor device below. Using a multi-wavelength Abbe refractometer (trade name “DR-M2”, manufactured by Atago Co., Ltd.) in a state where the prism and the test piece are in close contact using monobromonaphthalene as an intermediate solution, and 20 ° C. It can be determined by measuring the refractive index at the sodium D line.

The content (blending amount) of the rubber particles in the resin composition of the present invention is not particularly limited, but is 100% by mass for 100 parts by mass of the total amount of the compounds having an epoxy group contained in the resin composition of the present invention. 5 to 30 parts by mass is preferable.

Component (9): Additive The resin composition of the present invention may contain various additives of the component (9) within the range not impairing the effects of the present invention, in addition to those described above.

As such an additive, for example, when a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin is contained, the reaction can be allowed to proceed slowly. Other silane couplings such as silicone and fluorine antifoaming agents, leveling agents, γ-glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane, as long as the viscosity and transparency are not impaired. Conventional additives such as additives, surfactants, inorganic fillers such as silica and alumina, flame retardants, colorants, antioxidants, UV absorbers, ion adsorbents, pigments, phosphors, mold release agents, etc. be able to.

The resin composition of the present invention only needs to contain at least one epoxy resin as the component (1) described above, and the production method (preparation method) is not particularly limited. Specifically, for example, the components can be prepared by mixing each component at a predetermined ratio and defoaming under vacuum as necessary, or glycolurils represented by the general formula (B) A composition (sometimes referred to as an “epoxy resin”) containing a curing agent and a composition containing a curing agent and a curing accelerator, or a curing catalyst as an essential component (sometimes referred to as an “epoxy curing agent”) May be prepared separately, and the epoxy resin and the epoxy curing agent may be mixed at a predetermined ratio, and defoamed under vacuum as necessary.

In this case, the glass filler may be blended in advance as a component of the epoxy resin and / or the epoxy curing agent, or when the epoxy resin and the epoxy curing agent are mixed, the epoxy resin and the epoxy resin. You may mix | blend as components other than a hardening | curing agent.

The temperature at the time of mixing when preparing the epoxy resin is not particularly limited, but is preferably 30 to 150 ° C. Further, the mixing temperature when preparing the epoxy curing agent is not particularly limited, but is preferably 30 to 100 ° C. For mixing, a known apparatus such as a rotation / revolution mixer, a planetary mixer, a kneader, or a dissolver can be used.

In particular, when the resin composition of the present invention contains a curing agent and the polyester resin as essential components, the alicyclic polyester resin and the curing agent are mixed in advance from the viewpoint of obtaining a more uniform composition. After preparing a mixture (a mixture of a polyester resin and a curing agent), an epoxy curing agent was prepared by blending the mixture with a curing accelerator and other additives, and then an epoxy resin prepared separately from the epoxy curing agent. It is preferable to prepare by mixing.

The temperature at which the polyester resin and the curing agent are mixed is not particularly limited, but is preferably 60 ° C to 130 ° C. The mixing time is not particularly limited, but is preferably 30 to 100 minutes. Although mixing is not specifically limited, It is preferable to carry out in nitrogen atmosphere. Moreover, the above-mentioned well-known apparatus can be used for mixing.

Although there is no particular limitation after mixing the polyester resin and the curing agent, an appropriate chemical treatment (for example, hydrogenation, terminal modification of the polyester resin, etc.) may be performed. In the mixture of the polyester resin and the curing agent, a part of the curing agent may react with the polyester resin (for example, a hydroxyl group of the polyester resin).

By curing the resin composition of the present invention, it is possible to obtain a cured product having excellent heat resistance, light resistance and thermal shock resistance, and particularly excellent in moisture absorption reflow resistance. The heating temperature (curing temperature) at the time of curing is not particularly limited, but is preferably 45 to 200 ° C. Further, the heating time (curing time) during curing is not particularly limited, but is preferably 30 to 600 minutes. The curing conditions depend on various conditions. For example, when the curing temperature is increased, the curing time can be shortened, and when the curing temperature is decreased, the curing condition can be appropriately adjusted by increasing the curing time. .

The resin composition of the present invention can be preferably used as a resin composition for optical semiconductor encapsulation. By using it as a resin composition for encapsulating an optical semiconductor, an optical semiconductor device having a high heat resistance, light resistance, and thermal shock resistance, in which an optical semiconductor element is sealed with a cured product that is particularly excellent in moisture absorption reflow resistance. can get. Even if this optical semiconductor device is equipped with a high-output, high-brightness optical semiconductor element, the light intensity is less likely to decrease over time, especially when it is heated in a reflow process after being stored under high-humidity conditions. However, deterioration such as a decrease in luminous intensity is unlikely to occur.

The optical semiconductor device of the present invention is an optical semiconductor device in which an optical semiconductor element is sealed with a cured product of the resin composition (resin composition for sealing an optical semiconductor) of the present invention. The optical semiconductor element is sealed by injecting the resin composition prepared by the above-described method into a predetermined mold and heating and curing under predetermined conditions. Thereby, the optical semiconductor device with which the optical semiconductor element was sealed with the hardened | cured material of the curable epoxy resin composition is obtained. The curing temperature and the curing time can be set in the same range as when the cured product is prepared.

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1
First, 1,3,4,6-tetraglycidylglycoluril (TG-G, manufactured by Shikoku Kasei Kogyo Co., Ltd.), trade name “Celoxide 2021P” (unit: parts by mass) shown in Table 3 Alicyclic epoxy compound (manufactured by Daicel Corporation) and trade name “Glass Beads CF0018WB15C” (glass filler, manufactured by Nippon Fritz Co., Ltd.) -250) to prepare an epoxy resin by mixing and defoaming uniformly.

Next, the product name “Rikacid MH-700” (curing agent, manufactured by Shin Nippon Rika Co., Ltd.) and the product are used as the epoxy resin and epoxy curing agent so that the blending ratio (unit: parts by mass) shown in Table 3 is obtained. Uniform mixing and defoaming with the name “U-CAT18X” (curing accelerator, manufactured by San Apro Co., Ltd.) using a self-revolving stirrer (manufactured by Shinky Co., Ltd., Aritori Kentaro AR-250) Thus, an epoxy resin composition was obtained.

Furthermore, this epoxy resin composition is cast on an optical semiconductor lead frame (InGaN element, 3.5 mm × 2.8 mm), and then heated in an oven (resin curing oven) at 120 ° C. for 5 hours to thereby produce this epoxy resin. An optical semiconductor device in which the optical semiconductor element was sealed with the cured product of the resin composition was obtained.

Examples 2 and 3 and Comparative Example 1
An epoxy resin composition was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3, and an optical semiconductor device in which an optical semiconductor element was sealed was produced.

The following evaluation tests were carried out on the optical semiconductor devices obtained in the examples and comparative examples.
[Electrification test (high-temperature energization test)]
The total luminous flux of the optical semiconductor devices obtained in the examples and comparative examples was measured using a total luminous flux measuring machine, and this was defined as “total luminous flux for 0 hour”. Further, the total luminous flux after a current of 30 mA was passed through the optical semiconductor device for 100 hours in an 85 ° C. thermostat was measured, and this was designated as “total luminous flux after 100 hours”. And luminous intensity retention was computed from the following formula. The results are shown in the column “Luminance retention [%]” in Table 3.

{Luminance retention (%)}
= {Total luminous flux after 100 hours (Im)} / {total luminous flux after 100 hours (Im)} × 100
[Solder heat resistance test]
The optical semiconductor devices (two used for each epoxy resin composition) obtained in the examples and comparative examples were left to stand for 192 hours under conditions of a temperature of 30 ° C. and a relative humidity of 70% to perform a moisture absorption treatment. Next, the optical semiconductor device was put in a reflow furnace and heat-treated under the following heating conditions. Thereafter, this optical semiconductor device was taken out in a room temperature environment, allowed to cool, and then placed in a reflow furnace again and subjected to heat treatment under the same conditions. That is, in the solder heat resistance test, the thermal history under the following heating conditions was given twice to the optical semiconductor device.

[Heating conditions (based on surface temperature of optical semiconductor device)]
(1) Preheating: 150 to 190 ° C. for 60 to 120 seconds (2) Main heating after preheating: Above 217 ° C. for 60 to 150 seconds, maximum temperature 260 ° C.
However, the rate of temperature increase when shifting from preheating to main heating was controlled to 3 ° C./second at the maximum. Then, using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), the optical semiconductor device was observed, whether or not a crack with a length of 90 μm or more occurred in the cured product, and the electrode It was evaluated whether or not peeling (peeling of the cured product from the electrode surface) occurred.

Of the two optical semiconductor devices, the number of optical semiconductor devices having a crack of 90 μm or longer in the cured product is shown in the column of “Solder heat resistance test [number of cracks]” in Table 3, and electrode peeling occurred. The number of optical semiconductor devices is shown in the column of “Solder heat resistance test [number of electrode peeling]” in Table 3.

[Thermal shock test]
The optical semiconductor devices obtained in the examples and comparative examples (two used for each epoxy resin composition) were exposed in an atmosphere of −40 ° C. for 30 minutes, and subsequently 30 ° C. in an atmosphere of 120 ° C. Thermal shock with one minute exposure was applied for 200 cycles using a thermal shock tester. After that, the length of cracks generated in the cured product in the optical semiconductor device was observed using a digital microscope (trade name “VHX-900”, manufactured by Keyence Corporation), and cured among the two optical semiconductor devices. The number of optical semiconductor devices in which cracks having a length of 90 μm or more occurred in the object was measured. The results are shown in the column of “Thermal shock test [number of cracks]” in Table 3.

[Comprehensive judgment]
As a result of each test, those satisfying all of the following (1) were determined as ◯ (good). On the other hand, when any of the following (1) to (4) was not satisfied, it was determined as x (defective).
(1) Current test: luminous intensity retention of 90% or more (2) Solder heat resistance test: O number of optical semiconductor devices having cracks of 90 μm or longer in the cured product (3) Solder heat resistance test: Number of optical semiconductor devices in which electrode peeling occurred was O (4) Thermal shock test: The number of optical semiconductor devices in which a crack of 90 μm or more occurred in the cured product was O results. It is shown in the column.

In the thermosetting resin composition according to the present invention, as the glycidyl glycoluril,
1,3-diglycidyl glycoluril,
1,4-diglycidyl glycoluril,
1,6-diglycidyl glycoluril,
1,3,4-triglycidyl glycoluril,
1,3,4,6-tetraglycidylglycoluril,
1-glycidyl-3a-methyl-glycoluril,
1,3-diglycidyl-3a-methyl-glycoluril,
1,4-diglycidyl-3a-methyl-glycoluril,
1,6-diglycidyl-3a-methyl-glycoluril,
1,3,4-triglycidyl-3a-methyl-glycoluril,
1,3,4,6-tetraglycidyl-3a-methyl-glycoluril,
1-glycidyl-3a, 6a-dimethyl-glycoluril,
1,3-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,4-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,6-diglycidyl-3a, 6a-dimethyl-glycoluril,
1,3,4-triglycidyl-3a, 6a-dimethyl-glycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-dimethyl-glycoluril,
1-glycidyl-3a, 6a-diphenyl-glycoluril,
1,3-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,4-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,6-diglycidyl-3a, 6a-diphenyl-glycoluril,
1,3,4-triglycidyl-3a, 6a-diphenyl-glycoluril,
Examples include 1,3,4,6-tetraglycidyl-3a, 6a-diphenyl-glycoluril and the like.

In the present invention, an epoxy compound (resin) having two or more epoxy groups in one molecule can be used in combination with the glycidyl glycol uril compound. Examples of such epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, cresol novolac type epoxy resins, glycidyl ether type epoxy resins, alicyclic epoxy resins, and heterocyclic type epoxy resins. Etc.

In the present invention, the blending ratio of the epoxy component in which the glycidyl glycoluril and the epoxy compound are combined is preferably 10 to 60% by mass, more preferably 20 to 50% by mass in the entire thermosetting resin composition. % By mass.

In the present invention, the phenol compound (resin) acts as a curing agent for the epoxy compound (resin).

As such a phenol compound, various phenol resins conventionally used as a curing agent for an epoxy compound, specifically, a phenol resin such as a cresol novolac type resin or a phenol novolac type resin is mixed and used. can do.

In particular, a phenol resin or a cresol resin having a naphthol skeleton, a naphthalenediol skeleton, a biphenyl skeleton, or a dicyclopentadiene skeleton in the molecular structure is preferable.

Examples of such phenol resins include SN-485 (trade name, hydroxyl equivalent 215, manufactured by Nippon Steel Chemical Co., Ltd.), which is a cresol novolak resin having an α-naphthol skeleton, and a phenol novolak resin containing a naphthalenediol skeleton. SN-395 (trade name, hydroxyl equivalent 105, manufactured by Nippon Steel Chemical Co., Ltd.), MEH-7851-3H (trade name, hydroxyl equivalent 223, manufactured by Meiwa Kasei Co., Ltd.), which is a phenol novolac resin having a biphenyl skeleton, dicyclo And DPP-6125 (trade name, hydroxyl equivalent 185, manufactured by Nippon Petrochemical Co., Ltd.), which is a phenol novolac resin containing a pentadiene skeleton.

These phenol resins may be used alone or in combination of two or more.

The amount of the phenolic resin is preferably in a range where the ratio of the number of phenolic hydroxyl groups possessed by the phenolic resin to the number of epoxy groups possessed by the epoxy resin [number of phenolic hydroxyl groups / number of epoxy groups] is 0.5 to 1. The range of 8 to 1 is more preferable. By setting it to 0.5 or more, it is possible to prevent the heat resistance from being lowered, and by setting it to 1 or less, it is possible to prevent the adhesion with organic fibers described later from being lowered.

The thermosetting resin composition of the present invention includes an inorganic filler, a curing accelerator, a flame retardant such as a metal hydroxide or zinc borate, an antifoaming agent, and a leveling agent as long as the effects of the present invention are not impaired. Other commonly used additives can be blended as necessary.

Inorganic fillers include fused silica, synthetic silica, crystalline silica, alumina, zirconia, talc, clay, mica, calcium carbonate, magnesium hydroxide, aluminum hydroxide, titanium white, bengara, silicon carbide, boron nitride, silicon nitride, Examples thereof include powders such as aluminum nitride, beads obtained by spheroidizing these, single crystal fibers, and glass fibers. These can be used alone or in admixture of two or more.

Further, silica can be used after being surface-treated with a silane-based or titanium-based coupling agent or the like, if necessary.

Silane coupling agents include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane; γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) and aminosilanes such as -γ-aminopropyltrimethoxysilane.

The blending ratio of the inorganic filler is preferably 20 to 50% by mass, more preferably 30 to 40% by mass in the entire thermosetting resin composition. By making a mixture ratio 20 mass% or more, it can prevent that heat resistance falls.

Examples of the curing accelerator include 2-heptadecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 4-methylimidazole, 4-ethylimidazole, 2-phenyl -4-hydroxymethylimidazole, 2-enyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole Imidazole compounds such as trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, methyldiphenylphosphine Such as dibutylphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetraphenylborate, triphenylphosphinetriphenylborane, etc. Organic phosphine compounds; diazabicycloalkene compounds such as 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo (4,3,0) nonene-5; triethylamine, triethylenediamine And tertiary amine compounds such as benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol.

These can be used alone or in admixture of two or more.

The thermosetting resin composition in the present invention is prepared as a resin solution (varnish) by dissolving or dispersing in an appropriate solvent.

The solvent used for dissolving or dispersing the thermosetting resin composition is not particularly limited, but a solvent having a boiling point of 220 ° C. or lower is preferably used in order to minimize the amount remaining in the prepreg. Specific examples of the solvent include γ-butyrolactone, N-methyl-2-pyrrolidone, dimethylacetamide, methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone, propylene glycol monomethyl ether, and the like. A mixture of more than one species can be used. Among the above solvents, propylene glycol monomethyl ether is preferably used.

The solid content concentration of the varnish is not particularly limited, but when it is too low, the amount of resin impregnated in the prepreg decreases, and when it is too high, the viscosity of the varnish increases and the appearance of the prepreg may deteriorate. Therefore, the range of 40 to 80% by mass is preferable, and 60 to 70% by mass is more preferable.

A prepreg can be produced by applying or impregnating the varnish to a substrate and then drying to remove the solvent. The base material impregnated with varnish is preferably a woven or non-woven fabric made of glass fiber, aramid fiber, polyparabenzoxazole fiber, polyarylate fiber or the like. The weaving method for the woven fabric is not particularly limited, but plain weaving is preferable from the viewpoint of flatness.

The amount of varnish impregnated in the prepreg is preferably in the range of 40 to 70% by mass as the solid content in the total amount with the base material. By setting it as 40 mass% or more, it prevents that an unimpregnated part arises in a base material, and prevents a void and a blurring when it is set as a laminated board. Moreover, by setting it as 70 mass% or less, it will prevent that the dispersion | variation in thickness becomes large and it becomes difficult to obtain a uniform laminated board and a printed wiring board. The method of impregnating or applying the varnish to the substrate and the method of drying after the impregnation or application are not particularly limited, and conventionally known methods can be employed.

A required number of the prepregs thus obtained are laminated and pressed under heating to produce a laminate. Moreover, a metal-clad laminate can be manufactured by stacking a metal foil such as a copper foil on one side or both sides of a prepreg in which a required number of layers are laminated and pressurizing under heating.

Furthermore, the printed wiring board of the present invention can be manufactured by laminating semiconductor chips such as silicon chips by etching the metal-clad laminate in a conventional manner. The processing conditions for producing the laminate and the metal-clad laminate are not particularly limited, but usually a heating temperature of about 170 to 200 ° C., a pressure of about 5 to 50 MPa, and a heating / pressurizing time of 90 to It takes about 150 minutes.

The main raw materials used in the examples and comparative examples and the evaluation tests adopted in the examples and comparative examples are as follows.
[Main ingredients]
(I) Epoxy compound, 1,3,4,6-tetraglycidylglycoluril, product name “TG-G”, manufactured by Shikoku Kasei Kogyo Co., Ltd., bisphenol F type epoxy resin, product name “YDF8170”, Toto Kasei Co., Ltd.・ Naphthalene epoxy resin, product name “HP4032D”, manufactured by DIC Corporation ・ Naphthol aralkyl epoxy resin, product name “ESN-175”, manufactured by Toto Kasei Co., Ltd.

(Ii) Phenol compound / novolak type phenol resin, product name “MEH-7785-3H”, manufactured by Meiwa Kasei Co., Ltd. (iii) Inorganic filler / fused silica, product name “SE1050”, manufactured by Admatechs Co., Ltd. (iv ) Imidazole-based curing accelerator, 2-phenyl-4-methyl-5-hydroxymethylimidazole, product name “2P4MHZ”, manufactured by Shikoku Kasei Kogyo Co., Ltd.

[Evaluation test]
(1) Glass transition temperature It heated up at 5 degree-C / min using the DMA apparatus (The dynamic viscoelasticity measuring apparatus DMA983 by TA Instruments company), and made the peak position of tan-delta the glass transition temperature.

(2) Linear expansion coefficient The linear expansion coefficient in the plane direction (X direction) was measured using a TMA apparatus (manufactured by TA Instruments) at 5 ° C / min.

(3) Solder heat resistance It evaluated based on JISC6481. The evaluation was performed by performing PCT moisture absorption treatment at 121 ° C., 100% for 2 hours, and then immersing in a solder bath at 288 ° C. for 30 seconds, and then checking for an appearance abnormality.

Judgment of evaluation: “No abnormality” or “With bulge (there is a bulge in general)”
(4) Peel strength The peel strength at 23 ° C was measured. The peel strength measurement was performed according to JIS C 6481.

Example 1
<Preparation of varnish>
Propylene glycol as a solvent with 20 parts by mass of 1,3,4,6-tetraglycidylglycoluril, 50 parts by mass of novolac type phenolic resin, 40 parts by mass of fused silica, and 0.5 parts by mass of imidazole curing accelerator Monomethyl ether was added and stirred using a high-speed stirrer to obtain a resin varnish whose resin composition was 70% by mass on the basis of solid content.

<Preparation of prepreg>
Using this resin varnish, 100 parts by mass of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by mass of resin varnish in a solid content and dried in a drying oven at 190 ° C. for 7 minutes. Thus, a prepreg having a resin composition content of 44.4% by mass was produced.

<Production of laminated plate>
Two sheets of this prepreg are stacked, and an electrolytic copper foil with a thickness of 18 μm (YGP-18 manufactured by Nihon Electrolytic Co., Ltd.) is stacked on top and bottom, and heat-press molding is performed at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes. A double-sided copper-clad laminate was obtained.

<Evaluation of laminated board>
The entire surface of the double-sided copper-clad laminate was etched to produce a 6 mm × 25 mm test piece, and the glass transition temperature was measured.

The entire surface of the double-sided copper-clad laminate was etched to produce a 5 mm × 20 mm test piece, and the linear expansion coefficient was measured.

After the above double-sided copper-clad laminate was cut to 50 mm × 50 mm with a grinder saw, a test piece in which only 1/4 of the copper foil was left by etching was produced, and the solder heat resistance was measured.

A 100 mm × 20 mm test piece was prepared from the double-sided copper-clad laminate, and the peel strength was measured.

These measurement results are shown in Table 4.
<Production of printed wiring board>
The double-sided copper-clad laminate was subjected to through-hole processing using a 0.1 mm drill bit, and then the through-hole was filled with plating. Furthermore, both surfaces were patterned by etching to obtain an inner layer circuit board. Next, the prepared prepreg was placed on the front and back of the inner layer circuit board, and this was vacuum-heated and pressure-molded at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum-pressure laminator device. This was heated and cured at 170 ° C. for 60 minutes in a hot air drying apparatus to obtain a laminate.

Next, the surface electrolytic copper foil layer was subjected to blackening treatment, and a φ60 μm via hole for interlayer connection was formed with a carbon dioxide laser. Next, it is immersed in a swelling solution at 70 ° C. (Atotech Japan, Swelling Dip Securigant P) for 5 minutes, and further in an aqueous solution of potassium permanganate at 80 ° C. (Atotech Japan, Concentrate Compact CP) for 15 minutes. After soaking, neutralization was performed, and desmear treatment in the via hole was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 60 ° C. for 60 minutes. Next, the plating resist was peeled off and the entire surface was flash etched to form a pattern of L / S = 20/20 μm. Finally, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 20 μm was formed on the circuit surface to obtain a multilayer printed wiring board.

Examples 2 to 4 and Comparative Example 1
In the same manner as in Example 1, a resin varnish having the composition described in Table 4 (resin composition is 70% by mass based on solid content), prepreg (resin composition content 44.4% by mass), laminate and print A wiring board was produced.

For the laminate, the glass transition temperature, linear expansion coefficient, solder heat resistance and peel strength were measured in the same manner as in Example 1. The obtained measurement results are shown in Table 4.

In the present invention, the glycidyl glycoluril is a glycol glycoluril represented by the general formula (B), that is, an epoxy compound,
1-glycidyl glycoluril,
1,3-diglycidyl glycoluril,
1,4-diglycidyl glycoluril,
1,6-diglycidyl glycoluril,
1,3,4-triglycidyl glycoluril,
1,3,4,6-tetraglycidylglycoluril,
1-glycidyl-3a-methylglycoluril,
1,3-diglycidyl-3a-methylglycoluril,
1,4-diglycidyl-3a-methylglycoluril,
1,6-diglycidyl-3a-methylglycoluril,
1,3,4-triglycidyl-3a-methylglycoluril,
1,3,4,6-tetraglycidyl-3a-methylglycoluril,
1-glycidyl-3a, 6a-dimethylglycoluril,
1,3-diglycidyl-3a, 6a-dimethylglycoluril,
1,4-diglycidyl-3a, 6a-dimethylglycoluril,
1,6-diglycidyl-3a, 6a-dimethylglycoluril,
1,3,4-triglycidyl-3a, 6a-dimethylglycoluril,
1,3,4,6-tetraglycidyl-3a, 6a-dimethylglycoluril,
1-glycidyl-3a, 6a-diphenylglycoluril,
1,3-diglycidyl-3a, 6a-diphenylglycoluril,
1,4-diglycidyl-3a, 6a-diphenylglycoluril,
1,6-diglycidyl-3a, 6a-diphenylglycoluril,
1,3,4-triglycidyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetraglycidyl-3a, 6a-diphenylglycoluril and the like. These glycolurils may be used alone or in combination of two or more.

In the present invention, as an epoxy compound or an epoxy resin excluding the glycidyl glycoluril (hereinafter referred to as “epoxy resin” together), bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, Phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, diglycidyl ether of propylene glycol or polypropylene glycol, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane glycidyl ether, phenyl-1 , 3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6-hexanediol glycidyl ether, ethylene glycol 1 such as diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol glycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. Examples include compounds having two or more epoxy groups in the molecule.

In addition, S-triazine compounds such as melamine as reaction accelerators, imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole and derivatives thereof, and known curing accelerators for epoxy resins such as phenol compounds are used. By heat curing, the heat resistance, chemical resistance, adhesion, and pencil hardness of the cured film can be improved.

In the present invention, the photosensitive prepolymer having two or more unsaturated double bonds in one molecule is a polymer or oligomer having two or more epoxy groups in one molecule, for example, in one molecule. Polyfunctional epoxy compound having two or more epoxy groups (see the above-mentioned epoxy resin), copolymer of alkyl (meth) acrylate and glycidyl (meth) acrylate, hydroxyalkyl (meth) acrylate and alkyl (meth) acrylate Photosensitivity obtained by reacting an unsaturated monocarboxylic acid having an unsaturated double bond with a copolymer of glycidyl (meth) acrylate and the like, followed by addition reaction of an unsaturated or saturated polycarboxylic acid anhydride Prepolymers and oligomers or polymers having carboxyl groups, such as alkyl (meth) acrylates and (meth ) Unsaturated compound having a copolymer in 1 molecule unsaturated double bond and an epoxy group in the acrylic acid, for example, glycidyl (meth) acrylate photosensitive prepolymer obtained by reacting the like. Here, (meth) acrylate refers to acrylate, methacrylate, and a mixture thereof, and the same applies to (meth) acrylic acid.

Since the photosensitive prepolymer has many free carboxyl groups in the side chain, development with a dilute aqueous alkali solution is possible, and at the same time, after exposure / development, the film is post-heated to provide another thermosetting compounding component. As a result, an addition reaction takes place between the epoxy group of the added epoxy compound and the free carboxyl group of the side chain, resulting in a cured film with excellent properties such as heat resistance, solvent resistance, acid resistance, adhesion, and electrical properties. Obtainable.

The total content of glycoluril and epoxy resin excluding glycoluril is preferably 0.01 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

In the present invention, examples of the photopolymerization initiator include benzoins such as benzyl, benzoin, benzoin methyl ether, and benzoin isopropyl ether and zonzoin alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, N, N— Acetophenones such as dimethylaminoacetophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone Anthraquinones such as 2-aminoanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone Examples include ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, and 4,4′-bisdiethylaminobenzophenone; xanthones. These photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization initiator may be a known photosensitizer such as a tertiary amine such as triethylamine or triethanolamine, or a benzoic acid ester such as ethyl-4-dimethylaminobenzoate or 2- (dimethylamino) ethylbenzoate. You may use it in combination with 1 type, or 2 or more types of a sensitizer. Further, a titanocene photopolymerization initiator such as Irgacure 784 (manufactured by Ciba Specialty Chemicals) that initiates radical polymerization in the visible region, a leuco dye, or the like may be used in combination as a curing aid.

The content of the photopolymerization initiator is preferably 0.01 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

As the diluent used in the practice of the present invention, a photopolymerizable vinyl monomer and / or an organic solvent can be used.

Examples of the photopolymerizable vinyl monomer include mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; Acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; phenoxy acrylate, bisphenol A diacrylate and ethylene oxide or propylene oxide addition of these phenols Acrylates such as hexane; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol Polyols, polyhydric alcohols such as tris-hydroxyethyl isocyanurate, or polyvalent acrylates of these ethylene oxide or propylene oxide adducts; glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate Acrylates; melamine acrylate and / or methacrylates corresponding to the acrylates. These photopolymerizable vinyl monomers may be used alone or in combination of two or more.

The content of the photopolymerizable vinyl monomer is preferably 0.1 to 200 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ketones such as methyl ethyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, and acetic acid esterified products of the glycol ethers; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether Aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent is preferably 1 to 500 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

The purpose of using the photopolymerizable vinyl monomer is to enhance the photopolymerizability and dilute the photosensitive prepolymer to facilitate application. The purpose of using the organic solvent is to dissolve and dilute the photosensitive prepolymer and thereby apply it as a liquid. Therefore, depending on the type of diluent, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the film is adopted.

As the polyurethane compound used in the practice of the present invention, known polyurethane fine particles can be employed. The particle diameter of the polyurethane fine particles is preferably 0.01 to 100 μm.

Polyurethane fine particles are obtained by mechanically crushing solid polyurethane at low temperature, by precipitating and drying from an aqueous polyurethane emulsion, spray drying, and by adding a poor solvent to solution-polymerized polyurethane to precipitate polyurethane into granules. It can be prepared by a method such as drying to remove the solvent. The surface of the polyurethane fine particles may be coated with a hydrophobic silica coating or a fluorine compound-treated silica.

The purpose of using the polybutadiene compound used in the practice of the present invention is to make the film flexible. In particular, polybutadiene containing one or more internal epoxy groups (hereinafter referred to as “epoxidized polybutadiene”) undergoes a cross-linking reaction due to having an internal epoxy group and is polymerized, so that it has heat resistance, chemical resistance, and electroless resistance. Flexibility can be imparted without impairing properties such as gold plating properties.

Examples of the epoxidized polybutadiene include polybutadiene containing one or more oxirane oxygens bonded to carbon in the polybutadiene main chain. The epoxidized polybutadiene may contain one or more side groups and / or epoxy groups as end groups.

The content of the polybutadiene compound is preferably 0.4 to 60 parts by mass with respect to 100 parts by mass of the photosensitive prepolymer.

The resin composition of the present invention includes various antifoaming agents, leveling agents, extender pigments such as silica, alumina, barium sulfate, calcium carbonate, calcium sulfate, and talc, and pigments such as titanium oxide, azo, and phthalocyanine. Additives can be included.

Further, the resin composition of the present invention can contain a photosensitive prepolymer other than the photosensitive prepolymer. Other photosensitive prepolymers can be used without particular limitation as long as they have an unsaturated group and a carboxyl group.

The cured product of the resin composition of the present invention preferably has an elastic modulus at room temperature of 500 to 2000 MPa and an elongation of 5 to 100%. When the elastic modulus is less than 500 MPa, the flexibility and the thermal shock resistance are excellent, but the characteristics such as solder heat resistance may be deteriorated. On the other hand, when the elastic modulus exceeds 2000 MPa or the elongation is less than 5%, flexibility and thermal shock resistance may be reduced.

When a solder resist film is formed on a printed wiring board using the resin composition of the present invention, the resin composition is first adjusted to a viscosity suitable for the coating method, and then printed on a circuit pattern previously formed. A film can be formed by applying to a wiring board by a screen printing method, a curtain coating method, a roll coating method, a spray coating method or the like, and if necessary, a drying treatment at a temperature of 60 to 100 ° C., for example.

Besides, the film can be formed by a method such as making the resin composition into a dry film and directly laminating it on a printed wiring board. Then, it selectively exposes with actinic light through the photomask which formed the predetermined exposure pattern. It is also possible to directly expose and draw in a pattern with a laser beam. Next, the unexposed portion can be developed with an aqueous alkali solution to form a resist pattern. Further, for example, by heating to 140 to 180 ° C. and thermosetting, the photosensitive resin can be photosensitive in addition to the curing reaction of the thermosetting component. Polymerization of the resin component is promoted, and the resulting resist film can be improved in heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT (pressure cooker test) resistance, adhesion, electrical characteristics, etc. it can.

As the alkaline aqueous solution used for the development, an aqueous solution containing sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like can be used. As the irradiation light source for photocuring, a xenon lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, or the like is suitable. In addition, laser beams and the like can also be used as actinic rays.

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the following, “part” means “part by mass” unless otherwise specified.

Synthesis example 1
The epoxy equivalent is 217, and an average of 7 phenol nucleus residues in one molecule and 1 equivalent of a cresol novolac type epoxy resin having an epoxy group combined with 1.05 equivalent of acrylic acid are reacted. The resulting reaction product was reacted with 0.67 equivalent of tetrahydrophthalic anhydride by a conventional method to obtain a photosensitive prepolymer. The obtained photosensitive prepolymer was a viscous liquid containing 35 parts of carbitol acetate, and the acid value as a mixture was 65 mgKOH / g.

The main raw materials used in Examples and Comparative Examples are as follows.
(1) Epoxy compound or epoxy resin 1,3,4,6-tetraglycidylglycoluril (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: TG-G, hereinafter referred to as “TG-G”)
2,2 '-(3,3', 5,5'-tetramethyl (1,1'-biphenyl) -4,4'-diyl) bis (oxymethylene) bis-oxirane (manufactured by Japan Epoxy Resin, (Product name: YX-4000, hereinafter referred to as “YX-4000”)

(2) Photosensitive prepolymer / photosensitive prepolymer synthesized in Synthesis Example 1 (hereinafter referred to as “prepolymer”)
(3) Photopolymerization initiator, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 907, hereinafter “Irgacure 907” ")
2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name: DETX-S, hereinafter referred to as “DETX-S”)

(4) Diluent, dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”)
Diethylene glycol monoethyl ether acetate (hereinafter referred to as “carbitol acetate”)

(5) Polybutadiene compound / epoxidized polybutadiene (manufactured by Daicel Chemical Industries, trade name: Epolide PB3600, hereinafter referred to as “PB-3600”)
(6) Polyurethane compound / Polyurethane fine particles (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Dynamic Bead UCN, hereinafter referred to as “UCN”)

(7) Others / Antifoamer (Kyoeisha Chemical Co., Ltd., trade name: Floren AC-300, hereinafter referred to as “AC-300”)
・ Phthalocyanine green ・ Melamine

Example 1
A photocurable / thermosetting resin composition was prepared by mixing and dispersing each component with a three-roll mill so as to have the composition (parts by mass) shown in Table 5.

Comparative Example 1
A photocurable / thermosetting resin composition having the composition shown in Table 5 was prepared in the same manner as in Example 1 except that YX-4000 was used instead of TG-G.

The resin composition obtained in Example 1 and Comparative Example 1 was applied to the entire surface of a printed wiring board on which a pattern was formed by etching a glass-epoxy-based copper-clad laminate laminated with a 35 μm copper foil. It apply | coated by screen printing and it dried at 80 degreeC / 30 minutes using the hot air circulation type dryer, and set it as the test piece 1. FIG. Thereafter, a desired negative film is adhered to the test piece 1 and irradiated with ultraviolet rays of 600 mJ / cm ² from above, followed by development with a 1.0 wt% aqueous sodium carbonate solution for 60 seconds, and hot air circulation drying A test piece 2 having a cured film formed by thermosetting under a condition of 150 ° C./60 minutes using a machine was obtained. When the following evaluation tests were performed on test piece 1 and test piece 2, the test results were as shown in Table 5.

[Solder heat resistance]
The test piece 2 was coated with rosin flux and immersed in a solder bath at 260 ° C. for 10 seconds, and then the cured film was subjected to a peeling test using a cellophane tape to evaluate the state of the cured film thereafter. When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.

[Acid resistance]
After the test piece 2 was immersed in 10% hydrochloric acid for 30 minutes, the state of the cured film was visually observed. When there was no change, it was judged as ◯, and when it was swollen and peeled, it was judged as ×.

[Adhesion]
With respect to the cured film of the test piece 2, 100 crosscuts were put in a grid pattern, and then the state of peeling after a peeling test using a cellophane tape was visually determined. The test method was in accordance with the test method of JIS D-0202.

[sensitivity]
No. of Kodak No. on the test piece 1 film. The step tablet of No. ² was put on, exposed to light at 600 mJ / cm ² using an exposure machine of an ultrahigh pressure mercury lamp, developed, and then the sensitivity was evaluated from the number of steps obtained from the step tablet.

[Resolution]
A negative pattern with a line of 50 to 130 μm is exposed on the film of test piece 1 under the condition of 600 mJ / cm ² using an exposure machine of an ultra-high pressure mercury lamp, developed, and then the formed minimum width line is read. The resolution was evaluated.

[Elastic modulus and elongation]
The elastic modulus (tensile elastic modulus) and the elongation rate (tensile elongation at break) of the evaluation sample were measured by a tensile-compression tester (manufactured by Shimadzu Corporation).

[Flexibility]
The test piece 2 was judged in a state of being bent 180 °. When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.

[Heat resistance degradation]
The test piece 2 was allowed to stand at 125 ° C. for 5 days, and then judged in a state of being bent at 180 ° C.
When there was no peeling, it was judged as “good”, and when there was peeling, it was judged as “poor”.

[Thermal shock resistance]
The test piece 2 was subjected to 300 cycles of cooling / heating at −65 ° C./30 minutes and 150 ° C./30 minutes, and then judged by the presence or absence of cracks in the cured film.
When there was no crack, it was judged as “good”, and when there was a crack, it was judged as “poor”.

[Electroless gold plating resistance]
Using a commercially available electroless nickel plating bath and electroless gold plating bath, after plating the test piece 2 under the same conditions as those for obtaining a thickness of nickel 0.5 μm and gold 0.03 μm, tape peeling Thus, the presence or absence of peeling of the cured film was evaluated.
When there was no peeling, it was judged as ◯, when there was a slight peeling, Δ, and when there was peeling, it was judged as x.

According to the test results shown in Table 5, by including glycidyl glycoluril as an epoxy compound, excellent flexibility without impairing basic characteristics required for solder resist coating such as solder heat resistance. And a photocurable / thermosetting resin composition capable of providing a cured film having a thermal shock resistance.

Therefore, the photocurable / thermosetting resin composition of the present invention is useful for forming a solder resist film used for printed wiring boards for various applications.

Third invention (1) Novel allyl glycolurils Allyl glycolurils according to the present invention are represented by the general formula (C0)

That is, according to the present invention, the general formula (C0a)

(In the formula, R ¹ and R ² are the same as described above.)
1-allylglycoluril represented by the general formula (C0b)

(In the formula, R ¹ and R ² are the same as described above.)
1,3-diallylglycoluril represented by the general formula (C0c)

(In the formula, R ¹ and R ² are the same as described above.)
1,4-diallylglycoluril represented by the general formula (C0d)

(In the formula, R ¹ and R ² are the same as above.) C0e)

(In the formula, R ¹ and R ² are the same as described above.)
1,3,4-triallylglycoluril represented by the formula:

In the above general formula (C0) and allyl glycoluril represented by (C0a) to (C0e), when R ¹ or R ² is a lower alkyl group, the lower alkyl group usually has 1 carbon atom. -5, preferably 1-3, most preferably 1, so the most preferred lower alkyl group is a methyl group.

Accordingly, preferred specific examples of allyl glycolurils according to the present invention include, for example,
1-allyl glycoluril,
1,3-diallylglycoluril,
1,4-diallylglycoluril,
1,6-diallylglycoluril,
1,3,4-triallylglycoluril,
1-allyl-3a-methylglycoluril,
1,3-diallyl-3a-methylglycoluril,
1,4-diallyl-3a-methylglycoluril,
1,6-diallyl-3a-methylglycoluril,
1,3,4-triallyl-3a-methylglycoluril,
1-allyl-3a, 6a-dimethylglycoluril,
1,3-diallyl-3a, 6a-dimethylglycoluril,
1,4-diallyl-3a, 6a-dimethylglycoluril,
1,6-diallyl-3a, 6a-dimethylglycoluril,
1,3,4-triallyl-3a, 6a-dimethylglycoluril,
1-allyl-3a, 6a-diphenylglycoluril,
1,3-diallyl-3a, 6a-diphenylglycoluril,
1,4-diallyl-3a, 6a-diphenylglycoluril,
1,6-diallyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4-triallyl-3a, 6a-diphenylglycoluril.

The allyl glycolurils represented by the general formulas (C0a) to (C0e) can be usually obtained by the following first step and second step.

1-allylglycoluril reacts urea and glyoxal in the first step, usually in water in the presence of a base catalyst, and then the reaction product thus obtained is usually submerged in water in the second step. It can be obtained by reacting with allylurea in the presence of an acid catalyst.

Among diallyl glycolurils, for example, 1,3-diallylglycoluril is obtained by reacting urea and glyoxal in the first step, usually in water in the presence of a base catalyst, and then the reaction product thus obtained. In the second step, usually by reacting with diallyl urea in water in the presence of an acid catalyst.

Among triallyl glycolurils, for example, 1,3,4-triallylglycoluril, in the first step, allylurea and glyoxal are usually reacted in water in the presence of a base catalyst, The reaction product thus obtained can be obtained in the second step by reacting with diallylurea usually in water in the presence of an acid catalyst.

In any synthesis of 1-allylglycoluril, 1,3-diallylglycoluril and 1,3,4-triallylglycoluril, in the first step, glyoxal is used relative to 1 mol part of urea or allylurea. In general, it is used in the range of 0.5 to 2.0 mole parts, preferably in the range of 0.8 to 1.5 mole parts.

Examples of the base catalyst used in the first step include hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate and potassium carbonate. These base catalysts are usually used in the range of 0.1 to 1.0 mole part per mole part of urea or allylurea.

In the first step, when the solvent is used, it is not particularly limited as long as the reaction is not inhibited. For example, alcohols such as water, methanol, ethanol, isopropyl alcohol, Aliphatic hydrocarbons such as hexane and heptane, ketones such as acetone and 2-butanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride , Halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, Amides such as muamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone, hexamethylphosphorotriamide, sulfoxides such as dimethyl sulfoxide, etc. be able to. These solvents are used singly or in combination of two or more, and an appropriate amount is used.

The reaction temperature in the first step is usually in the range of −10 to 150 ° C., preferably in the range of 0 ° C. to 100 ° C. Although depending on the reaction temperature, the reaction time is usually in the range of 1 to 24 hours, preferably in the range of 1 to 6 hours.

After completion of the first step, excess glyoxal and the solvent are distilled off to obtain a reaction product as a concentrate, which may be subjected to the second step, or obtained after the completion of the first step. The reaction mixture obtained may be used as it is in the second step.

In the second step, allyl urea or diallyl urea is usually used in a range of 0.5 to 2.0 mol parts, preferably 1 mol part of urea or allyl urea used in the first step. , 0.8 to 1.5 mole parts.

Examples of the acid catalyst used in the second step include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid and the like. These acid catalysts can be used alone or in combination of two or more. These acid catalysts are usually used in the range of 0.1 to 100 parts by mole with respect to 1 part by mole of urea or allylurea used in the first step.

Also in the second step, the solvent is not particularly limited as long as it does not inhibit the reaction, and the same solvent as in the first step can be used.

The reaction temperature in the second step is usually in the range of −10 to 200 ° C., preferably in the range of 0 ° C. to 150 ° C. Although the reaction time depends on the reaction temperature, it is usually in the range of 1 to 24 hours, preferably in the range of 1 to 12 hours.

After completion of the second step, the produced allyl glycoluril can be appropriately taken out from the obtained reaction mixture by an extraction operation or the like. If necessary, the obtained allyl glycoluril can be further purified by washing with a solvent such as water, activated carbon treatment, silica gel chromatography and the like.

In the following, urea, allyl urea, and 40% glyoxal aqueous solution were manufactured by Tokyo Chemical Industry Co., Ltd., and diallyl urea was manufactured by Sigma-Aldrich.

Example 1
(Synthesis of 1-allylglycoluril)
A 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to the resulting mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. The resulting reaction mixture was then concentrated under reduced pressure. To the obtained concentrate, 5.01 g (50.0 mmol) of allylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added and stirred at 110 ° C. overnight. The resulting reaction mixture was cooled to room temperature, 50 mL of acetone was added, the oil was separated and dried to give 1.86 g of 1-allylglycoluril as a white viscous oil. Yield 20%.

An IR spectrum of the obtained 1-allylglycoluril is shown in FIG. Further, the δ value in the ¹ H-NMR spectrum (d6-DMSO) was as follows.

7.41 (s, 1H), 7.37 (s, 1H), 7.28 (s, 1H), 5.62-5.79 (m, 1H), 5.08-5.28 (m, 4H), 3.86-3.94 (m, 1H), 3.44 (dd, 1H)

Example 2
(Synthesis of 1,3-diallylglycoluril)
A 100 mL flask equipped with a thermometer was charged with 3.00 g (50.0 mmol) of urea and 8.71 g (60.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to the obtained mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. The resulting reaction mixture was then concentrated under reduced pressure. To the resulting concentrate, 7.00 g (50.0 mmol) of diallylurea, 50 mL of acetic acid and 490 mg (5.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C. overnight. After cooling the obtained reaction mixture to room temperature, 50 mL of acetone was added, and the oil was separated and dried to obtain 4.28 g of 1,3-diallylglycoluril as a white viscous oil. Yield 39%.

FIG. 9 shows the IR spectrum of the obtained 1,3-diallylglycoluril. Further, the δ value in the ¹ H-NMR spectrum (d6-DMSO) was as follows.

7.52 (s, 2H), 5.69-5.84 (m, 2H), 5.08-5.23 (m, 6H), 3.92-3.97 (m, 2H), 3. 52 (dd, 2H)

Example 3
(Synthesis of 1,3,4-triallylglycoluril)
A 100 mL flask equipped with a thermometer was charged with 3.00 g (30.0 mmol) of allylurea and 5.22 g (36.0 mmol) of 40% aqueous glyoxal solution. Two drops of 40% aqueous sodium hydroxide solution were added to the obtained mixture at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. The resulting reaction mixture was then concentrated under reduced pressure. To the obtained concentrate, 4.21 g (30.0 mmol) of diallylurea, 30 mL of acetic acid and 294 mg (3.0 mmol) of sulfuric acid were added, and the mixture was stirred at 110 ° C. overnight. After cooling the obtained reaction mixture to room temperature, 30 mL of chloroform was added and liquid-separated. The obtained organic layer was washed with 30 mL of water and then concentrated under reduced pressure to obtain 6.80 g of 1,3,4-triallylglycoluril as a pale yellow oil. Yield 87%.

FIG. 10 shows the IR spectrum of the obtained 1,3,4-triallylglycoluril. Further, the δ value in the ¹ H-NMR spectrum (d6-DMSO) was as follows.

6.22 (br, 1H), 5.72-5.83 (m, 3H), 5.16-5.32 (m, 8H), 4.11-4.26 (m, 2H), 4. 00-4.06 (m, 1H), 3.68-3.85 (m, 3H)

(2) Olefin Resin Composition The olefin resin composition according to the present invention includes allyl glycoluril represented by the general formula (C) and an olefin polymer.

The olefin polymer used in the olefin resin composition according to the present invention refers to a polymer of an olefin monomer, a polymer of a polar monomer, a copolymer of an olefin monomer and a polar monomer, and the like.

Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, and 4-methyl. -1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1 An α-olefin compound having 2 to 20 carbon atoms, such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene;
Cyclopentene, cycloheptene,
2-norbornene,
5-methyl-2-norbornene,
5,6-dimethyl-2-norbornene,
5-ethyl-2-norbornene,
5-butyl-2-norbornene,
5-ethylidene-2-norbornene,
5-methoxycarbonyl-2-norbornene,
5-cyano-2-norbornene,
5-methyl-5-methoxycarbonyl-2-norbornene,
5-hexyl-2-norbornene,
5-octyl-2-norbornene,
5-octadecyl-2-norbornene tetracyclododecene,
1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene,
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene,
1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc. A cyclic olefin compound having 3 to 20 carbon atoms;
Aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, substituted allylnaphthalenes;
Alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, allyl norbornane;
Silane unsaturated compounds such as allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-decene;
Examples thereof include conjugated or non-conjugated diene compounds such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, norbornadiene, and dicyclopentadiene.

Examples of the polar monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid. α, β-unsaturated carboxylic acids and their metal salt compounds such as sodium, potassium, lithium, zinc, magnesium, calcium;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid ester compounds such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
Unsaturated dicarboxylic acids such as maleic acid and itaconic acid;
Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
Examples thereof include unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

In the practice of the present invention, the olefin polymers exemplified in these may be used alone or in combination of two or more.

In the practice of the present invention, allyl glycoluril represented by the general formula (C) is used as a crosslinking aid.

In the allyl glycol urils represented by the general formula (C), when R ¹ and R ² are lower alkyl groups, the carbon number thereof is preferably 1 to 3, and more preferably 1. That is, R ¹ and R ² are more preferably methyl groups.

As such allyl glycolurils,
1-allyl glycoluril,
1,3-diallylglycoluril,
1,4-diallylglycoluril,
1,6-diallylglycoluril,
1,3,4-triallylglycoluril,
1,3,4,6-tetraallylglycoluril,
1-allyl-3a-methylglycoluril,
1,3-diallyl-3a-methylglycoluril,
1,4-diallyl-3a-methylglycoluril,
1,6-diallyl-3a-methylglycoluril,
1,3,4-triallyl-3a-methylglycoluril,
1,3,4,6-tetraallyl-3a-methylglycoluril,
1-allyl-3a, 6a-dimethylglycoluril,
1,3-diallyl-3a, 6a-dimethylglycoluril,
1,4-diallyl-3a, 6a-dimethylglycoluril,
1,6-diallyl-3a, 6a-dimethylglycoluril,
1,3,4-triallyl-3a, 6a-dimethylglycoluril,
1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril,
1-allyl-3a, 6a-diphenylglycoluril,
1,3-diallyl-3a, 6a-diphenylglycoluril,
1,4-diallyl-3a, 6a-diphenylglycoluril,
1,6-diallyl-3a, 6a-diphenylglycoluril,
1,3,4-triallyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetraallyl-3a, 6a-diphenylglycoluril and the like.

In addition, in the range which does not impair the effect of this invention, it is also possible to use together the unsaturated compound which has an allyl group, a (meth) acryloxy group, etc. as another crosslinking adjuvant.

Such unsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl glycidyl isocyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate;
Poly (meth) acryloxy compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate;
Examples include divinylbenzene.

In the practice of the present invention, the crosslinking aid is preferably blended at a rate of 0.1 to 100 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the olefin polymer. More preferred.

The crosslinking of the olefin-based resin composition of the present invention can be performed by adopting a method of mixing and heating a peroxide or a method of irradiating active energy rays.

In addition, the heating temperature in the case of heating by adding a peroxide is not particularly limited, but is preferably set in the range of 50 to 300 ° C.

In addition, what is necessary is just to determine a heating time suitably according to the said heating temperature, the peroxide to be used, a crosslinking adjuvant, or those usage-amounts.

As the peroxide,
1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (t-hexylperoxy) cyclohexane,
1,1-bis (t-butylperoxy) cyclododecane,
1,1-bis (t-butylperoxy) cyclohexane,
2,2-bis (t-butylperoxy) octane,
n-butyl-4,4-bis (t-butylperoxy) butane,
peroxyketal compounds such as n-butyl-4,4-bis (t-butylperoxy) valerate;
Di-t-butyl peroxide,
Dicumyl peroxide,
t-butyl cumyl peroxide,
α, α'-bis (t-butylperoxy-m-isopropyl) benzene,
α, α'-bis (t-butylperoxy) diisopropylbenzene,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane,
Dialkyl peroxide compounds such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;
Acetyl peroxide,
Isobutyryl peroxide,
Octanoyl peroxide,
Decanoyl peroxide,
Lauroyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Benzoyl peroxide,
2,4-dichlorobenzoyl peroxide,
diacyl peroxide compounds such as m-trioyl peroxide;
t-butyl peroxyacetate,
t-butyl peroxyisobutyrate,
t-butylperoxy-2-ethylhexanoate,
t-butyl peroxylaurate,
t-butyl peroxybenzoate,
Di-t-butylperoxyisophthalate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
t-butyl peroxymaleic acid,
t-butyl peroxyisopropyl carbonate,
Peroxyester compounds such as cumyl peroxyoctate;
t-butyl hydroperoxide,
Cumene hydroperoxide,
Diisopropylbenzene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide,
Examples thereof include hydroperoxide compounds such as 1,1,3,3-tetramethylbutyl peroxide, and may be blended at a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the olefin polymer. preferable.

In addition, the peroxide illustrated in these may be used independently and may be used in combination of 2 or more types.

Examples of the active energy rays include particle beams and electromagnetic waves. Examples of the particle beams include electron beams (EB) and α rays. Examples of electromagnetic waves include ultraviolet rays (UV), visible rays, infrared rays, γ rays, and X rays. Etc.

Of these, electron beams and ultraviolet rays are preferably used as active energy rays.

These active energy rays can be irradiated using a known apparatus. In the case of an electron beam, the acceleration voltage is preferably 0.1 to 10 MeV, and the irradiation dose is preferably 1 to 500 kGy. In the case of ultraviolet rays, a lamp having a radiation wavelength of 200 to 450 nm can be used as the radiation source.

In the case of an electron beam, for example, a tungsten filament is used, and in the case of ultraviolet light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultraviolet mercury lamp, a carbon arc lamp, a xenon lamp, a zirconium lamp, and the like.

When ultraviolet rays are used as the active energy ray, a photopolymerization initiator can be further blended. Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1- [4- (methylthio) phenyl] -2. Acetophenones such as morpholinopropan-1-one;
Benzoins such as benzyldimethyl ketal;
Benzophenones such as benzophenone, 4-phenylbenzophenone, hydroxybenzophenone;
Thioxanthones such as isopropylthioxanthone and 2,4-diethylthioxanthone;
And methylphenylglyoxylate.

The photopolymerization initiators exemplified in these may be used alone or in combination of two or more. When the photopolymerization initiator is blended, it is preferably blended at a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the olefin copolymer.

If necessary, known photopolymerization accelerators such as benzoic acids such as 4-dimethylaminobenzoic acid and tertiary amines can be used in combination.

In the olefin resin composition of the present invention, a silane coupling agent can be blended in order to enhance the adhesion when compounded with materials of different materials.

Examples of such silane coupling agents include γ-chloropropylmethoxysilane, vinylethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, and γ-glycidoxypropyl. Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β- (aminoethyl) -γ-aminopropyltrimethoxysilane and the like can be mentioned.

The silane coupling agents exemplified in these may be used alone or in combination of two or more, and 0.1 to 5 parts by mass with respect to 100 parts by mass of the olefin copolymer. It is preferable to mix | blend in the ratio.

In the olefin resin composition of the present invention, an antioxidant, a light stabilizer (ultraviolet absorber) and the like can be blended in order to prevent deterioration due to ultraviolet rays in sunlight.

Among the antioxidants, phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, Monophenol compounds such as stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate;
2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t -Butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-) Bisphenol compounds such as 5-methylphenyl) propionyloxy] ethyl} 2,4,8,10-tetraoxaspiro [5.5] undecane;
1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 ′ -Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) -S-triazine-2 , 4,6- (1H, 3H, 5H) trione, tocophenol, and the like.

Among the antioxidants, phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2, 4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentane Tetraylbi (2,4-di-tert-butyl-4-methylphenyl) phosphite, bis {2-tert-butyl-6-methyl-4- [2- (octadecyloxycarbonyl) ethyl] phenyl} hydrogenphos Phosphite compound such as fight ;
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10 And oxaphosphaphenanthrene oxide compounds such as phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

Examples of the light stabilizer include salicylic acid compounds such as phenyl salicylate, pt-butylphenyl salicylate, and p-octylphenyl salicylate;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, Benzophenone compounds such as 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone;
2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′- Di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5 '-Di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-amylphenyl) benzotriazole, 2-[(2'-hydroxy-3 Benzotriazole compounds such as', 3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole;
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6) And hindered amine compounds such as -pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate.

The antioxidants and light stabilizers exemplified in these are preferably blended at a ratio of 0.1 to 3 parts by mass with respect to 100 parts by mass of the olefin polymer.

In addition to these, for example, a fatty acid salt of a metal such as cadmium or barium can be added to the olefin resin composition of the present invention as an anti-discoloration agent. In addition, pigments, dyes, inorganic fillers and the like can be blended for the purpose of coloring and the like. Examples of these include white pigments such as titanium oxide and calcium carbonate, blue pigments such as ultramarine, black pigments such as carbon black, and glass beads and light diffusing agents.

These additives are preferably blended at a ratio of 0.5 to 50 parts by mass with respect to 100 parts by mass of the olefin polymer.

The olefin resin composition of the present invention, for example, using a tank mixer, a high-speed stirrer, a closed kneader, an internal mixer, a single screw extruder, a twin screw extruder, etc., if necessary, under a nitrogen atmosphere, At an appropriate temperature, the olefin polymer and the allyl glycoluril represented by the general formula (C), if necessary, together with a peroxide, a photopolymerization initiator, and other optional components, It can be prepared by wet mixing, dry mixing or melt mixing.

When using the peroxide to crosslink the olefin resin composition of the present invention, it can be cross-linked during the melt mixing.

The olefin-based resin composition of the present invention is suitably used as a raw material to be processed into various shapes of molded products such as films, sheets, cases (containers), etc. by a known molding method.

Known molding methods include, for example, inflation molding method, T-die molding method, tubular stretch molding method, tenter stretch molding method, extrusion laminate molding method, dry laminate molding method, calendar molding method, bank molding method, injection molding method. , Compression molding method, injection compression molding method, compressed air molding method, vacuum molding method, pipe molding method, profile extrusion molding method, hollow molding method, injection hollow molding method, injection stretch hollow molding method and the like.

When a peroxide is used to crosslink the olefin resin composition of the present invention, it can also be crosslinked during molding by these molding methods.

Moreover, when irradiating an active energy ray and bridge | crosslinking the olefin resin composition of this invention, it irradiates simultaneously with shaping | molding by these shaping | molding methods (inline system), or it irradiates and bridge | crosslinks after shaping | molding. You can also

The olefin resin composition of the present invention is
Various rubber materials such as packing and sealing materials for automobiles,
Solar cell encapsulant (EVA),
Insulation coatings and adhesives for electrical and electronic equipment and parts,
Wire coating materials,
Laminates, structural composite materials, adhesives and anticorrosive materials for civil engineering, paints,
Molded products such as various switches, relays, transformers, coil bobbins, connectors, etc. for electronic components that require heat resistance at a level that does not cause melting deformation when soldering,
LED sealing material,
Various plastic materials for optical materials such as reflectors and lenses,
Suitable for applications such as automobiles, electrical / electronic parts, etc.

It is also suitable for engineering plastic materials such as polybutylene terephthalate resin, which is a crystalline thermoplastic polyester resin with excellent mechanical properties, electrical properties, and other physical and chemical properties and good workability. .

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the measuring method of a haze value and a total light transmittance is shown below.

[Measurement of haze value / total light transmittance]
A sheet of a test piece was sandwiched between two blue glasses having a thickness of 3 mm, and bonded by pressing at 150 ° C. for 15 minutes using a vacuum bonding machine, and the haze value and total light transmittance were measured according to JIS K7105.

Example 1
100 parts by mass of ethylene / vinyl acetate copolymer (vinyl acetate content: 25%, melt index value: 4) as an olefin polymer, 1 part by mass of dicumyl peroxide as a peroxide, 1,3 as a crosslinking aid 5,4,6-tetraallylglycoluril and 5 parts by mass of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent were mixed to prepare an olefin-based resin composition.

From this resin composition, a sheet having a thickness of 0.5 mm was prepared for a test piece at a processing temperature of 100 ° C. using a profile extruder.

For the obtained sheet, the haze value and total light transmittance were measured and shown in Table 6.

Examples 2-6 and Comparative Examples 1-2
A sheet having the composition shown in Table 6 was prepared in the same manner as in Example 1, and the haze value and total light transmittance were measured and shown in Table 6.

According to the present invention, the component (B) is preferably (B-1) an organic compound having at least two alkenyl groups and (B-2) a chain having at least two hydrosilyl groups in one molecule. And / or (B-3) an organically modified silicone compound obtained by a hydrosilylation reaction with a cyclic organohydrogensiloxane.

According to the present invention, the component (B-1) is preferably polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, trivinylcyclohexane, triallyl isocyanurate, methyldiallyl isocyanurate and the general formula ( C2)

(Wherein R ¹ , R ² , R ³ and R ⁴ are all organic groups, at least two of which are alkenyl groups, and X represents a hydrogen atom, an alkyl group or an aryl group.)
At least one compound selected from the group consisting of glycolurils represented by general formula (C2), preferably glycolurils represented by the above general formula (C2).

In the present invention, the component (B-1) is preferably a tetraallyl glycoluril represented by the general formula (C1).

The component (B-2) is a cyclic and / or chain polyorganosiloxane having at least two hydrosilyl groups in one molecule, and preferably a cyclic polyorganosiloxane having at least two hydrosilyl groups in one molecule. Organosiloxane.

<(A) Organic compound having an alkenyl group>
The organic compound having an alkenyl group in the present invention is not particularly limited as long as it is an organic compound having at least one alkenyl group in one molecule. The organic compound does not contain a siloxane unit such as polysiloxane-organic block copolymer or polysiloxane-organic graft copolymer, and may contain only C, H, N, O, S and halogen atoms as constituent elements. preferable. Further, the bonding position of the alkenyl group is not particularly limited, and may be present at any position in the skeleton.

Specific examples of the component (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, di Arylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, monoallyl dimethyl isocyanurate, 1,2,4-trivinylcyclohexane, diallyl monomethyl isocyanurate, divinylbenzenes (having a purity of 50 to 100%, preferably Has a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably In addition to the allyl ether of novolak phenol, allylated polyphenylene oxide, etc., tetraallylglycolurils represented by the above general formula (C1) and oligomers thereof are exemplified. May be used alone or in combination of two or more.

Among the specific examples, for example, from the viewpoint of adhesion to a substrate when the curable composition is cured with the substrate, it is preferable to use the tetraallylglycoluril, and further, a balance of heat and light resistance. From the viewpoint of reducing the thermal stress effectively, it is preferable to use the tetraallylglycolurils.

As the tetraallyl glycoluril,
1,3,4,6-tetraallylglycoluril,
1,3,4,6-tetraallyl-3a-methyl-glycoluril,
1,3,4,6-tetraallyl-3a, 6a-dimethyl-glycoluril,
Examples include 1,3,4,6-tetraallyl-3a, 6a-diphenyl-glycoluril and the like.

In addition, the skeleton of the component (A) may have a functional group other than an alkenyl group, but from the viewpoint of compatibility with the component (B), a straight chain such as a methyl group, an ethyl group, or a propyl group. A functional group having a low polarity such as the above aliphatic hydrocarbon group is preferred. When a highly polar glycidyl group, carboxyl group, or the like is used, the compatibility with the component (B) is deteriorated, and a transparent cured product may not be obtained.

In addition, these (A) components may be used alone or in combination of two or more, but from the viewpoint of controlling the physical properties of the cured product, it is preferable to use two or more in combination, and heat resistance as described above. From the viewpoint of balance between light resistance and adhesiveness, it is more preferable to use tetraallyl glycoluril.

<(B) Compound having at least three hydrosilyl groups in one molecule>
The component (B) in the present invention is mainly used as a curing agent, and is not particularly limited as long as it is an organosiloxane having at least three hydrosilyl groups in the molecule.

For example, an organohydrogenorganosiloxane, an organic compound having at least two alkenyl groups (component (B-1)), and a chain and / or cyclic structure having at least two hydrosilyl groups in one molecule. Examples thereof include organically modified silicone compounds (component (B-3)) obtained by hydrosilylation reaction of organohydrogenorganosiloxane (component (B-2)).

Here, the organohydrogenorganosiloxane refers to a siloxane compound having a hydrocarbon group or a hydrogen atom on a silicon atom.

Of these components (B), it is preferable to use an organically modified silicone compound (B-3) from the viewpoint of compatibility with the component (A) which is an organic compound.

Examples of the organohydrogenorganosiloxane include a chain or cyclic group represented by the general formula (1), the general formula (2) or the general formula (3), and a polyhedral polysiloxane containing a hydrosilyl group. .

(3 <m + n ≦ 50, 3 <m, 0 ≦ n, R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.)

(1 <m + n ≦ 50, 1 <m, 0 ≦ n, R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.)

(3 ≦ m + n ≦ 20, 3 <m ≦ 19, 0 ≦ n <18, R may be a hydrocarbon having 2 to 20 carbon atoms in the main chain and may contain one or more phenyl groups.)

In addition, as the organically modified silicone as the component (B-3), various types can be synthesized and used by combining the components (B-1) and (B2).

The component (B-1) is not particularly limited as long as it is an organic compound having at least two alkenyl groups. Specific examples thereof include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, Pentaerythritol triallyl ether, 1,1,2,2-tetraallyloxyethane, diarylidene pentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes ( Having a purity of 50 to 100%, preferably having a purity of 80 to 100%), divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, diallyl monoglycidyl isocyanurate, diallyl monomer Ruisocyanurate, diallyl ether of bisphenol A, diallyl ether of bisphenol S, tetraallylglycoluril and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1,2 ratio of 50 to 100%), allyl ether of novolak phenol, allylated polyphenylene oxide, and those in which part or all of the glycidyl group of a conventionally known epoxy resin is replaced with an allyl group.

The component (B-1) is preferably an organic compound having a heterocyclic skeleton from the viewpoint that a cured product having good characteristics can be obtained. The organic compound having a heterocyclic skeleton is not particularly limited as long as it is a compound having a hetero element in the cyclic skeleton, but those containing Si in the atoms forming the ring are excluded. Moreover, there is no restriction | limiting in particular in the number of atoms which forms a ring, Although it should just be 3 or more, it is preferable that it is 10 or less from the point of availability.

Specific examples of the heterocyclic ring include epoxy, oxetane, furan, thiophene, pyralol, oxazole, furazane, triazole, tetrazole, pyran, pyridine, oxazine, thiazine, pyridazine, In addition to pyrimidine-based, pyrazine-based, piperazine-based, and the like, glycoluril-based ones may be mentioned, but glycoluril-based heterocycles are preferable in that the effects of the present invention are dramatically achieved.

That is, as the component (B-1), it is preferable to use the glycoluril represented by the general formula (C2), and it is more preferable to use the tetraallylglycoluril.

In addition, as the allyl glycoluril including the tetraallyl glycoluril,
1-allyl glycoluril,
1,3-diallylglycoluril,
1,4-diallylglycoluril,
1,6-diallylglycoluril,
1,3,4-triallylglycoluril,
1,3,4,6-tetraallylglycoluril,
1-allyl-3a-methyl-glycoluril,
1,3-diallyl-3a-methyl-glycoluril,
1,4-diallyl-3a-methyl-glycoluril,
1,6-diallyl-3a-methyl-glycoluril,
1,3,4-triallyl-3a-methyl-glycoluril,
1,3,4,6-tetraallyl-3a-methyl-glycoluril,
1-allyl-3a, 6a-dimethyl-glycoluril,
1,3-diallyl-3a, 6a-dimethyl-glycoluril,
1,4-diallyl-3a, 6a-dimethyl-glycoluril,
1,6-diallyl-3a, 6a-dimethyl-glycoluril,
1,3,4-triallyl-3a, 6a-dimethyl-glycoluril,
1,3,4,6-tetraallyl-3a, 6a-dimethyl-glycoluril,
1-allyl-3a, 6a-diphenyl-glycoluril,
1,3-diallyl-3a, 6a-diphenyl-glycoluril,
1,4-diallyl-3a, 6a-diphenyl-glycoluril,
1,6-diallyl-3a, 6a-diphenyl-glycoluril,
Examples include 1,3,4-triallyl-3a, 6a-diphenyl-glycoluril and 1,3,4,6-tetraallyl-3a, 6a-diphenyl-glycoluril.

The component (B-2) in the present invention is not particularly limited as long as it is an organohydrogensiloxane compound having at least two hydrosilyl groups in one molecule. For example, it is described in International Publication No. 96/15194 pamphlet. A compound having at least two hydrosilyl groups in one molecule can be used. Among these, from the viewpoint of availability, a linear and / or cyclic organopolysiloxane having at least two hydrosilyl groups in one molecule is preferable, and the compatibility in the silicone-based curable composition is good. From the viewpoint, cyclic organopolysiloxane is preferable.

Examples of cyclic siloxanes containing hydrosilyl groups include 1,3,5,7-tetramethylcyclotetrasiloxane, 1-propyl-3,5,7-trihydrogen-1,3,5,7-tetramethylcyclotetra. Siloxane, 1,5-dihydrogen-3,7-dihexyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5-trihydrogen-trimethylcyclosiloxane, 1,3,5, 7,9-pentahydrogen-1,3,5,7,9-pentamethylcyclosiloxane, 1,3,5,7,9,11-hexahydrogen-1,3,5,7,9,11 -Hexamethylcyclosiloxane and the like are exemplified, but 1,3,5,7-tetramethylcyclotetrasiloxane is preferable from the viewpoint of availability.

The molecular weight of the component (B-2) is not particularly limited and any can be used, but from the viewpoint of fluidity, those having a low molecular weight are preferably used. In this case, the lower limit of the molecular weight is 58, and the upper limit is 100,000, more preferably 1,000, and still more preferably 700.

<(C) Hydrosilylation catalyst>
There is no restriction | limiting in particular about the kind of hydrosilylation catalyst of (C) component in this invention, Arbitrary things can be used.

For example, solid platinum is supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black, etc .; platinum-vinylsiloxane complex {for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi ) _N , Pt [(MeViSiO) ₄ ] _m }; platinum-phosphine complex {eg Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ } (wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent an integer), Pt ( acac) ₂ Also, platinum-hydrocarbon complexes described in Ashby et al., US Pat. Nos. 3,159,601 and 3,159,662, and Lamoreaux The platinum alcoholate catalyst described in U.S. Pat. No. 3,220,972 is also mentioned.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₃ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like.

These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt (acac) _{2 and the} like are preferable.

The catalyst amount of component (C) is not particularly limited, but is preferably in the range of 10 ⁻¹ to 10 ⁻⁸ mol per mol of alkenyl group in component (A), and is preferably 10 ⁻² to 10 ^−. More preferably, it is used in the range of ⁶ moles. When the amount is less than 10 ⁻⁸ mol, hydrosilylation may not proceed sufficiently. When an amount exceeding 10 ⁻¹ mol is used, the storage stability of the composition may be deteriorated. In addition, these (C) components may be used independently and may use 2 or more types together.

<Curable composition>
The curable composition in the present invention is not particularly limited as long as it is a composition that cures by a hydrosilylation reaction and contains a compound having an alkenyl group, a compound having a hydrosilyl group, and a hydrosilylation catalyst.

The composition ratio of the component (A) and the component (B) in the curable composition is not particularly limited, but from the viewpoint of efficiently proceeding the curing reaction, the molar ratio is in the range of 0.5 to 2.0. Preferably, it is in the range of 0.7 to 1.5, more preferably in the range of 0.8 to 1.3. (However, the molar ratio represents (number of moles of hydrosilyl group of component (B)) / (number of moles of alkenyl group of component (A)).)

When the molar ratio is less than 0.5, for example, when the composition is cured, excessive alkenyl groups may remain in the system, which may cause problems with the heat resistance of the cured product. Is more than 1.3, excess hydrosilyl groups may remain in the system. For example, a condensation reaction between hydrosilyl groups may occur during a long-term heat test, and the properties of the cured product may deteriorate. .

The viscosity of the curable composition is preferably 2000 cP or less, more preferably 1000 cP or less, and further preferably 500 cP or less from the viewpoint of handling properties.

When the viscosity exceeds 2000 cP, when the curable composition is applied with a dispenser, there is a possibility that resin clogging is likely to occur or it is difficult to apply uniformly.

<Curing retarder>
A curing retarder can be used for the purpose of improving the storage stability of the curable composition of the present invention or for adjusting the reactivity of the hydrosilylation reaction during the production process. Examples of the curing retardant include compounds having an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin-based compounds, organic peroxides, and the like, and these may be used in combination.

Examples of the compound having an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide and the like. Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Of these curing retarders, benzothiazole, thiazole, dimethyl malate, and 3-hydroxy-3-methyl-1-butyne are preferable from the viewpoint of good retarding activity and easy availability of raw materials.

The addition amount of the storage stability improving agent, compared hydrosilylation catalyst 1 mole to be used, the lower limit 10 ^-1 mol, the range of the upper limit 10 ³ moles, more preferably, is at the lower limit 1 mol, the range of the upper limit 50 mol .

<Adhesive agent>
To the curable composition of the present invention, an adhesion-imparting agent can be added as an additive for the purpose of improving the adhesion to an adherend. For example, a silane coupling agent, a boron-based coupling agent, titanium A coupling agent, an aluminum coupling agent, or the like can be used.

Examples of the silane coupling agent include at least one functional group selected from an epoxy group, a methacryl group, an acrylic group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group in the molecule, and a silicon atom-bonded alkoxy group. A silane coupling agent having a group is preferred. About this functional group, it is more preferable that they are an epoxy group, a methacryl group, and an acryl group from the point of sclerosis | hardenability and adhesiveness.

For example, as organosilicon compounds having an epoxy functional group and a silicon atom-bonded alkoxy group, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Examples include trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

Examples of the organosilicon compound having a methacrylic group or an acrylic group and a silicon atom-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- Examples include acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

Examples of the boron coupling agent include trimethyl borate, triethyl borate, tri-2-ethylhexyl borate, normal trioctadecyl borate, trinormal octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, Trinormal butyl borate, tri-sec borate -Butyl, boric acid tri-tert. -Butyl, triisopropyl borate, trinormalpropyl borate, triallyl borate, boron methoxyethoxide.

Examples of the titanium coupling agent include tetra (n-butoxy) titanium, tetra (i-propoxy) titanium, tetra (stearoxy) titanium, di-i-propoxy-bis (acetylacetonate) titanium, i- Propoxy (2-ethylhexanediolate) titanium, di-i-propoxy-diethylacetoacetate titanium, hydroxy-bis (lactate) titanium, i-propyltriisostearoyl titanate, i-propyl-tris (dioctylpyrophosphate) titanate, Tetra-i-propyl) -bis (dioctyl phosphite) titanate, tetraoctyl-bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) Chirenchitaneto, i- propyl trioctanoyl titanate include i- propyl dimethacryl -i- stearoyl titanate.

Examples of the aluminum coupling agent include aluminum butoxide, aluminum isopropoxide, aluminum acetylacetonate, aluminum ethylacetoacetonate, and acetoalkoxyaluminum diisopropylate.

These adhesiveness-imparting agents may be used alone or in combination of two or more. The addition amount of the adhesion-imparting agent is preferably 5 parts by mass or less with respect to 100 parts by mass in total of the component (A) and the component (B).

<Other additives>
As long as the effects of the present invention are not impaired, additives can be used for the purpose of imparting tackiness and adhesion to a cured product obtained by curing the curable composition of the present invention. Although there is no restriction | limiting in particular in the kind of additive to be used, From a viewpoint of suppressing the bleeding from hardened | cured material, it is a compound which has an alkenyl group or a hydrosilyl group, Comprising: At the time of hardening by hydrosilylation, (A) component or (B ) It is preferable to use a compound capable of forming a chemical bond with the component.

Examples of the compound having an alkenyl group include a dimethylpolysiloxane blocked with a dimethylvinylsiloxy group at both ends of the molecular chain having an alkenyl group, a dimethylpolysiloxane blocked with a methylphenylvinylsiloxy group at both ends of the molecular chain, and a dimethylvinylsiloxy group blocked at both ends of the molecular chain. Dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, both molecular chains Terminal dimethylvinylsiloxy group-blocked methyl (3,3,3-trifluoropropyl) polysiloxane, molecular chain both-end silanol group-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both-end sila Lumpur group dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers.

These can be used either individually or in combination of two or more. Moreover, it is preferable that the addition amount of these additives is 5 mass parts or less with respect to a total of 100 mass parts of (A) component and (B) component. In addition, depending on the type or amount of the additive, the influence on the hydrosilylation reaction must be considered.

<Hardened product obtained by curing curable composition>
The cured product of the present invention is excellent in heat resistance and light resistance, and also has excellent adhesion to various substrates because of its small curing shrinkage after curing. Therefore, it can be used as a resin layer for various optical devices. it can.

From the viewpoint of reducing thermal stress, the cured product of the present invention preferably has a glass transition temperature of 150 ° C. or lower, more preferably 145 ° C. or lower, and even more preferably 140 ° C. or lower. When the glass transition temperature exceeds 150 ° C., thermal stress at the time of curing or in a high temperature environment increases, and for example, warping may occur when cured on a base material, or adhesion to the base material may be reduced. is there.

In addition, as described above, the cured product of the present invention preferably has a storage elastic modulus at 150 ° C. of 500 MPa or less, more preferably 200 MPa or less, and 100 MPa or less from the viewpoint of reducing thermal stress. More preferably. When the storage elastic modulus exceeds 500 MPa, the thermal stress increases, and there is a possibility that warping may occur or the adhesion to the substrate may be reduced when cured on the substrate.

Various methods can be employed for measuring the glass transition temperature, and examples include dynamic viscoelasticity measurement and thermomechanical measurement, and the storage elastic modulus can be measured by dynamic viscoelasticity measurement. it can.

<Optical device>
Examples of the optical device having the curable composition of the present invention as a resin layer include light emitting diodes, various light receiving elements, display displays, solar cells, and the like.

A light emitting diode can be produced using the curable composition of the present invention. In this case, the light emitting diode can be coated with the light emitting element with the curable composition of the present invention.

The light emitting element is a light emitting element used in a conventionally known light emitting diode. As such a light emitting element, for example, a semiconductor material is laminated on a substrate provided with a buffer layer of GaN, AlN or the like, if necessary, by various methods such as MOCVD, HDVPE, and liquid phase growth. Things. Various materials can be used as the substrate in this case, and examples thereof include sapphire, spinel, SiC, Si, ZnO, and a GaN single crystal. Among these, it is preferable to use sapphire from the viewpoint that GaN having good crystallinity can be easily formed and has high industrial utility value.

Examples of the semiconductor material to be stacked include GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, SiC, and the like. Of these, nitride-based compound semiconductors (Inx GayAlz N) are preferable from the viewpoint of obtaining high luminance. Such a material may contain an activator or the like.

Examples of the structure of the light-emitting element include a MIS junction, a pn junction, a homojunction having a PIN junction, a heterojunction, and a double heterostructure. Moreover, it can also be set as a single or multiple quantum well structure.

The light emitting element may or may not be provided with a passivation layer. An electrode can be formed on the light emitting element by a conventionally known method.

The electrode on the light emitting element can be electrically connected to the lead terminal etc. by various methods. As the electrical connection member, a material having good ohmic mechanical connectivity with the electrode of the light emitting element is preferable, and examples thereof include a bonding wire using gold, silver, copper, platinum, aluminum, or an alloy thereof. . Alternatively, a conductive adhesive or the like in which a conductive filler such as silver or carbon is filled with a resin can be used. Of these, it is preferable to use an aluminum wire or a gold wire from the viewpoint of good workability.

A light-emitting element can be obtained as described above. In the light-emitting diode of the present invention, any light intensity can be used as long as the light intensity in the vertical direction is 1 cd or more. The effect of the present invention is more remarkable when a light emitting element of 2 cd or more is used, and the effect of the present invention is further remarkable when a light emitting element of 3 cd or more is used.

The light emission output of the light emitting element can be arbitrarily selected without any particular limitation. The light emission wavelength of the light emitting element may be various wavelengths from the ultraviolet region to the infrared region.

The light-emitting element to be used may emit a single color with a single type of light-emitting element, or a combination of a plurality of light-emitting elements may emit a single color or multiple colors.

The lead terminal used in the light emitting diode of the present invention preferably has good adhesion to an electrical connecting member such as a bonding wire, electrical conductivity, etc., and the electrical resistance of the lead terminal is preferably 300 μΩ-cm or less. More preferably, it is 3 μΩ-cm or less. Examples of these lead terminal materials include iron, copper, iron-containing copper, tin-containing copper, and those plated with silver, nickel, or the like. The glossiness of these lead terminals may be adjusted as appropriate in order to obtain a good light spread.

The light-emitting diode of the present invention can be produced by coating the light-emitting element with the curable composition of the present invention. In this case, the coating is not limited to the one directly sealing the light-emitting element, but indirectly. It also includes the case of coating. Specifically, the light emitting device may be sealed by various methods conventionally used directly with the curable composition of the present invention, and conventionally used epoxy resins, silicone resins, acrylic resins, urea resins, imide resins, etc. After sealing the light emitting element with the sealing resin or glass, the top or the periphery thereof may be coated with the curable composition of the present invention. Further, after sealing the light emitting element with the curable composition of the present invention, it may be molded with a conventionally used epoxy resin, silicone resin, acrylic resin, urea resin, imide resin or the like. Various effects such as a lens effect can be provided by the difference in refractive index and specific gravity by the above method.

Various methods can be employed as the sealing method. For example, a liquid composition may be injected into a cup, cavity, package recess, or the like in which a light emitting element is arranged at the bottom by a dispenser or other method and cured by heating, or a solid or highly viscous liquid composition The material may be heated and flowed, and similarly injected into the package recesses and further heated to be cured. The package in this case can be made using various materials, such as polycarbonate resin, polyphenylene sulfide resin, epoxy resin, acrylic resin, silicone resin, ABS resin, polybutylene terephthalate resin, polyphthalamide resin, and the like. be able to. In addition, a method of injecting a composition into a mold form in advance, dipping a lead frame or the like on which the light emitting element is fixed, and then curing the composition can be adopted. Alternatively, the sealing layer made of the composition may be molded and cured by injection with a dispenser, transfer molding, injection molding or the like. Furthermore, a composition that is simply in a liquid or fluid state may be dropped or coated into a light emitting element shape and cured.

Also, the curable resin can be molded and cured by applying it on the light emitting element through stencil printing, screen printing or a mask. In addition, a method in which a composition partially cured or cured in a plate shape or a lens shape in advance is fixed on the light emitting element may be used. Further, it can be used as a die bond agent for fixing the light emitting element to a lead terminal or a package, or can be used as a passivation film on the light emitting element. It can also be used as a package substrate.

The shape of the covering portion is not particularly limited, and may be various shapes. Examples thereof include a lens shape, a plate shape, a thin film shape, and a shape described in JP-A-6-244458. These shapes may be molded by molding and curing the composition, or may be molded by post-processing after curing the composition.

The light emitting diode of the present invention can be of various types, for example, any type such as a lamp type, an SMD type, and a chip type. Various types of SMD type and chip type package substrates are used, and examples thereof include epoxy resin, BT resin, and ceramic.

In addition, various conventionally known methods can be applied to the light emitting diode of the present invention. For example, a method of providing a layer for reflecting or condensing light on the back surface of the light emitting element, a method of forming a complementary colored portion at the bottom corresponding to yellowing of the sealing resin, a thin film that absorbs light having a wavelength shorter than the main emission peak On the light-emitting element, a method in which the light-emitting element is sealed with a soft or liquid sealing material, and the periphery is molded with a hard material, and a phosphor that absorbs light from the light-emitting element and emits longer wavelength fluorescence A method in which the light emitting element is sealed with a material containing, and then the periphery is molded. A method in which a phosphor-containing material is molded in advance and then molded together with the light emitting element. As described in JP-A-6-244458, a molding material is used. A method that increases luminous efficiency as a special shape, a method that makes the package a two-stage recess to reduce uneven brightness, a method that inserts and fixes light emitting diodes in through holes, Examples include a method of forming a thin film that absorbs light having a wavelength shorter than the light wavelength, and a method of extracting light from the substrate direction by connecting the light emitting element to a lead member by flip chip connection using a solder bump or the like. .

The light emitting diode of the present invention can be used for various known applications. Specific examples include a backlight, illumination, sensor light source, vehicle instrument light source, signal light, indicator light, display device, planar light source, display, decoration, various lights, and the like.

[Adhesion test: Cross-cut method]
3 cc of the curable composition was coated on a 10 cm × 10 cm glass substrate, coated to a thickness of 40-60 μm using a bar coater, and cured by convection oven at 150 ° C. for 1 hour. A coated film was obtained. Using the obtained coating material, a cross-cut test was conducted in accordance with JIS 5600-5-6, and the adhesion was evaluated in six stages from 0 to 5 according to the criteria of the same standard.

[Heat resistance test: Long-term heat test]
The curable composition was poured into a mold produced by sandwiching a 3 mm thick silicone rubber spacer between two glass substrates, and was subjected to 60 ° C./6 hours, 70 ° C./1 hour, 80 ° C./1 hour, 120 ° C. / A measurement cured product (3 mm thickness) is produced by stepwise heating at 150 ° C./1 hour for 1 hour, then cured at 120 ° C. for 100 hours in a convection oven, and then the cured product is not colored. Was evaluated visually, and it was evaluated as ◎ when not colored at all and ◯ when the surface was slightly colored.

[Light resistance test]
Use Suga Test Instruments Co. metering weather meter, black panel temperature 120 ° C., at irradiance 0.53 kW / m ^2, after irradiation until the integrated irradiance 50 MJ / m ^2, the change in appearance before and after irradiation The presence or absence was observed, and when there was no change, it was evaluated as ○, and when there was a change such as coloring, it was evaluated as ×.

Synthesis example 1
A stirrer, a condenser tube and a dropping funnel were attached to a 5 L two-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the mixture was heated and stirred in an oil bath at 120 ° C. To this solution, 240 g of 1,3,4,6-tetraallylglycoluril, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain 720 g of a product.

^{According to 1} H-NMR, the product is a product in which a part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane has reacted with 1,3,4,6-tetraallylglycoluril. I understood. The modified product thus obtained was used as the component (A) in Examples and Comparative Examples.

Synthesis example 2
To a 5 L separable flask, 1380 g of toluene and 1360 g of 1,3,5,7-tetramethylcyclotetrasiloxane were added and heated to an internal temperature of 100 ° C. Thereto was added dropwise a mixture of 330 g of 1,3,4,6-tetraallylglycoluril, 1.36 mL of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) and 300 g of toluene. The dropping was completed in 30 minutes. During the dropping, the internal temperature rose to 109 ° C. Unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure.

^{According to 1} H-NMR, the obtained product was obtained by reacting part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane with 1,3,4,6-tetraallylglycoluril. I found out. The modified product thus obtained was used as the component (B) in Examples and Comparative Examples.

Synthesis example 3
A stirrer, a condenser tube and a dropping funnel were attached to a 5 L two-necked flask. To this flask, 1800 g of toluene and 1440 g of 1,3,5,7-tetramethylcyclotetrasiloxane were placed, and the mixture was heated and stirred in an oil bath at 120 ° C. To this solution, 200 g of triallyl isocyanurate, 200 g of toluene and 1.44 ml of a xylene solution of platinum vinylsiloxane complex (containing 3 wt% as platinum) were added dropwise over 50 minutes. The resulting solution was heated and stirred as it was for 6 hours. After adding 2.95 mg of 1-ethynyl-1-cyclohexanol, unreacted 1,3,5,7-tetramethylcyclotetrasiloxane and toluene were distilled off under reduced pressure to obtain 710 g of a product.

^{From 1} H-NMR, it was found that the product was obtained by reacting part of the hydrosilyl group of 1,3,5,7-tetramethylcyclotetrasiloxane with triallyl isocyanurate. The modified product thus obtained was used as the component (A) in the comparative example.

Examples 1 to 3 and Comparative Example 1
Each component was mix | blended by the compounding ratio (mass part) shown in Table 7, the curable composition was prepared, the hardened | cured material for various evaluation was obtained on the predetermined hardening conditions, and each evaluation was implemented.

The examples show excellent adhesion without impairing the heat and light resistance, but the comparative examples have insufficient heat stress and light resistance due to insufficient reduction of thermal stress.

From the above, the curable composition in the present invention gives a cured product having excellent heat and light resistance without impairing the adhesion to various substrates.

The thermosetting resin composition according to the present invention is an organopolysiloxane having an alkenyl group-containing organopolysiloxane as a main agent (base polymer) in which both molecular chain ends represented by the general formula (C3) are blocked with an allyl glycoluril ring. A siloxane polymer, that is, an organopolysiloxane polymer having an alkenyl group (allyl group) at both ends of the molecular chain, is used as a curing agent (crosslinking agent) at the end of the siloxane chain represented by the general formula (C4). Cured product utilizing hydrosilylation (addition reaction) characteristics by using a glycoluril ring-containing organohydrogenpolysiloxane polymer having a hydrogen atom (Si—H group) bonded to at least two silicon atoms Can be given.

The component (A) is an organopolysiloxane polymer having an allyl glycoluril ring structure at both ends of the molecular chain represented by the general formula (C3).

In the composition of the present invention, the organopolysiloxane polymer represented by the general formula (C3) is used as the alkenyl group-containing organopolysiloxane which is the main agent (base polymer).

In the general formula (C3), R independently of each other is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and the curing characteristics, flexibility, and synthesis of the composition From the standpoint of ease, it is preferably a methyl group, and 50 mol% or more (50 to 100 mol%) of all R groups are preferably methyl groups.

Further, p is an integer of 1 to 30, preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.

The weight average molecular weight of the organopolysiloxane polymer is usually 500 to 10,000, preferably 600 to 5,000.

The viscosity of the organopolysiloxane polymer at 25 ° C. is usually 0.5 to 1,000 Pa · s, preferably 1 to 100 Pa · s.

Here, the weight average molecular weight can be determined by, for example, gel permeation chromatography analysis using toluene, THF or the like as a developing solvent, and the viscosity can be determined by, for example, a rotational viscometer (BL type, BH type, BS type, cone plate). Type etc.) (hereinafter the same).

The component (A) glycoluril ring-containing organopolysiloxane polymer includes, for example, tetraallylglycoluril represented by the following chemical formula (1) and terminal hydrogensiloxy group-capped organopolysiloxane represented by the following general formula (2): (Hereinafter referred to as the first terminal hydrogensiloxy group-blocked organopolysiloxane) can be obtained by a hydrosilylation addition reaction by a conventionally known method.

The reaction temperature is usually room temperature (25 ° C.) to 250 ° C., preferably 50 to 180 ° C. The reaction time is usually 0.1 to 120 hours, preferably 1 to 10 hours.

(In the formula, R and n are as defined above.)

The tetraallyl glycoluril and the first terminal hydrogensiloxy group-capped organopolysiloxane are the first terminal hydrogensiloxy group-capped organopolysiloxane with respect to 1 equivalent of the allyl group in the tetraallylglycoluril molecule. The reaction is carried out in such an amount that the Si—H group in the molecule is 0.1 to 0.9 equivalent, preferably 0.4 to 0.7 equivalent (allyl group excess system). As a result, an organopolysiloxane polymer having diallyl glycoluril rings at both ends (hereinafter sometimes referred to as a glycoluril ring-containing organopolysiloxane polymer) can be obtained.

In this reaction, for example, a platinum group metal compound containing platinum, rhodium, or palladium can be used as a catalyst. Of these, compounds containing platinum are preferred, such as hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol. A complex, platinum supported on activated carbon, or the like can be used.

The amount of the catalyst blended (in terms of metal mass) is preferably 0.01 to 10,000 ppm, more preferably 0.1 to 100 ppm, based on the tetraallylglycoluril (mass). preferable.

Further, in the production of the glycoluril ring-containing organopolysiloxane polymer, a solvent can be added as necessary. As the solvent, toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether and the like can be used.

Component (B) is a glycoluril ring-containing organohydrogenpolysiloxane polymer having hydrogen atoms (Si—H groups) bonded to at least two silicon atoms at the ends of the siloxane chain represented by the general formula (C4). It is.

In the composition of the present invention, a glycoluril ring-containing organohydrogenpolysiloxane polymer represented by the general formula (C4) is used as a curing agent (crosslinking agent).

As the component (B), an organohydrogenpolysiloxane (hereinafter referred to as glycoluril) having at least two hydrogen atoms (Si—H groups) bonded to a silicon atom at the end of the siloxane chain (that is, in a monofunctional siloxy unit) Ring-containing terminal hydrogen polysiloxane polymer)), and a hydrogen atom ((H) (R) bonded to the terminal silicon atom of the highly reactive siloxane chain) By having at least 2, preferably 2-50 Si—H groups in 2SiO1 / 2 unit, rapid hydrosilylation addition with alkenyl groups (allyl groups) at both ends of molecular chain in component (A) The reaction becomes possible.

In the general formula (C4), R independently of each other is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, or a propyl group, or a phenyl group, and the curing characteristics, flexibility, and ease of synthesis of the composition. In this respect, a methyl group is preferable, and 50 mol% or more (50 to 100 mol%) of all R is preferably a methyl group.

The weight average molecular weight of the organohydrogenpolysiloxane polymer as the component (B) is usually 500 to 10,000, preferably 600 to 5,000.

The viscosity of the organohydrogenpolysiloxane polymer at 25 ° C. is usually 0.1 to 100 Pa · s, preferably 0.5 to 10 Pa · s.

The glycoluril ring-containing terminal hydrogen polysiloxane polymer as the component (B) includes, for example, tetraallylglycoluril represented by the chemical formula (1) and a terminal hydrogensiloxy group-blocked organo group represented by the following general formula (3). Polysiloxane (hereinafter referred to as second terminal hydrogensiloxy group-blocked organopolysiloxane) can be obtained by hydrosilylation addition reaction by a conventionally known method. The reaction temperature is usually room temperature (25 ° C.) to 250 ° C., preferably 50 to 180 ° C. The reaction time is usually 0.1 to 120 hours, preferably 1 to 10 hours.

(In the formula, R, m and n are the same as described above. Moreover, the siloxane repeating unit may be bonded at random.)

The tetraallyl glycoluril and the second terminal hydrogensiloxy group-blocked organopolysiloxane are the same in the second terminal hydrogensiloxy group-blocked organopolysiloxane molecule with respect to 1 equivalent of the allyl group in the tetraallylglycoluril molecule. The Si—H group is reacted in an amount of 1.1 to 5.0 equivalents, preferably 1.1 to 3.5 equivalents (Si—H group excess system).

Thereby, a glycoluril ring-containing organohydrogenpolysiloxane polymer having at least two hydrogensiloxy groups at the end of the siloxane chain can be obtained.

Examples of the second terminal hydrogensiloxy-blocked organopolysiloxane include those represented by chemical formulas or general formulas (4) to (6).

The amount of the catalyst (in terms of metal mass) is preferably 0.01 to 10,000 ppm with respect to tetraallylglycoluril (mass) represented by the chemical formula (1), preferably 0.1 to 100 ppm. It is more preferable to set the ratio.

Further, in the production of the organohydrogenpolysiloxane polymer, a solvent can be added as necessary. As the solvent, toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether and the like can be used.

Examples of the organohydrogenpolysiloxane polymer obtained by the above-described method include those represented by the following general formula (7).

(In the formula, R is as defined above.)

The blending amount of the glycoluril ring-containing terminal hydrogen polysiloxane polymer as the component (B) is in the component (B) with respect to 1 mol of allyl groups in the allyl glycoluril ring-blocked organopolysiloxane polymer as the component (A). The amount of Si—H groups is 0.8 to 4.0 moles, and the “Si—H group / allyl group” ratio is preferably 1.0 to 3.0.

When the above-mentioned “Si—H group / allyl group” ratio is less than 0.8 or more than 4.0, there is a risk of poor curing or a spotted pattern on the resin surface after compression molding (compression molding). There is.

Crosslinks between the (A) component and the (B) component glycoluril ring-containing organopolysiloxane polymer provide excellent low elasticity, mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, and gas permeability. Cured product can be provided.

The organopolysiloxane polymer represented by the general formula (C3) that is the main agent (base polymer) and the organohydrogenpolysiloxane polymer represented by the general formula (C4) that is the curing agent (crosslinking agent) are a semiconductor. In order to seal the element, halogen ions such as chlorine and alkali ions such as sodium are preferably reduced as much as possible. Normally, when extracted at 120 ° C., all ions are 10 ppm or less. It is desirable.

As the curing accelerator (curing catalyst) of the component (C), a hydrosilylation addition reaction catalyst can be used, and it is preferable to use a platinum group metal catalyst such as a platinum-based catalyst or a palladium-based catalyst, iron oxide, or the like. Among these, platinum group metal catalysts are preferable, and platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts. From the viewpoint of cost and the like, platinum-based metal catalysts such as platinum, platinum black, and chloroplatinic acid are used. For example, H ₂ PtCl ₆ · xH ₂ O, K ₂ PtCl ₆ , KHPtCl ₆ · xH ₂ O, K ₂ PtCl ₄ , K ₂ PtCl ₄ · xH ₂ O, PtO ₂ · xH ₂ O (x is positive Integers) and the like, and hydrocarbons such as olefins, complexes of alcohols and vinyl group-containing organopolysiloxanes, and the like. These may be used alone or in combination of two or more. it can.

The addition amount of the curing accelerator is a catalyst amount (effective amount of curing acceleration), but the addition amount of the platinum group metal catalyst is in terms of mass of the platinum group metal with respect to the total of the component (A) and the component (B). About 0.1 to 500 ppm is preferable. In other addition ranges, there is a concern that poor curing occurs, curing is too fast, and the viscosity rises rapidly, resulting in a decrease in workability.

(D) Inorganic filler of component is not particularly limited The amount of inorganic filler such as silica of (D) component added to the thermosetting resin composition of the present invention is the allyl end of component (A) which is the main component. 30 to 900 parts by weight, preferably 40 to 40 parts by weight per 100 parts by weight in total of the glycoluril ring-blocked organopolysiloxane polymer and the glycoluril ring-containing terminal hydrogen polysiloxane polymer of component (B) as a curing agent. When 600 parts by mass is added and the resin component (the total of the components (A) and (B)) is less than 30 parts by mass, sufficient strength cannot be obtained, and when it exceeds 900 parts by mass. There is a possibility that the fluidity is lowered due to the thickening, and it becomes difficult to seal the semiconductor elements arranged on the submount due to the poor filling property.

Various additives can be further blended into the thermosetting resin composition of the present invention as necessary. For example, curing suppression of organic silicon-based adhesion improvers having epoxy groups, organic phosphorus-containing compounds such as ethynylmethyldecylcarbinol, triphenylphosphine, organic nitrogen-containing compounds such as tributylamine, tetramethylethylenediamine, and benzotriazole Additives, colorants such as various carbon blacks such as acetylene black and furnace black can be added arbitrarily as long as the effects of the present invention are not impaired.

The thermosetting resin composition of the present invention can be prepared by uniformly mixing the above components by a conventional method.

The obtained thermosetting resin composition is cured by heating, and the curing conditions are 110 to 200 ° C., particularly 120 to 180 ° C., 1 to 6 hours, particularly 2 to 3 hours. can do.

Further, although it becomes a solid state depending on the selected polysiloxane or the degree of polymerization of polysiloxane, the semiconductor can be similarly sealed by a method such as transfer molding.

The thermosetting resin composition of the present invention can provide a cured product having excellent low elasticity, mechanical properties, heat resistance, electrical insulation, chemical resistance, water resistance, gas permeability, and the like. It is a material suitable as a sealing material.

The thermosetting resin composition of the present invention can provide a semiconductor device that is suppressed in warpage and excellent in heat resistance and moisture resistance even when a semiconductor element is sealed.

In the present invention, the semiconductor device manufacturing method is not particularly limited.

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in the following example, room temperature shows 25 degreeC and a part shows a mass part.

Synthesis example 1
400 g (1.79 mol) of tetraallylglycoluril, 400 g of toluene, and 0.32 g of toluene solution of chloroplatinate (containing 0.5 mass% as platinum) were charged into a 2 L separable flask and heated to 100 ° C. 1,3,3-tetramethyldisiloxane (120 g, 0.89 mol) was added dropwise and stirred at 100 ° C. for 8 hours, and then toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid.

As a result of measuring ¹ H-NMR spectrum, it was confirmed that a part of the allyl group of tetraallylglycoluril reacted with 1,1,3,3-tetramethyldisiloxane.

Synthesis example 2
900 g (2.73 mol) of tris (dimethylhydrogensiloxy) phenylsilane and 900 g of toluene were charged into a 3 L separable flask, heated to 100 ° C., and 0.71 g of toluene chloroplatinate solution (0.5% by mass as platinum). Content) was added dropwise, and then 300 g (1.34 mol) of tetraallylglycoluril and 300 g of toluene were added dropwise. After stirring at 100 ° C. for 8 hours, toluene was distilled off under reduced pressure to obtain a colorless and transparent liquid.

According to the result of measuring ¹ H-NMR spectrum, it was confirmed that all of tetraallylglycoluril was consumed and that the allyl group of tetraallylglycoluril reacted with one Si—H group of terminal hydrogensiloxane. .

Example 1
A resin composition in which the blending ratio of the main agent and the curing agent was 1.0 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.

<1> As the main agent (Synthesis Example 1) 58.0 parts by mass <2> As a curing agent (Synthesis Example 2) 37.0 parts by mass <3> As a curing accelerator, chloroplatinic acid (octyl of chloroplatinic acid) Alcohol-modified solution (platinum concentration 2% by mass)) 0.5 part by mass <4> As inorganic filler, silica filler 157.8 parts by mass <5> Curing inhibitor (ethynylmethyldecylcarbinol) 0.5 part by mass <6> As a colorant, acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.)
3.0 parts by mass

These <1> to <6> components are stirred and mixed with a planetary mixer, kneaded three times with a three roll set to a pitch of 80 μm, and further mixed with a planetary mixer under vacuum to form a liquid. A thermosetting resin composition was obtained.

Example 2
A resin composition in which the blending ratio of the main agent and the curing agent was 1.8 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.

<1> As main agent, (Synthesis Example 1) 43.9 parts by mass <2> As a curing agent (Synthesis Example 2) 51.1 parts by mass <3> As a curing accelerator, chloroplatinic acid (octyl chloride of chloroplatinic acid) Alcohol-modified solution (platinum concentration 2% by mass)) 0.5 part by mass <4> silica filler 157.8 parts by mass <5> curing inhibitor (ethynylmethyldecylcarbinol) 0.5 part by mass <6> as a colorant , Acetylene black (Denka Black, Electrochemical Industry)
3.0 parts by mass

Example 3
A resin composition in which the mixing ratio of the main agent and the curing agent was 2.2 in terms of Si—H group / allyl group and the silica filler filling amount was 60% by mass was prepared as shown below.

<1> As main agent, (Synthesis Example 1) 39.1 parts by mass <2> As a curing agent, (Synthesis Example 2) 55.9 parts by mass <3> As a curing accelerator, chloroplatinic acid (octyl chloride of chloroplatinic acid) Alcohol-modified solution (platinum concentration 2% by mass) 0.5 part by mass <4> As an inorganic filler, silica filler 157.8 parts by mass <5> Curing inhibitor (ethynylmethyldecylcarbinol) 0.5 part by mass <6 > As a colorant, acetylene black (Denka Black, Electrochemical Industry)
3.0 parts by mass

Comparative Example 1
The main agent is vinylpolysiloxane, the curing agent is branched organohydrogenpolysiloxane, the blending ratio of the main agent and curing agent is 2.0 in the ratio of Si-H group / Si-Vi group, and the silica filler filling amount A resin composition with a high loading of 82% by mass was prepared as shown below.

<1> Vinyl group-containing linear dimethylpolysiloxane 87.2 parts by mass as main agent-1 <2> Branched organohydrogenpolysiloxane 2.8 parts by mass as curing agent-2 <3> Curing accelerator As chloroplatinic acid (octyl alcohol-modified solution of chloroplatinic acid (platinum concentration 2 mass%)) 0.5 part by mass <4> Silica filler 465.7 parts by mass <5> Curing inhibitor (ethynyl) Methyl decyl carbinol) 0.5 parts by mass <6> As a colorant, acetylene black (Denka Black, Electrochemical Industry)
3.0 parts by mass

[Test method]
Using the resin compositions obtained in Examples and Comparative Examples, evaluation tests (viscosity, DSC measurement, tensile strength) were performed by the following methods.

The test results obtained were as shown in Table 8.
(I) Viscosity Viscosity measurement at room temperature was performed with a Brookfield programmable rheometer type: DV-III ultra viscometer (cone spindle CP-51 / 1.0 rpm).

(Ii) DSC measurement The DSC measurement was performed with a model DSC821e of METTTLER.

(Iii) Tensile strength Tensile strength is obtained by molding a sample obtained by molding a cured product of a thermosetting resin composition into a 1.0 mm thick plate (150 ° C. × 2 hours heat curing) using a No. 2 dumbbell, and then AUTOGRAPH. Measurement was performed with a Loadcell type SBL-5KN (distance between grips: 100.0 mm, pulling speed: 2.0 mm / min) manufactured by Shimadzu Corporation.

As the main agent (base polymer) and curing agent (crosslinking agent), both ends of allyl glycoluril ring-blocked organopolysiloxane polymer (compound A) and glycoluril ring-containing terminal hydrogen polysiloxane polymer (compound B) are used as skeletons. The resin compositions of Examples 1 to 3 using only the resin can be obtained by changing the ratio of Si—H group / allyl group in the resin to 1.0, 1.8, and 2.2. The cured product used had good heat resistance and tensile shear adhesion.

On the other hand, in the resin composition of the comparative example, good results were not obtained in both heat resistance and tensile shear adhesive strength.

(In the formula, m is an integer of 0 to 16.)
Or general formula <C6>

(In the formula, n is 0 or 1.)
It is an isocyanurate compound represented by these.

The electron beam curable resin composition according to the present invention preferably contains a polyolefin resin and a crosslinking agent, and the crosslinking agent is represented by the general formula (C).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an allyl group.)
These are allyl glycolurils represented by the formula:

Thus, the electron beam curable resin composition according to the present invention contains a polyolefin resin and a specific crosslinking agent.

The polyolefin resin used in the practice of the present invention is a polymer of an olefin monomer, a polymer of a polar monomer, or a copolymer of an olefin monomer and a polar monomer.

Examples of the olefin monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, Α-olefin compounds having 2 to 20 carbon atoms, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene;
Cyclopentene, cycloheptene, 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl- 2-norbornene, tetracyclododecene, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-methyl-1 , 4: 5,8-Dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 1,4: 5 10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene 3 to 20 carbon atoms A cyclic olefin compound of
Aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, substituted allylnaphthalenes;
Alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, allyl norbornane;
Silane unsaturated compounds such as allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-decene;
Examples thereof include conjugated or non-conjugated diene compounds such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 1,8-nonadiene, 1,9-decadiene, norbornadiene, and dicyclopentadiene.

Examples of the polar monomer include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid, etc. Α, β-unsaturated carboxylic acids and metal salt compounds thereof such as sodium, potassium, lithium, zinc, magnesium, calcium;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid ester compounds such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate;
Unsaturated dicarboxylic acids such as maleic acid and itaconic acid;
Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate;
Examples thereof include unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

In the practice of the present invention, the polymer of olefin monomers, the polymer of polar monomers, or the copolymer of olefin monomers and polar monomers may be used alone or in combination of two or more.

Among such polyolefin resins, in particular, a homopolymer of 4-methyl-1-pentene or a copolymer with other olefin monomer containing 90 mol% or more of 4-methyl-1-pentene (polymethylpentene) Since the refractive index is 1.46, which is close to the refractive index of silica particles, it is possible to suppress the inhibition of optical properties such as reflectance even when blended, and it can be used as a reflector for semiconductor light emitting devices. It is suitable for.

However, heat resistance is not sufficient in the reflow process, and application to such applications is difficult. In response to this problem, according to the present invention, a polymethylpentene containing a cross-linking agent made of an isocyanurate compound or glycoluril is irradiated with an electron beam, thereby exhibiting sufficient heat resistance even in a reflow process. As a result, it can be used as a reflector of a semiconductor light emitting device.

The crosslinking agent used in the practice of the present invention is the isocyanurate compound represented by the general formula (C5) or the general formula (C6) and the glycoluril represented by the general formula (C).

As the isocyanurate compound represented by the general formula (C5),
Ethylene bis (diallyl isocyanurate),
Trimethylene bis (diallyl isocyanurate),
Tetramethylene bis (diallyl isocyanurate),
Pentamethylene bis (diallyl isocyanurate),
Hexamethylene bis (diallyl isocyanurate),
Heptamethylenebis (diallyl isocyanurate),
Octamethylene bis (diallyl isocyanurate),
Nonamethylene bis (diallyl isocyanurate),
Decamethylene bis (diallyl isocyanurate),
Examples include dodecamethylene bis (diallyl isocyanurate). You may use these individually or in combination of 2 or more types.

As an isocyanurate compound represented by the general formula (C6),
Examples thereof include oxydiethylene bis (diallyl isocyanurate) and 1,2-bis (3,5-diallyl isocyanurethoxy) ethane, and each may be used alone or in combination.

As the allyl glycoluril represented by the general formula (C),
1-allyl glycoluril,
1,3-diallylglycoluril,
1,4-diallylglycoluril,
1,6-diallylglycoluril,
1,3,4-triallylglycoluril,
1,3,4,6-tetraallylglycoluril,
1-allyl-3a-methylglycoluril,
1,3-diallyl-3a-methylglycoluril,
1,4-diallyl-3a-methylglycoluril,
1,6-diallyl-3a-methylglycoluril,
1,3,4-triallyl-3a-methylglycoluril,
1,3,4,6-tetraallyl-3a-methylglycoluril,
1-allyl-3a, 6a-dimethylglycoluril,
1,3-diallyl-3a, 6a-dimethylglycoluril,
1,4-diallyl-3a, 6a-dimethylglycoluril,
1,6-diallyl-3a, 6a-dimethylglycoluril,
1,3,4-triallyl-3a, 6a-dimethylglycoluril,
1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril,
1-allyl-3a, 6a-diphenylglycoluril,
1,3-diallyl-3a, 6a-diphenylglycoluril,
1,4-diallyl-3a, 6a-diphenylglycoluril,
1,6-diallyl-3a, 6a-diphenylglycoluril,
1,3,4-triallyl-3a, 6a-diphenylglycoluril,
Examples include 1,3,4,6-tetraallyl-3a, 6a-diphenylglycoluril and the like. You may use these individually or in combination of 2 or more types.

In the electron beam curable resin composition of the present invention, the amount of the crosslinking agent used is preferably 0.1 to 50 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably.

In addition, in the range which does not impair the effect of this invention, the unsaturated compound which has an allyl group, a (meth) acryloxy group, etc. can also be used together as another crosslinking agent.

Such unsaturated compounds include polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl glycidyl isocyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, tetraallyl glycoluril; ethylene glycol diacrylate, Examples include poly (meth) acryloxy compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; divinylbenzene and the like.

The electron beam curable resin composition of the present invention preferably contains a white pigment or other inorganic particles.

As the white pigment, titanium oxide, zinc sulfide, zinc oxide, barium sulfide or the like can be used alone or in combination of two or more, and titanium oxide is particularly preferable. The amount of the white pigment used is preferably 1 to 500 parts by mass and more preferably 5 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin. The average particle size of the white pigment is preferably 0.10 to 1.00 μm in the primary particle size distribution and 0.10 to 0.50 μm from the viewpoint of obtaining high reflectivity in consideration of moldability. Is more preferable. An average particle diameter can be calculated | required as mass average value D50 in the particle size distribution measurement by a laser beam diffraction method.

Other inorganic particles include spherical fused silica particles, modified cross-section glass fibers, and other glass fibers. Spherical fused silica particles and / or modified cross-section glass fibers are preferred.

The spherical fused silica particles and the modified cross-section glass fibers may be blended with ordinary thermoplastic resin compositions or thermosetting resin compositions such as epoxy resins, acrylic resins, and silicone resins, alone or in combination of two or more. Can be used.

Spherical fused silica particles are prepared, for example, through a process in which a silicon dioxide powder raw material such as silica is entrained in a powdered state with a carrier gas such as air in a flame formed in a melting zone in a furnace and injected from a burner. The In general, commercially available products can be used.

The volume average particle diameter of the spherical fused silica particles is preferably 0.1 to 500 μm, and more preferably 1 to 300 μm. The volume average particle diameter can be obtained as a mass average value D50 in particle size distribution measurement by a laser light diffraction method.

In addition, the irregular cross-section glass fiber is a fiber having a cross-sectional shape having a different major axis and minor axis, and can be reinforced almost equally in the resin flow direction (MD) and its vertical direction (TD). Excellent in preventing warping.

In the present invention, the cross-sectional shape has a minor axis (D1) of 0.5 to 25 μm, a major axis (D2) of 0.6 to 300 μm, and a ratio D2 / D1 of D2 to D1 of 1.2 to 30. Glass fibers having an average fiber length of 0.75 to 300 μm are preferable. The fiber diameter and the fiber length can be obtained by randomly extracting a predetermined amount of glass fiber from an arbitrary point of the glass fiber laminate, pulverizing the extracted fiber with a mortar or the like, and measuring with an image processing apparatus.

The content of the spherical fused silica particles and / or the modified cross-section glass fibers is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the polyolefin resin.

The electron beam curable resin composition of the present invention is prepared by blending a polyolefin resin and a crosslinking agent and, if necessary, a white pigment or other inorganic particles in the above-mentioned predetermined ratio. The electron beam curable resin composition containing a white pigment or other inorganic particles is particularly suitable for a reflector.

Moreover, various additives can be blended in the electron beam curable resin composition of the present invention as long as the effects of the present invention are not impaired. For example, various whisker, silicone powder, organic synthetic rubber, thermoplastic elastomer, fatty acid ester, zinc stearate, calcium stearate, glycerate ester, etc. Additives such as antioxidants such as isocyanurates, phenols, salicylic acids, oxalic anilides, benzoates, hindered amines, benzotriazoles, and light stabilizers such as hindered amines, benzoates Can be blended.

The electron beam curable resin composition of the present invention is a known material such as a three-roll, two-roll, homogenizer, planetary mixer, or other stirrer, polylab system, or melt kneader such as a lab plast mill. It is obtained by mixing using the means. These may be performed at normal temperature, cooling state, heating state, normal pressure, reduced pressure state, or pressurized state.

Various molded products can be molded using the electron beam curable resin composition of the present invention as a raw material, and molded products such as thinner reflectors can also be produced.

Such a molded body is prepared by using the electron beam curable resin composition of the present invention as a raw material, an injection molding process at a cylinder temperature of 200 to 400 ° C., a mold temperature of 20 to 100 ° C., and before or after the injection molding process. It is preferable to produce by the shaping | molding method including the electron beam irradiation process which performs an electron beam irradiation process. As long as the moldability is not impaired, the crosslinking reaction by electron beam irradiation can be performed before molding.

The acceleration voltage of the electron beam can be appropriately selected according to the resin used and the thickness of the layer. For example, in the case of a molded product having a thickness of about 1 mm, it is preferable to cure the uncured resin layer usually at an acceleration voltage of about 250 to 2000 kV. In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam, the electron beam transmission depth and the resin layer thickness are made equal. By appropriately selecting the acceleration voltage, it is possible to suppress the irradiation of the electron beam to the base material and to minimize the deterioration of the base material due to the excess electron beam. The absorbed dose when irradiating with an electron beam is appropriately set depending on the composition of the resin composition, but is preferably such that the crosslink density of the resin layer is saturated, preferably 10 to 400 kGy, and preferably 50 to 200 kGy. More preferably. There is no restriction | limiting in particular as an electron beam source, Various electron beam accelerators, such as a Cockloft Walton type, a resonance transformation type, an insulated core transformer type, a bande graft type, a linear type, a dynamitron type, a high frequency type, can be used.

Thus, the cured product of the electron beam curable resin composition of the present invention includes a heat-resistant insulating film, a heat-resistant release sheet, a heat-resistant transparent substrate, a solar cell light reflecting sheet, LED lighting, and a light source for TV. It can be applied to various uses such as a reflector.

Next, the reflector resin frame of the present invention will be described.

The reflector resin frame of the present invention is made of a cured product obtained by molding the above-described electron beam curable resin composition. Specifically, the resin frame for a reflector of the present invention can be produced by forming the electron beam curable resin composition of the present invention into a pellet and forming a resin frame by injection molding. The thickness of the resin frame for the reflector is preferably 0.1 to 5.0 mm, more preferably 0.1 to 2.0 mm.

By using the electron beam curable resin composition of the present invention, a thinner resin frame can be produced as compared with a resin frame using anisotropic glass fibers. Specifically, a resin frame having a thickness of 0.1 to 3.0 mm can be produced. In addition, the reflector resin frame of the present invention does not generate warp due to the inclusion of an anisotropic filler such as glass fiber even when the thickness is reduced. It is what

The resin frame for a reflector of the present invention can be made into a semiconductor light emitting device by mounting an LED element on the reflector, sealing it with a known sealing agent, and forming it into a desired shape by die bonding. In addition, the resin frame for reflectors of the present invention functions not only as a reflector but also as a package for fixing the semiconductor light emitting device.

In addition, in the resin frame for a reflector of the present invention, since spherical fused silica particles are contained, foaming due to water is suppressed in the manufacturing process of the frame as compared with the case where porous silica particles are blended. Micropores that cause defects are not formed. Therefore, in a product such as a semiconductor light-emitting element using the frame, defects due to the fine holes that have been a problem in the past are reduced, so that durability as the product can be improved.

Next, the reflector of the present invention will be described.

The reflector of the present invention is made of a cured product of the electron beam curable resin composition described above.

The reflector of the present invention may be used for a semiconductor light emitting device described later, or may be used in combination with a semiconductor light emitting device such as an LED mounting substrate made of other materials.

The reflector of the present invention mainly has a function of reflecting light from the LED element in the semiconductor light emitting device toward the lens of the light emitting part. The details of the reflector are the same as those of the reflector applied to the semiconductor light-emitting device of the present invention, and are omitted here.

In addition, in the reflector of the present invention, by containing spherical fused silica particles, compared with the case where porous silica particles are blended, in the manufacturing process of the reflector, since foaming due to water is suppressed, a defect is caused. The resulting micropores are not formed. Therefore, in a product such as a semiconductor light emitting device using the reflector, defects due to the fine holes, which has been a problem in the past, are reduced, so that the durability of the product can be improved.

Further, as described above, in the semiconductor light emitting device in which the reflector is formed using the electron beam curable resin composition containing the spherical fused silica particles, the micropores that cause defects in the reflector are not formed. Therefore, since the defects caused by the fine holes, which has been a problem in the past, are reduced, the durability as a product is improved.

Next, the semiconductor light emitting device of the present invention will be described.

The semiconductor light-emitting device of the present invention includes an optical semiconductor element such as an LED element and at least a part of which is fixed around the optical semiconductor element and reflects light from the optical semiconductor element in a predetermined direction. A reflector formed of a cured product of the resin composition is provided on the substrate.

In the case of a white light LED, an optical semiconductor element is an n-type hexahedron having an active layer made of AlGaAs, AlGaInP, GaP, GaN, or the like that emits UV or blue radiant light. And a semiconductor chip (light-emitting body) having a double hetero structure sandwiched between p-type cladding layers, and in the case of a wire bonding mounting method, is connected to an electrode as a connection terminal via a lead wire.

The shape of the reflector conforms to the shape of the joint portion of the lens, and there are a circular shape, a rectangular shape, an elliptical shape, or a cylindrical shape, but it is generally a cylindrical shape (annular shape) and all end faces of the reflector. Is in contact with and fixed to the surface of the substrate.

Note that the inner surface of the reflector may be tapered upward to improve the directivity of light from the optical semiconductor element. Further, the reflector can also function as a lens holder when the end portion on the lens side is processed into a shape corresponding to the shape of the lens.

In the reflector, only the light reflection surface side may be a light reflection layer made of a cured product of the electron beam curable resin composition of the present invention. In this case, the thickness of the light reflection layer is 500 μm from the viewpoint of reducing thermal resistance and the like. It is preferable to set it as follows, and it is more preferable to set it as 300 micrometers or less. In addition, the member in which a light reflection layer is formed can be comprised with well-known heat resistant resin.

As described above, a lens is provided on the reflector, but this is usually made of resin, and various structures and colors are adopted depending on the purpose and application.

The space formed by the substrate, the reflector, and the lens may be a gap or a transparent sealing part, but is generally a transparent sealing part filled with a material that provides translucency and insulation. In wire bonding mounting, the lead wire may be short-circuited from the connection portion with the optical semiconductor element and / or the connection portion with the electrode due to pressure caused by direct contact with the lead wire and indirectly applied vibration, impact, etc. Therefore, it is possible to reduce electrical problems caused by disconnection or cutting. Furthermore, the optical semiconductor element can be protected from dust, moisture, etc., and reliability can be maintained over a long period of time.

As the transparent sealing agent used for this material, there are usually epoxy resin, silicone resin, epoxy silicone resin, acrylic resin, polyimide resin, polycarbonate resin and the like. Of these, silicone resins are preferred from the viewpoints of discoloration resistance, heat resistance, weather resistance, and low shrinkage.

<Preparation of electron beam curable resin composition>
2 parts by mass of the isocyanurate compound or glycoluril shown in Table 9 as the cross-linking agent, 100 parts by mass of polymethylpentene resin (trade name: TPX RT18, molecular weight MW 500,000 to 600,000) manufactured by Mitsui Chemicals, Inc. as the resin, inorganic 60 parts by mass of irregularly shaped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG3PA-820) as particles, 45 parts by mass of titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd .: PF-691) as a white pigment, and silane coupling agent (Shin-Etsu Chemical) as an additive Company: KBM-303) 1.5 parts by mass, antioxidant (BASF: IRGANOX1010) 1 part by mass, processing stabilizer (IRGAFOS168) 0.5 part by mass and mold release agent (manufactured by Sakai Chemical Industry Co., Ltd .: SZ -2000) An electron beam curable resin composition containing 0.5 part by mass is 750 mm under the condition of 250 ° C./30 seconds / 20 MPa. A molded body was formed by press-molding to × 750 mm × thickness 0.2 mm. The compact was irradiated with an electron beam at an acceleration voltage of 250 kV and an absorbed dose of 100 kGy, and this was used as a test piece.

<Long-term heat test>
With respect to the test piece obtained by the above operation, first, the reflectance of the initial light in the wavelength range of 230 to 780 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-2550). Subsequently, after the test piece was allowed to stand at 150 ° C./500 hours, the light reflectance was measured by the same method as described above. Table 9 shows the test results with light having a wavelength of 450 nm.

<Reflow heat resistance test>
The test piece obtained by the above operation was first passed through a small nitrogen atmosphere reflow apparatus (Matsushita Electric Works: RN-S) set so that the maximum temperature was maintained at 260 ° C./10 seconds. The rate of change (the sum of the rate of change in the horizontal and vertical directions) was measured. The test results obtained are shown in Table 9.

According to the test results shown in Table 9, it is recognized that the electron beam curable resin composition of the present invention is excellent in long-term heat resistance and the shape change due to reflow heating is significantly reduced. Therefore, the electron beam curable resin composition of the present invention is useful as a reflector or a reflective material for a semiconductor light emitting device.

(6) Silicone resin composition The silicone resin composition according to the present invention comprises:
(A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
Component (D): General formula (C)

(In the formula, R ¹ and R ² each independently represents a hydrogen atom, a lower alkyl group or a phenyl group, a R ^3, R ⁴ and R ⁵ independently represent hydrogen atom or an allyl group.)
And allyl glycoluril represented by
The component (D) is contained in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B).

The component (A) used in the practice of the present invention is not particularly limited as long as it is an organopolysiloxane having at least two alkenyl groups bonded to silicon atoms in one molecule and having a polysiloxane structure as a main chain.

(A) A component is the main ingredient (base polymer) of the silicone resin composition of this invention. In view of excellent toughness and elongation, the component (A) preferably has 2 or more alkenyl groups bonded to a silicon atom in one molecule, more preferably 2 to 20, more preferably 2 to 10 More preferably, it has.

The component (A) may be a polysiloxane having one vinyl group and / or hydrosilyl group in one molecule from the viewpoint that the viscosity of the composition is low.

The alkenyl group can be bonded to a silicon atom via an organic group. The organic group is not particularly limited, and can have, for example, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.

Examples of the alkenyl group include an unsaturated hydrocarbon group having 2 to 8 carbon atoms such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group; and a (meth) acryloyl group. Among these, from the viewpoint of excellent curability, a vinyl group or a (meth) acryloyl group is preferable, and a vinyl group is more preferable.

In the present invention, the (meth) acryloyl group means one or both of an acryloyl group and a methacryloyl group.

Examples of the bonding position of the alkenyl group include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane. The alkenyl group can be bonded to one end or both ends of the polysiloxane molecular chain.

Examples of the organic group bonded to the silicon atom other than the alkenyl group include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; phenyl group, tolyl group, xylyl group, Aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group and 3,3,3-trifluoropropyl group, cyclopentyl group, cyclohexyl group and the like And the like. Of these, a methyl group and a phenyl group are preferable from the viewpoint of excellent heat resistance.

Further, the polysiloxane as the component (A) may have a hydrosilyl group.

(A) As the main chain of the component (A), for example, organopolysiloxane can be mentioned. Specific examples include polydimethylsiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane. Of these, polydimethylsiloxane is preferred from the viewpoint of excellent heat resistance and light resistance. In addition, in this invention, light resistance means durability (for example, discoloration and a burning hardly occur) with respect to the light emission from LED.

(A) Component is not particularly limited in terms of molecular structure. Examples thereof include a straight chain, a partially branched straight chain, a ring, a branched chain, and a three-dimensional network. One preferred embodiment is linear.

(A) The component (A) is mentioned as one of the preferred embodiments in which the main chain is composed of repeating diorganosiloxane units.

When the vinyl group-containing polysiloxane and / or the hydrosilyl group-containing polysiloxane is used as the component (A), the structure of the component (A) may have an alkylene group and / or a phenylene skeleton.

Further, the molecular terminal of the component (A) can be terminated with a silanol group (silicon atom-bonded hydroxyl group) or an alkoxysilyl group, or can be blocked with a triorganosiloxy group such as a trimethylsiloxy group or a vinyl group.

(A) As a component, what is shown by following General formula (1) is mentioned, for example.

(In the formula, R ¹ , R ² and R ³ each independently represent an alkenyl group, R ⁴ independently represents a monovalent hydrocarbon group other than an alkenyl group, a hydroxy group or an alkoxy group, and each R represents an independent group. A + b + n represents an integer of 2 or more, a and b each independently represent an integer of 0 to 3, and m and n each independently represents an integer of 0 or more.)
When the polysiloxane is a polysiloxane having an unsaturated hydrocarbon group as an alkenyl group, the curability is excellent.

Examples of the polysiloxane having an unsaturated hydrocarbon group as an alkenyl group include a siloxane unit represented by the formula: (R ¹ ) ₃ SiO _1/2 and a formula: (R ¹ ) ₂ R ² SiO _1/2. An organosiloxane copolymer comprising a siloxane unit represented by formula: (R ¹ ) ₂ SiO _2/2 and a siloxane unit represented by formula: SiO _4/2 , formula: (R ¹ ) ₃ SiO _An organosiloxane copolymer comprising a siloxane unit represented by _1/2 and a siloxane unit represented by the formula: (R ¹ ) ₂ R ² SiO _1/2 and a siloxane unit represented by the formula: SiO _4/2 ; siloxane units of the formula ^{_{^{_{R 1) 2 R 2 SiO 1/2}}}} : ( siloxane units of the formula _R 1) _{2 SiO _2/2:} with _{SiO 4/2} Organosiloxane copolymers consisting of siloxane units of the ^formula: siloxane units of the formula _{^{_{(R 1) 2 R 2 SiO}}} 1/2: siloxane units or of the formula represented by R _{1 SiO ^3/2:} R 2 _SiO _An organosiloxane copolymer composed of siloxane units represented by _3/2 is exemplified.

When the polysiloxane is a polysiloxane having an unsaturated hydrocarbon group as an alkenyl group, the polysiloxane structure may have an alkylene group and / or a phenylene skeleton.

Here, R ¹ in the above formula is a monovalent hydrocarbon group other than an alkenyl group. Examples of the monovalent hydrocarbon group other than the alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Aryl groups such as a group; aralkyl groups such as a benzyl group and a phenethyl group; and halogenated alkyl groups such as a chloromethyl group, a 3-chloropropyl group, and a 3,3,3-trifluoropropyl group.

Also, R ² in the formula is an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.

When the component (A) has a vinyl group as an alkenyl group, it is excellent in curability. The polysiloxane having a vinyl group as an alkenyl group may be hereinafter referred to as “vinyl group-containing polysiloxane”.

When the component (A) is a polysiloxane having a (meth) acryloyl group as an alkenyl group, it is excellent in curability. The polysiloxane having a (meth) acryloyl group as an alkenyl group may be hereinafter referred to as “(meth) acryloyl group-containing polysiloxane”.

Examples of the (meth) acryloyl group-containing polysiloxane include those represented by the following average composition formula (2).

(Wherein R ¹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms or an aryl group, and R ² is represented by CH ₂ ═CR ³ —CO—O— (CH ₂ ) _c —. that _{^{.CH 2 = CR 3 -CO-O-}} (CH 2) c- R 3 medium representing the (meth) acryloxy group is a hydrogen atom or a methyl group, c is an integer of 2-6, More preferably, it is 2, 3 or 4. a is from 0.8 to 2.4, more preferably from 1 to 1.8, b is from 0.1 to 1.2, and More preferably, it is 2 to 1, more preferably 0.4 to 1. a + b is 2 to 2.5, and more preferably 2 to 2.2.

In the formula, examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples of the aryl group for R ¹ include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Of these, a methyl group, an ethyl group, a propyl group, and a phenyl group are preferable, and a methyl group is more preferable.

The molecular weight (weight average molecular weight) of component (A) is preferably 500 to 100,000, and preferably 1,000 to 100,000 from the viewpoint of excellent curability, toughness, elongation and workability. Is more preferably 5,000 to 50,000. In addition, in this-application specification, a weight average molecular weight is a polystyrene conversion value by GCP (gel permeation column chromatography).

The viscosity of component (A) at 23 ° C. is preferably 5 to 10,000 mPa · s because the physical properties of the resulting silicone resin are good and the handling workability of the silicone resin composition is good. More preferably, it is ˜1,000 mPa · s. In the present invention, the viscosity is measured with an E-type viscometer at 23 ° C.

(A) A component can be used individually or in combination of 2 or more types. Component (A) is not particularly limited with respect to its preparation method, and conventionally known components can be used.

Component (B) used in the practice of the present invention is an organohydrogenpolysiloxane having at least two hydrogen groups bonded to silicon atoms (that is, SiH groups) in one molecule and having a polysiloxane structure as the main chain. If it is, it will not be restrict | limited in particular.

The component (B) preferably has 2 to 300 hydrogen groups bonded to silicon atoms in one molecule, and more preferably 3 to 150 hydrogen groups. Examples of the molecular structure of the component (B) include linear, branched, cyclic, and three-dimensional network structures.

In the component (B), examples of the bonding position of the hydrogen group bonded to the silicon atom include one or both of the molecular chain terminal and the molecular chain side chain of polysiloxane. Further, the hydrogen group bonded to the silicon atom can be bonded to one end or both ends of the molecular chain of the polysiloxane.

Examples of the component (B) include organohydrogenpolysiloxanes represented by the following average composition formula (3).

(Wherein R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond. A and b are 0 <a <2, 0.8 ≦ b ≦ 2 and 0 .8 <a + b ≦ 3, a number satisfying 0.05 ≦ a ≦ 1, 0.9 ≦ b ≦ 2, and 1.0 ≦ a + b ≦ 2.7 is more preferable. (The number of silicon atoms is 2 to 300, more preferably 3 to 200.)

In the formula, examples of the unsubstituted or substituted monovalent hydrocarbon group R ³ not containing an aliphatic unsaturated bond include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Alkyl group; aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl group such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. And halogenated alkyl groups.

Among these, from the viewpoint of excellent heat resistance and light resistance, a lower alkyl group having 1 to 3 carbon atoms such as a methyl group, a phenyl group, or a 3,3,3-trifluoropropyl group is preferable.

As the component (B), for example, molecular chain both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-capped methyl Hydrogen polysiloxane, Silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Molecular chain both ends dimethylhydrogensiloxy group-blocked methylhydrogen polysiloxane with both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane ^copolymers; _(R 3) or 2 _{HSiO 1/2} units and _{SiO 4/2} units It optionally ^(R _{₃₎ 3} _{SiO 1/2} ^units, _(R 3) _{2 SiO 2/2} ^units, R 3 _{HSiO 2/2} units, _{(H) SiO 3/2} units or ^R 3 _{SiO 3/2} units In which R ³ is the same as the above-described unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, and the like. Examples thereof include those in which part or all of the groups are substituted with other alkyl groups such as ethyl group and propyl group, phenyl groups and hydrosilyl groups.

In addition, examples of the component (B) include those represented by the following general formulas (4) to (7).

(In the formula, each R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group not containing an aliphatic unsaturated bond, c represents 0 or an integer of 1 or more, and d represents an integer of 1 or more. .)
(B) A component can be used individually or in combination of 2 or more types.

Component (B) can be prepared by a conventionally known method. Specifically, for example, the following chemical formulas: R ³ SiHCl ₂ and (R ³ ) ₂ SiHCl (wherein R ³ is the same as the unsubstituted or substituted monovalent hydrocarbon group not containing the aliphatic unsaturated bond). . present) cohydrolysis of at least one chlorosilane selected from, or the chlorosilanes with the following chemical ^formula: _(R 3) 3 SiCl and ^(R ₃₎ ₂ SiCl 2 ⁽ⁱⁿ the formula, ^{R 3} is an aliphatic said non It is the same as an unsubstituted or substituted monovalent hydrocarbon group that does not contain a saturated bond.) And can be obtained by cohydrolyzing at least one chlorosilane selected from the group.

Moreover, what equilibrated polysiloxane obtained by cohydrolysis can be used as (B) component.

From the viewpoint that the amount of component (B) used is excellent in rubber physical properties (toughness, elongation) after curing, hydrogen bonded to silicon atoms of component (B) per mole of alkenyl group in component (A) The mixing ratio of atoms (SiH groups) is preferably 0.1 to 5 mol, more preferably 0.5 to 2.5 mol, and more preferably 1.0 to 2.0 mol More preferably.

When the amount of SiH group is 0.1 mol or more, a rubber cured product (silicone resin) that is sufficiently cured and strong can be obtained. When the amount of SiH groups is 5 mol or less, the cured product does not become brittle and a strong rubber cured product can be obtained.

In the present invention, the component (A) and the component (B) can be used as a mixture of the component (A) and the component (B).

The component (C) used in the practice of the present invention promotes the addition reaction between the alkenyl group of the component (A) and the hydrogen atom (that is, SiH group) bonded to the silicon atom of the component (B). It is a reaction catalyst. The silicone resin composition of this invention can be made into the composition excellent in sclerosis | hardenability by including (C) component.

The component (C) is not particularly limited, and conventionally known components can be used. For example, platinum group metals such as platinum (including platinum black), rhodium, palladium, etc .; H ₂ PtCl ₄ · nH ₂ O, H ₂ PtCl ₆ · nH ₂ O, NaHPtCl ₆ · nH ₂ O, KHPtCl ₆ · nH ₂ O, Na ₂ PtCl ₆ · nH ₂ O, K ₂ PtCl ₄ · nH ₂ O, PtCl ₄ · nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · nH ₂ O (where n is an integer of 0 to 6) And preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972); Complex with olefin (see U.S. Pat. Nos. 3,159,601, 3,159,662, and 3,775,452); platinum such as platinum black and palladium Metal supported on a support such as alumina, silica, carbon, etc .; rhodium-olefin complex; chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst); platinum chloride, chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane In particular, a platinum group metal catalyst such as a complex with a vinyl group-containing cyclic siloxane may be mentioned.

The amount of the component (C) used is a blending ratio of 0.1 to 500 ppm in terms of the mass of the platinum group metal with respect to the total amount of the components (A) and (B) from the viewpoint of achieving excellent curability. The blending ratio is preferably 10 to 100 ppm.

The component (D) used in the practice of the present invention is allyl glycoluril represented by the general formula (C). In particular,
1-allyl glycoluril,
1,3-diallylglycoluril,
1,4-diallylglycoluril,
1,6-diallylglycoluril,
1,3,4-triallylglycoluril,
1,3,4,6-tetraallylglycoluril,
1-allyl-3a-methyl-glycoluril,
1,3-diallyl-3a-methyl-glycoluril,
1,4-diallyl-3a-methyl-glycoluril,
1,6-diallyl-3a-methyl-glycoluril,
1,3,4-triallyl-3a-methyl-glycoluril,
1,3,4,6-tetraallyl-3a-methyl-glycoluril,
1-allyl-3a, 6a-dimethyl-glycoluril,
1,3-diallyl-3a, 6a-dimethyl-glycoluril,
1,4-diallyl-3a, 6a-dimethyl-glycoluril,
1,6-diallyl-3a, 6a-dimethyl-glycoluril,
1,3,4-triallyl-3a, 6a-dimethyl-glycoluril,
1,3,4,6-tetraallyl-3a, 6a-dimethyl-glycoluril,
1-allyl-3a, 6a-diphenyl-glycoluril,
1,3-diallyl-3a, 6a-diphenyl-glycoluril,
1,4-diallyl-3a, 6a-diphenyl-glycoluril,
1,6-diallyl-3a, 6a-diphenyl-glycoluril,
1,3,4-triallyl-3a, 6a-diphenyl-glycoluril,
1,3,4,6-tetraallyl-3a, 6a-diphenyl-glycoluril and the like.

In the silicone resin composition of the present invention, the component (D) is blended in an amount of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B), so that the cured product has resistance to sulfur. Can be granted. Thereby, discoloration (corrosion) of silver can be prevented and the transparency of the cured product can be maintained.

Further, the cured product obtained by using the silicone resin composition of the present invention is excellent in sulfidation resistance even if the resin is not hardened, so that it can be made into a silicone resin which is not easily cracked. For this reason, when hardened | cured material is used as an optical semiconductor element sealing body, disconnection of the wire contained in this sealing body can be prevented.

In the silicone resin composition according to the present invention, the amount of the component (D) used is the amount of the component (A) and the component (B) from the viewpoint of suppressing coloring by heat and exhibiting transparency and sulfidation resistance. The blending ratio is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total. When the component (D) is less than 0.1 parts by mass with respect to 100 parts by mass in total of the components (A) and (B), there is a possibility that the sulfidation resistance is not sufficiently exhibited. Moreover, when it exceeds 10 mass parts, it will become easy to produce coloring by a heat | fever and there exists a possibility that transparency may fall.

(D) component can be used individually or in combination of 2 or more types.

Furthermore, in addition to the above components, an additive may be used in combination with the silicone resin composition of the present invention within a range not impairing the effects of the present invention.

Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property imparting agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, physical property modifiers, adhesion imparting agents, adhesion assistants, and the like, and known ones can be used.

Examples of the adhesion-imparting agent or adhesion assistant include known epoxy silane coupling agents, bis (alkoxy) alkanes, isocyanurate derivatives, and the like, and bis (alkoxy) alkanes and / or isocyanurate derivatives are preferred.

Examples of the bis (alkoxy) alkane include 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8- It is preferably at least one selected from the group consisting of bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane. More preferred is 6-bis (trimethoxysilyl) hexane.

The method for preparing the silicone resin composition of the present invention is not particularly limited. For example, the component (A), the component (B), the component (C), the component (D), and an additive that can be used as necessary. And can be prepared by mixing. Moreover, the silicone resin composition of this invention can be made into 1 liquid type or 2 liquid type.

When the silicone resin composition of the present invention is a two-component type, it is divided into a first liquid containing the component (B) and the component (C) and a second liquid containing the component (A) and the component (D). Can be prepared. The additive can be added to one or both of the first liquid and the second liquid.

The silicone resin composition of the present invention is prepared at a temperature of 23 ° C. for 24 hours after mixing the liquid containing the component other than the component (B) with the component (B) from the viewpoint that the length of the pot life is appropriate. The subsequent viscosity is preferably 5 to 10,000 mPa · s, and more preferably 5 to 5,000 mPa · s.

In addition, the silicone resin composition of the present invention is mixed and placed under a condition of 23 ° C., and the viscosity measurement performed on the composition 24 hours after mixing is performed using an E-type viscometer at 23 ° C. and a humidity of 55%. It is done under conditions.

Examples of the method of using the silicone resin composition of the present invention include applying the composition of the present invention to a substrate (for example, an optical semiconductor element) and curing the composition.

The method for applying and curing the silicone resin composition of the present invention is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, injection molding and the like.

The silicone resin composition of the present invention can be cured by heating. The heating temperature for curing the silicone resin composition of the present invention by heating is usually 100 ° C. or higher, and is preferably 120 ° C. or higher, and preferably 120 to 200 ° C. from the viewpoint of being excellent in curability. More preferably, it is 120 to 180 ° C.

The use of the silicone resin composition of the present invention is not particularly limited. For example, the sealing material composition for electronic materials, the sealing material composition for buildings, the sealing material composition for motor vehicles, the adhesive composition, etc. are mentioned.

Electronic materials include, for example, lead frames, wired tape carriers, wiring boards, glass, silicon wafers and other supporting members; optical semiconductor elements; active elements such as semiconductor chips, transistors, diodes, thyristors; capacitors, resistors, Examples include passive elements such as coils.

The silicone resin composition of the present invention is used in applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. be able to.

The silicone resin composition of the present invention can be substantially free of a silicon compound having a silanol group from the viewpoint of storage stability.

Further, the silicone resin composition of the present invention can be used in the presence of silver. By producing the silicone resin by curing the silicone resin composition in the presence of silver, silver discoloration (corrosion) can be prevented, and the transparency of the resulting silicone resin can be maintained.

Next, the silicone resin will be described.

The silicone resin of the present invention can be obtained by curing the silicone resin composition. By using the silicone resin composition of the present invention, for example, a silicone resin having excellent sulfidation resistance can be obtained.

The silicone resin of the present invention can be obtained by curing the silicone resin composition by heating.

When the silicone resin composition is cured by heating, it has excellent curability, the curing time and pot life can be set to appropriate lengths, suppress foaming, suppress cracks in the silicone resin, and smooth the silicone resin. From the viewpoint of excellent moldability and physical properties, a method of curing the silicone resin composition at 120 to 180 ° C. (preferably 150 ° C.) within 20 hours (preferably 12 hours) is preferable.

The silicone resin of the present invention can be used as a sealing material for LED chips. The LED chip is not particularly limited with respect to its emission color. For example, blue, red, yellow, green, and white are mentioned. The LED chips can be used alone or in combination of two or more.

Next, the sealed optical semiconductor element will be described.

In the sealed optical semiconductor element of the present invention, the LED chip is sealed with the silicone resin.

The silicone resin used for the sealed optical semiconductor element of the present invention is not particularly limited as long as it is the silicone resin of the present invention.

The sealed optical semiconductor element of the present invention exhibits excellent performance in sulfidation resistance, rubber elasticity and flexibility by using the silicone resin composition.

Further, the LED chip used in the sealed optical semiconductor element of the present invention is not particularly limited with respect to the emission color. For example, a blue LED chip can be coated with a silicone resin composition of the present invention containing a fluorescent material such as yttrium, aluminum, and garnet to form a white LED.

When the red, green and blue LED chips are used and the emission color is white, for example, each LED chip is sealed with the silicone resin composition of the present invention, and the LED chips of these three colors are sealed. The body can be used. Further, the LED chips of three colors can be combined and sealed with the silicone resin composition of the present invention to form one light source.

The size and shape of the LED chip are not particularly limited.

The type of the LED chip is not particularly limited, and examples thereof include a high power LED, a high luminance LED, a general luminance LED, a white LED, and a blue LED.

Examples of the optical semiconductor element used for the sealed optical semiconductor element of the present invention include, in addition to LEDs, organic electroluminescent elements (organic EL), laser diodes, and LED arrays.

As the optical semiconductor element, for example, an optical semiconductor element bonded to a substrate such as a lead frame by die bonding and connected to the substrate or the like by chip bonding, wire bonding, wireless bonding, or the like can be used. .

The cured product used for the sealed optical semiconductor element of the present invention only needs to seal the optical semiconductor element. As the optical semiconductor element sealing body of the present invention, for example, when the cured product directly seals the optical semiconductor element, when it is a shell type, when it is a surface mounting type, a plurality of optical semiconductor element sealing bodies The case where it fills between is mentioned.

The sealed optical semiconductor element of the present invention includes a coating step of coating the LED chip with the silicone resin composition of the present invention, and curing the silicone resin composition by heating the LED chip coated with the silicone resin composition. It can be manufactured by a curing step.

In the coating step, the coating method is not particularly limited, and examples thereof include potting, transfer molding, injection molding, and screen printing.

In the curing step, the LED chip coated with the silicone resin composition can be heated to cure the silicone resin composition to obtain a cured product. Here, the temperature which heats the said silicone resin composition is the same as the conditions shown at the process of manufacturing the said silicone resin.

The production of the sealed optical semiconductor element of the present invention is not particularly limited except that the silicone resin of the present invention is used as the silicone resin. For example, a conventionally well-known thing is mentioned. In addition, the heating temperature at the time of producing the sealed optical semiconductor element of the present invention is the same as the heating temperature at the time of curing the silicone resin composition of the present invention, so that excellent curability can be exhibited. To preferred.

Applications of the sealed optical semiconductor element of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, stage lighting fixtures, displays, signals, and projectors. Etc., but is not particularly limited.

Examples Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the raw material used by the Example and the comparative example is as follows.

Component (A): Both end vinyl-blocked dimethylpolysiloxane (“DMS-V31” manufactured by Gelest, hereinafter abbreviated as (A))
Component (B): Hydrogen polysiloxane (“KF-9901” manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter abbreviated as (B))
Component (C): Platinum-cyclovinylmethylsiloxane complex (“SIP6832.2” manufactured by Gelest, hereinafter abbreviated as (C))
Component (D): 1,3,4,6-tetraallylglycoluril (“TA-G” manufactured by Shikoku Kasei Kogyo Co., Ltd., hereinafter abbreviated as (D))

The evaluation test methods employed in the examples and comparative examples are as follows.

[Transmissivity test]
The obtained silicone resin composition was sandwiched between glass plates (length 10 cm, width 10 cm, thickness 4 mm), and cured at 150 ° C. for 12 hours so as to obtain a cured product having a thickness of 2 mm. About the obtained initial cured product and the cured product after the heat resistance test obtained by further heating the initial cured product at 150 ° C. for 10 days, an ultraviolet / visible absorption spectrum measuring apparatus (Shimadzu Corporation) in accordance with JIS K0115: 2004 And the transmittance at a wavelength of 400 nm was measured.

Further, the transmittance retention was calculated from the obtained transmittance according to the following formula.

Transmittance retention rate (%) = (transmittance of cured product after heat test) / (transmittance of initial cured product) × 100
[Heat resistant coloring stability test]
The obtained silicone resin composition was sandwiched between glass plates (length 10 cm, width 10 cm, thickness 4 mm), and cured at 150 ° C. for 4 hours so as to obtain a cured product having a thickness of 2 mm. The obtained initial cured product and the cured product after the heat resistance test obtained by further heating the initial cured product at 150 ° C. for 10 days are visually observed, and the cured product after the heat test is compared with the initial cured product. It was evaluated whether it turned yellow.

[Sulfuration resistance test]
A silicone resin composition was applied on silver plating so as to have a thickness of about 1 mm, and then heated and cured at 150 ° C. for 3 hours to prepare a test piece.

Subsequently, 10 g of iron sulfide pulverized in a powder form (large excess with respect to 0.5 mmol of hydrochloric acid) is placed on the bottom of a 10 L desiccator, and a plate (through-hole) is provided above the iron sulfide so as not to contact the iron sulfide. Was mounted in a desiccator, and a test piece was placed on the eye plate. Then, 0.25 mmol of hydrogen sulfide (theoretical value of concentration: 560 ppm) was generated by dropping 0.5 mmol of hydrochloric acid into iron sulfide. (Reaction formula: FeS + 2HCl → FeCl ₂ + H ₂ S)

The color change of the silver of the test piece 24 hours after the start of hydrogen sulfide generation was visually confirmed and evaluated according to the following evaluation criteria.
○: Discoloration was not confirmed.
X: Discoloration was confirmed.

[Adhesion test]
The obtained silicone resin composition was poured into an LED package and cured by heating at 150 ° C. for 3 hours to obtain an evaluation sample.

Next, with respect to the obtained sample for evaluation, the cured product was rubbed with a spatula, and the adhesion was evaluated according to the following evaluation criteria.
○: The cured product was not easily peeled off.
X: Hardened | cured material peeled easily.
Examples 1 to 3 and Comparative Example 1

Each raw material was uniformly mixed using a vacuum stirrer so that the blending ratio shown in Table 10 was obtained, to prepare a silicone resin composition.

When the obtained silicone resin composition was subjected to a transmittance test, a heat resistant color stability test, a sulfidation resistance test and an adhesion test, the test results obtained were as shown in Table 10.

According to the test results shown in Table 10, a cured product having excellent sulfidation resistance and transparency can be obtained by using the silicone resin composition of the present invention. Moreover, the hardened | cured material excellent in adhesiveness can be obtained.

Claims

General formula (Z)

(In the formula, group Z represents a carboxyalkyl group, a glycidyl group or an allyl group; R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group; and R 3 , R 4 and R 5 represent each Independently represents a hydrogen atom or the same group as the group Z. provided that when the group Z is a carboxyalkyl group, R 3 , R 4 and R 5 represent the same carboxyalkyl group as the group Z; In some instances, R 5 represents a hydrogen atom.)
Glycolurils represented by
Formula (A)

(Wherein, n represents 0 or 1, indicating each R 1 and R 2 are independently a hydrogen atom, a lower alkyl group or a phenyl group.)
1,3,4,6-tetrakis (carboxyalkyl) glycoluril represented by the formula:
3. An epoxy resin composition comprising the crosslinking agent comprising 1,3,4,6-tetrakis (carboxyalkyl) glycoluril according to claim 2 and a curing agent comprising amines.
(A) a polyester resin obtained by a polycondensation reaction between the 1,3,4,6-tetrakis (carboxyalkyl) glycoluril according to claim 2 and a glycol;
(B) A polyester resin composition for powder coatings comprising a β-hydroxyalkylamide curing agent.
General formula (B)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or a glycidyl group.)
The glycidyl glycoluril represented by these.
An epoxy resin composition comprising the glycidyl glycoluril according to claim 5 as a crosslinking agent.
An epoxy resin composition comprising an epoxy resin, wherein at least one component in the epoxy resin is the glycidyl glycoluril according to claim 5.
The epoxy resin composition according to claim 7, comprising at least one component selected from a glass filler, a curing agent, a curing accelerator, a curing catalyst, a polyester resin, an organosiloxane, rubber particles, and an additive.
A thermosetting resin composition comprising the glycidyl glycoluril according to claim 5 and a phenol resin as components.
(A) the glycidyl glycoluril according to claim 5,
(B) An alkali development type photocurable / thermosetting resin composition comprising a photosensitive prepolymer having two or more unsaturated double bonds in one molecule and (c) a photopolymerization initiator.
Furthermore, the alkali development type photocurable / thermosetting resin composition according to claim 10, further comprising an epoxy compound or an epoxy resin excluding the glycidyl glycoluril according to claim 5.
The alkali development type photocurable / thermosetting resin composition according to claim 10 or 11, comprising a diluent, a polybutadiene compound and a polyurethane compound.
General formula (C0)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 and R 4 each independently represent a hydrogen atom or an allyl group.)
Allyl glycoluril represented by
General formula (C)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or an allyl group.)
An olefin-based resin composition comprising an allyl glycoluril represented by formula (II) and an olefin-based polymer.
(A) an organic compound having an alkenyl group,
(B) A curable composition comprising a compound having at least three or more hydrosilyl groups in one molecule and (C) a hydrosilylation catalyst,
As said (A) component, general formula (C1)

(In the formula, X represents a hydrogen atom, a lower alkyl group or an aryl group.)
The curable composition which uses tetraallyl glycoluril represented by these as an essential component.
(B) component is (B-1) an organic compound having at least two alkenyl groups, and (B-2) a linear and / or cyclic organohydrogensiloxane having at least two hydrosilyl groups in one molecule. The curable composition according to claim 15, which is (B-3) an organically modified silicone compound obtained by hydrosilylation reaction.
The component (B-1) is polybutadiene, vinylcyclohexane, cyclopentadiene, divinylbiphenyl, bisphenol A diarylate, trivinylcyclohexane, triallyl isocyanurate, methyldiallyl isocyanurate, and general formula (C2)

(Wherein R 1 , R 2 , R 3 and R 4 are all organic groups, at least two of which are alkenyl groups, and X represents a hydrogen atom, a lower alkyl group or an aryl group.)
The curable composition according to claim 16, which is at least one compound selected from the group consisting of glycolurils represented by:
The curable composition according to claim 16, wherein the component (B-1) is a glycoluril represented by the general formula (C2).
The curable composition according to claim 16, wherein the component (B-1) is a tetraallylglycoluril represented by the general formula (C1).
The curable composition according to claim 16, wherein the component (B-2) is a cyclic and / or chain polyorganosiloxane having at least two hydrosilyl groups in one molecule.
The curable composition according to claim 16, wherein the component (B-2) is a cyclic polyorganosiloxane having at least two hydrosilyl groups in one molecule.
A cured product obtained by curing the curable composition according to any one of claims 15 to 21.
(A) General formula (C3) as alkenyl group-containing organopolysiloxane

(In the formula, each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, and p is an integer of 1 to 30.)
An organopolysiloxane polymer represented by:
(B) As organohydrogenpolysiloxane, general formula (C4)

(In the formula, each R independently represents an alkyl group or a phenyl group, n is an integer of 1 to 50, m is an integer of 0 to 5, and each siloxane repeating unit in the formula is bonded randomly. May be.)
A glycoluril ring-containing organohydrogenpolysiloxane polymer represented by:
(C) A thermosetting resin composition containing a curing accelerator.
The thermosetting resin composition according to claim 23, further comprising (D) an inorganic filler.
The thermosetting resin composition according to claim 23 or 24, wherein the Si-H group in the component (B) is 0.8 to 4.0 mol with respect to 1 mol of the allyl group in the component (A).
A polyolefin resin and a crosslinking agent are contained, and the crosslinking agent is represented by the general formula (C5)

(In the formula, m is an integer of 0 to 16.)
Or general formula <C6>

(In the formula, n is an integer of 0 or 1.)
The electron beam curable resin composition which is the isocyanurate compound represented by these.
A polyolefin resin and a crosslinking agent are contained, and the crosslinking agent is represented by the general formula (C)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or an allyl group.)
An electron beam curable resin composition which is an allyl glycoluril represented by the formula:
(A) component: polysiloxane having at least two alkenyl groups bonded to silicon atoms;
(B) component: a polysiloxane crosslinking agent having at least two hydrogen groups bonded to silicon atoms;
(C) component: a hydrosilylation reaction catalyst;
Component (D): General formula (C)

(In the formula, R 1 and R 2 each independently represent a hydrogen atom, a lower alkyl group or a phenyl group, and R 3 , R 4 and R 5 each independently represent a hydrogen atom or an allyl group.)
And allyl glycoluril represented by
A silicone resin composition comprising 0.1 to 10 parts by mass of the component (D) with respect to a total of 100 parts by mass of the component (A) and the component (B).
The silicone resin composition according to claim 28, substantially free of a silicon compound having a silanol group.
The silicone resin composition according to claim 28 or 29, wherein the alkenyl group is a vinyl group or a (meth) acryloyl group.
The silicone resin composition according to any one of claims 28 to 30, which is used for sealing an optical semiconductor element.