WO2000042622A1

WO2000042622A1 - Resin composition for dielectric layer formation and film for dielectric layer formation

Info

Publication number: WO2000042622A1
Application number: PCT/JP1999/000116
Authority: WO
Inventors: Koji Tomita
Original assignee: Soken Chemical & Engineering Co., Ltd.
Priority date: 1999-01-14
Filing date: 1999-01-14
Publication date: 2000-07-20
Also published as: KR20010108038A; JP3498308B2; CN1188868C; KR100605543B1; CN1333911A

Abstract

A resin composition for dielectric layer formation and a film for dielectric layer formation, from each of which a dielectric layer having an even thickness can be easily formed by applying the composition or film to a desired part of a substrate and baking it. The dielectric layer thus formed neither contains residual carbon nor has craters. The resin composition is obtained by adding 100 to 500 parts by weight of a powder of an inorganic dielectric to 100 parts by weight of a self-adhesive resin which is obtained by polymerizing 80 to 100 wt.% C1-12 methacrylic ester with 0 to 20 wt.% other monomer copolymerizable therewith and optionally with 0.5 to 10 wt.% carboxylated monomer and has a weight-average molecular weight of 20,000 to 1,000,000 and a glass transition temperature of 15° C or lower. The film is obtained by spreading the resin composition on a flexible film.

Description

Description Dielectric layer forming resin composition and dielectric layer forming film

The present invention relates to a resin composition for forming a dielectric layer, a film for forming a dielectric layer using the same, and a method for forming a dielectric layer on a substrate using the same.

More specifically, a resin composition for forming a dielectric layer having excellent adhesiveness and high flexibility, and using this resin composition, can be attached to a substrate of a material such as ceramics or metal, The present invention relates to a film for forming a dielectric layer capable of forming a dielectric layer having a uniform thickness by firing it, and a method for forming a dielectric layer on a substrate using the film. Background technology

Conventionally, as a method for forming a dielectric layer on a substrate, a method is known in which a dielectric inorganic powder is mixed with a binder as required, and then applied and baked by a method such as screen printing. Have been.

However, this method has a drawback that the accuracy of the coating thickness is poor, and that the thickness of the dielectric layer also varies. Further, this method has a drawback that the steps are long because the steps involve printing and baking.

—Slurry consisting of ceramic powder, organic binder, solvent, plasticizer, etc. is molded into a green sheet by doctor blade method, etc., baked, and ceramic plate (layer) There is also known a method of forming (for example, JP-A-62-23064, JP-A-62-28358). However, this green sheet requires a process such as solvent removal in production, There was a problem that was not enough in terms of flexibility.

In addition, when an organic binder is used to form an inorganic layer such as a ceramic material of a green sheet, the formation layer may be formed if the amount of carbon (hereinafter referred to as “residual coal”) caused by the organic binder is large. Therefore, it was necessary to reduce residual coal as much as possible, and it was difficult to select an organic binder.

In addition, a fundamental problem is that green sheets do not have adhesive properties, and must be fixed by some means to form a ceramic layer on another substrate. There was a problem.

Recently, a technology has been developed to form a dielectric layer on a glass substrate by transferring the film-forming material layer formed on the supporting film onto a glass substrate on which the electrodes are fixed and baking it. (Japanese Unexamined Patent Application Publication No. 9-110273).

However, in this technique, a tackifier such as ethylene glycol diacrylate is essential to transfer the film-forming material layer onto the glass surface, and when the film-forming material layer is baked, the tackifier is used. There was a problem that crater-shaped depressions could be formed.

Crater-like depressions in the dielectric layer are, for example, fatal defects in the production of plasma display panels (hereinafter referred to as PDPs) that require a uniform dielectric layer. Therefore, the solution was strongly desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described circumstances. It is possible to form a dielectric inorganic layer having a uniform thickness on a desired portion of a substrate by a simple method, and The task is to provide technologies that do not cause problems such as residual coal or crater-like depressions. Disclosure of the invention

The present inventors have proposed a means for forming a dielectric layer having a uniform thickness over a large area. Focused on the technology of forming adhesive tapes, and conducted research on means that can provide adhesiveness without using a tackifier.As a result, a dielectric inorganic powder was compounded in an adhesive layer with a specific composition. By doing so, it was found that excellent adhesion can be obtained.

Furthermore, the adhesive composition of this composition can solve the problem of residual carbon in the dielectric ceramic layer after firing, the problem of crater-like depressions, and provide a dielectric material with extremely high uniformity. It was found that a layer was obtained, and the present invention was completed. That first aspect of the present invention, C, ~ C _{1 2} of main Taku acrylic acid ester 8 0 - 1 0 0 Weight ^_0/0, which is copolymerizable other mono- Ma one possible 0-2 0% Of a self-adhesive resin having a weight average molecular weight of 20,000 to 100,000 and a glass transition temperature of 15 ° C or lower. A dielectric layer-forming resin composition comprising 100 to 500 parts by weight of a dielectric inorganic powder.

Further, the second invention of the present invention relates to the following: 80 to 100% by weight of a C, to C, ₂ metaacrylic acid ester; 0.5 to 10% by weight of a monomer having a carboxyl group; It is obtained by copolymerizing 0 to 20% by weight of another polymerizable monomer, has a weight average molecular weight of 20,000 to 100,000, and has a glass transition temperature of "I. Provided is a resin composition for forming a dielectric layer, wherein 100 to 500 parts by weight of a dielectric inorganic powder is added to 100 parts by weight of a self-adhesive resin having a temperature of 5 ° C or less. Is what you do.

Further, a third invention of the present invention is a film for forming a dielectric layer, wherein any one of the above-mentioned resin compositions for forming a dielectric is spread on a flexible film subjected to a release treatment.

Still further, in a fourth aspect of the present invention, the film for forming a dielectric layer is attached to a surface of a substrate, a dielectric forming layer containing a dielectric inorganic powder is transferred, and then fired. A method for forming a dielectric layer on a substrate, You. BEST MODE FOR CARRYING OUT THE INVENTION

The resin composition for forming a dielectric layer (hereinafter referred to as “the composition of the present invention” IJ), which is the first invention of the present invention, comprises (1a) C, to C, ₂ metaacrylic acid esters It is obtained by copolymerizing 80 to 100% by weight and other monomers copolymerizable therewith with 0 to 20% by weight <½, and has a weight average molecular weight of 20,000 to 100%.

It is prepared from a self-adhesive resin having a glass transition temperature of 15 ° C. or less and (2) a dielectric inorganic powder.

The self-adhesive resin (a) is obtained by copolymerizing (1) 80 to 100% by weight of a metaacrylic acid ester and (2) 0 to 20% by weight of another copolymerizable monomer. It is obtained by doing. Examples of meta acrylates used are: methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, 2 — Ethylhexyl methacrylate, lauryl methacrylate, and the like, and examples of other monomers used include acrylic acid, methacrylic acid, Droche Shechia Clerate, 2—Hydroxy Sheechi Meta Crate, Benzimea Meta Crate, Alimea Mete Crate, Dimethyl Chia Mino Ethyl Mete Crate, Jetyl Amino Ethyl Mete Crate Rates. Moreover, as the dielectric inorganic powder (2) _{is, P b O, B 2 0} 3, S i O, low melting glasses containing such AIO _3, include powders such Sera Mi click, typically Typical particle sizes are in the range of about 1 to 100 m.

On the other hand, the resin composition for forming a dielectric layer according to the second invention of the present invention (hereinafter referred to as “the composition 2J of the present invention”) comprises a (meth) acrylic acid ester of (lb) C, to 0 to 100% by weight ⁰ / o, monomer having a carboxyl group 0.5 to 10% by weight and another monomer copolymerizable therewith 0 to 20% by weight A self-adhesive resin having a weight average molecular weight of 20,000 to 100,000 and a glass transition temperature of 15 ° C or lower; and (2) a dielectric inorganic material. Prepared from powder.

The self-adhesive resin (1b) includes: (1) 80 to 100% by weight <½ of a metaacrylic acid ester; (2) 0.5 to 10% by weight of a monomer having a carboxyl group and (3) It can be obtained by copolymerizing 0 to 20% by weight of another copolymerizable monomer. Examples of metal acrylates used include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, and n-butyl methacrylate. 2—Ethylhexylmethacrylate, laurylmethacrylate, etc. Examples of the monomer having a carboxyl group include acrylic acid, metaacrylic acid, carboxyl acrylate, and the like. These are the dielectric inorganic powders for the polymer. It plays a role in improving the dispersibility of the material. Furthermore, examples of other monomers ③ used include 2-hydroxyhydracrylate, 2-hydroxymethacrylate, benzylmethacrylate, and arylmetacrylate. Crylate, dimethylaminoethyl methacrylate, getylaminoethyl methacrylate, and the like. The self-adhesive resin (la) has excellent dispersibility of the dielectric inorganic powder in the polymer due to the presence of a monomer having a carboxyl group. It is particularly excellent in terms of its properties.

The resin (la) or (1b) used in the present invention is a self-adhesive composition having excellent adhesive properties and high flexibility. Here, self-adhesiveness means that at least at a temperature of 150 ° C or less, preferably at a temperature of 120 ° C or less, components such as a tackifier are not blended. This means that the resin composition itself has adhesiveness. The self-adhesive resins (1a) and (1b) have a weight average molecular weight of 20,000 to 100,000 and a glass transition temperature of Must be 15 ° C or less. For this purpose, the above-mentioned metaacrylates, monomers having a carboxyl group and other monomers include organic peroxides such as benzoyl peroxide and lauryl peroxide, diazobisisobutyronitrile. It is desirable to polymerize by a radical polymerization reaction using an azo-based polymerization initiator as described above, and it is particularly preferable to polymerize by a solution polymerization method.

The composition of the present invention is prepared by adding 100 to 500 parts by weight of the dielectric inorganic powder (2) to 100 parts by weight of the resin (1a), and optionally adding other optional components. This is done by adding the ingredients and mixing uniformly. Examples of the optional component include plasticizers such as DBP and DOP, but generally it is more preferable to add a small amount of plasticizer.

The composition 2 of the present invention was also prepared by adding 100 to 500 parts by weight of a dielectric inorganic powder (2) to 100 parts by weight of the self-adhesive resin composition (1b), This is done by adding other optional components and mixing them as necessary. As an optional component, a plasticizer such as DBP or DOP is exemplified, and it is generally preferable that a small amount of a plasticizer is added, as in the preparation of the composition 1 of the present invention. It is.

The obtained compositions 1 and 2 of the present invention each maintain a certain degree of adhesiveness, although they contain a relatively large amount of inorganic powder as compared with the resin component. That is, the composition of the present invention does not show adhesiveness at room temperature, and is 60 to 150 ° C, preferably 80 to 150 ° C, and more preferably 80 to 12 ° C. It shows adhesiveness in the temperature range of 0 ° C. In addition, this property is that the sheet using the composition does not adhere to the substrate at room temperature, but the adhesive property is obtained by applying pressure with a roller having a certain temperature or more, and the transferred image is transferred. This means that there is no rubbing or fraying at the time of bonding, and that bonding to wrong places is eliminated, and workability can be improved. The compositions 1 and 2 of the present invention thus obtained were further spread on a flexible film, and formed into a film for forming a dielectric layer (hereinafter referred to as “dielectric forming film”). Is obtained. As the flexible film, sheets, tapes, and the like of flexible polymers such as polyester, polypropylene, and polyethylene can be used. I prefer that there be. The spreading is performed by a known method, and the film thickness is determined by the intended dielectric layer.

The dielectric-forming film of the present invention obtained in this manner has high flexibility to prevent cracking of the film at the time of rewinding and generation of burrs at the cut portion at the time of slitting. Can be prevented. Further, as described above, it has excellent adhesiveness at 60 to 150 ° C, preferably <80 to 150, and more preferably 80 to 120 ° C. However, by applying heat, it is possible to adhere and fix to a necessary portion without usually adhering to an unnecessary portion.

Next, a method for forming a dielectric layer using the dielectric film of the present invention will be described. In forming a dielectric layer, first, a specific part on the substrate to be formed is cleaned, and a dielectric forming film having a predetermined shape is applied thereto, and necessary heat is applied to bond the film. . Examples of the substrate on which the dielectric layer is to be formed include substrates made of ceramics, metal, and the like. In particular, to manufacture a PDP, a glass substrate provided with appropriate electrodes is used. Means for cutting the dielectric forming film into a predetermined shape include methods such as cutting and die cutting. It goes without saying that the dielectric layer can be formed over a wide area by using the dielectric forming film as it is.

Next, the flexible film on the dielectric material forming film is removed and baked. The firing temperature varies depending on the dielectric powder contained, but is generally 500 About 600 ° C. The firing time also varies depending on the dielectric powder included and the substrate used, but may be about 20 minutes to 1 hour.

By doing so, a uniform dielectric layer having a desired shape can be formed on the substrate.

The dielectric-forming film of the present invention has excellent adhesiveness and high flexibility even when the self-adhesive resin (1 or (1b)) is blended with a large amount of dielectric inorganic powder, and after firing. Utilizing the property that there is little residual coal, and because it does not use a tackifier, it is difficult to form pinholes and it is possible to form a dielectric layer with good uniformity over a wide range. Industrial applicability

The dielectric-forming film of the present invention is characterized in that the layer containing the dielectric inorganic powder is uniform over a wide range and has an adhesive property at a certain temperature or higher. The dielectric layer can be easily formed even if the area is larger and the area is not flat. In addition, it is also possible to easily cut and paste into a predetermined shape, and it is also possible to form a dielectric layer of an arbitrary shape at an arbitrary portion.

The characteristics of such a dielectric-forming film are clearer than those of a commonly used green sheet. That is, since the dielectric formed film of the present invention can be dried in a short time, it can be mass-produced and the cost can be reduced. In addition, the film thickness can be set and the film thickness can be easily made constant as compared with a green sheet using a doctor blade or the like. Furthermore, since the sheet can be formed in a short time, the process can be shortened, and the cost can be reduced in this aspect as well. Furthermore, layer separation occurs in green sheets when powder with a high specific gravity is used. However, the dielectric film of the present invention does not have such a problem. As described above, according to the dielectric film of the present invention, a uniform dielectric layer can be easily prepared, and a PDP which is being developed for a wall-mounted large display display or the like is being developed. It is highly promising as a method for producing a dielectric glass layer and the like with high accuracy and low cost. In addition, it can be said that it is an advantageous method for simply forming a dielectric layer in various circuits. Example

Next, the present invention will be described in more detail with reference to Examples, Synthesis Examples and Test Examples, but the present invention is not limited to these Examples and the like. Synthesis example 1

A reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube was charged with 100 parts of 2-ethylhexyl methacrylate and 80 parts of toluene, and 0.2 parts of azobisisoptyronitrile was added. Was added, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. After the completion of the reaction, the reaction mixture was diluted with toluene and adjusted to a solid content of 50% to obtain a polymer solution having a viscosity of 7 OO cp, a Tg of 10 ° C and a weight average molecular weight of 150,000. Synthesis example 2

The same apparatus as in Synthesis Example 1 was charged with 50 parts of 2-ethylhexyl methacrylate, 50 parts of n-butyl methacrylate, and 100 parts of toluene, and azobisisobutylonitrile was added. 2 parts were added, and the polymerization reaction was carried out at 0 ° C. for 8 hours in a nitrogen gas stream. After completion of the reaction, to give a solid content 50%, viscosity _{5 0 0 0 cp, T g} 5 ° C, the polymer solution having a weight average molecular weight of 1 20,000. Synthesis example 3

The same equipment as in Synthesis Example 1 was charged with 20 parts of 2-ethylhexyl methacrylate, 80 parts of n-butyl methacrylate and 120 parts of toluene, and 0.2 parts of azobis isopyronitrile. Was added and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated, and a polymer solution having a solid content of 45%, a viscosity of 3200 cp, a Tg of 14 ° C, and a weight average molecular weight of 14,000 was obtained. Synthesis example 4

The same apparatus as in Synthesis Example 1 was charged with 50 parts of lauryl methacrylate, 50 parts of n-butyl methacrylate, and 75 parts of toluene, and 0.2 parts of azobisisobutyronitrile was added. The polymerization was carried out at 70 ° C for 8 hours. After the completion of the reaction, the reaction mixture was diluted with toluene and adjusted to a solid content of 50% to obtain a polymer solution having a viscosity of 900 cp, a Tg of 7 ° C, and a weight average molecular weight of 180,000. Synthesis example 5

In the same apparatus as in Synthesis Example 1, 100 parts of i-butyl methacrylate and 120 parts of toluene were charged, and 0.5 part of azobisisobutyronitrile was added. The polymerization reaction was carried out at ° C for 8 hours. The reaction was terminated, and a polymer solution having a solid content of 45%, a viscosity of 5300 cp, a Tg of 50 ° C, and a weight average molecular weight of 150,000 was obtained. Synthesis example 6

The same equipment as in Synthesis Example 1 was charged with 50 parts of ί-butyl methacrylate, 50 parts of η-butyl methacrylate, and 120 parts of toluene, and azobisisob 0.5 parts of thyronitrile was added, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated to obtain a polymer solution having a solid content of 45%, a viscosity of 480 cp, a Tg of 35 ° C, and a weight average molecular weight of 150,000. Synthesis example 7

The same apparatus as in Synthesis Example 1 was charged with 50 parts of 2-ethylhexyl methacrylate, 50 parts of i-butyl methacrylate, and 80 parts of toluene, and 0.2 parts of azobisisobutyronitrile. Was added, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated to obtain a polymer solution having a solid content of 45%, a viscosity of 420 cp, a Tg of 18 ° C, and a weight average molecular weight of 120,000. Synthesis example 8

The same apparatus as in Synthesis Example 1 was charged with 50 parts of methyl acrylate, 50 parts of butyl acrylate, and 120 parts of toluene, and 0.5 part of azobisisobutyronitrile was added. The polymerization reaction was performed at 5 ° C for 8 hours. The reaction was terminated to obtain a polymer solution having a solid content of 45%, a viscosity of 1,200,000 cp, a weight average molecular weight of 150,000, and a Tg of 25 ° C. Synthesis example 9

A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube was charged with 100 parts of 2-ethylhexyl methacrylate, 2 parts of acrylic acid, and 80 parts of toluene. 0.2 part of sobutyronitrile was added, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. After completion of the reaction, the reaction mixture was diluted with toluene and adjusted to a solid content of 50% to obtain a polymer solution having a viscosity of 700 cp, a Tg of 8 ° C, and a weight average molecular weight of 150,000. Synthesis example 10

The same apparatus as in Synthesis Example 9 was charged with 50 parts of 2-ethylhexyl methacrylate, 50 parts of n-butyl methacrylate, 2 parts of acrylic acid, and 100 parts of toluene. 0.2 parts of azobisisobutyronitrile was added and a polymerization reaction was carried out for 8 hours in a nitrogen gas stream at 70 ° C. After completion of the reaction, the solid content was 50%, the viscosity was 500 cp, and the Tg was 6%. A polymer solution having a weight average molecular weight of 120,000 at ° C was obtained.

The same apparatus as in Synthesis Example 9 was charged with 20 parts of 2-ethylhexyl methacrylate, 80 parts of n-butyl methacrylate, 1 part of acrylic acid, and 120 parts of toluene, and azobisisobutyroni. To the mixture was added 0.2 part of a toluene, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated, and a polymer solution having a solid content of 45%, a viscosity of 3200 cp, a Tg of 14 ° C, and a weight average molecular weight of 14,000 was obtained. Synthesis example 1 2

50 parts of lauryl methacrylate and 50 parts of n-butyl methacrylate, 2 parts of acrylic acid and 75 parts of toluene were charged into the same apparatus as in Synthesis Example 9, and azobisisobutyronitrile was prepared. 0.2 part was added, and a polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. After completion of the reaction, the reaction mixture was diluted with toluene and adjusted to a solid content of 50% to obtain a polymer solution having a viscosity of 900,000 cp, Tg of 5 ° C, and a weight average molecular weight of 180,000. Synthesis example 1 3

In the same device as in Synthesis Example 9, i-butyl meta-relate 50 copies, n-petit 50 parts of lume acrylate, 2 parts of acrylic acid and 120 parts of toluene are charged, and 0.5 parts of azobisisobutyronitrile are added, and the mixture is heated at 0 ° C for 8 hours in a nitrogen gas stream. A polymerization reaction was performed. The reaction was terminated, and a polymer solution having a solid content of 45%, a viscosity of 480 cp, a Tg of 36 ° C, and a weight average molecular weight of 150,000 was obtained. Synthesis example 1 4

The same apparatus as in Synthesis Example 9 was charged with 50 parts of 2-ethylhexyl methacrylate, 50 parts of dibutyl methacrylate, 2 parts of acrylic acid, and 80 parts of toluene. 0.2 parts were added, and the polymerization reaction was carried out at 70 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated to obtain a polymer solution having a solid content of 45%, a viscosity of 420 cp, a Tg of 20 ° C, and a weight average molecular weight of 120,000. Synthesis example "1 5

In the same apparatus as in Synthesis Example 9, 50 parts of methyl acrylate, 50 parts of butyl acrylate,

Acrylic acid (2 parts) and toluene (120 parts) were charged, and azobisisobutyl mouth nitrate (0.5 part) was added. The polymerization reaction was carried out at 5 ° C. for 8 hours in a nitrogen gas stream. The reaction was terminated to obtain a polymer solution having a solid content of 45%, a viscosity of 1,200,000 cp, a weight average molecular weight of 150,000, and a Tg of 23 ° C. Synthesis example 1 6

The same apparatus as in Synthesis Example 9 was charged with 90 parts of methyl acrylate, 10 parts of methacrylic acid and 150 parts of toluene, and 0.2 parts of azobisisobutyronitrile was added. The polymerization reaction was carried out at 70 ° C for 8 hours. Anti The reaction was terminated to obtain a polymer solution having a solid content of 40%, a viscosity of 2000 cp, a weight average molecular weight of 100,000, and a Tg of 113 ° C. Synthesis example 1 7

A polymer solution obtained by adding 30 parts of ethylene glycol diacrylate to the polymer solution obtained in Synthesis Example 16 was obtained. Synthesis example 1 8

A polymer solution having a viscosity of 650 cp, a weight average molecular weight of 140,000 and a Tg of 10 ° C. was obtained in the same manner as in Synthesis Example 9 except that no acrylic acid was added. Example 1

To 100 parts of the polymer obtained in Synthesis Example 1, 300 parts of a dielectric glass powder (PbO composition ratio: about 75 <½) was added and mixed to prepare a resin composition for forming a dielectric layer. Made. This composition was applied to a silicone-coated 75-inch polyester film so that the thickness after drying became 30. After drying by heating, the silicone-coated 25-polyester film was dried. A dielectric film was created using a film. Example 2

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 1 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 2. Example 3

Add 300 parts of dielectric glass powder to 100 parts of the polymer obtained in Synthesis Example 3. Except for the above, a resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1. Example 4

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1, except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 4. Example 5

To 100 parts of the polymer obtained in Synthesis Example 9, 300 parts of a dielectric glass powder (PbO composition ratio is about 75%) was added and mixed to prepare a resin composition for forming a dielectric layer. did. This composition was applied to a silicone-coated 75-polyester film so as to have a thickness of 30 after drying, heated and dried, and then coated with a silicone-coated 25; u-polyester. A dielectric film was made with an ester film. Example 6

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5, except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 10. .

Example 7

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 5, except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 11. Was. Example 8

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 5, except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 12. .

Comparative Example 1

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 5. Comparative Example 2

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 6. Comparative Example 3

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1, except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 7. Comparative Example 4

A resin composition for forming a dielectric layer and a dielectric film were obtained in the same manner as in Example 1 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 8.

Comparative Example 5 A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 13. Obtained. Comparative Example 6

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 14. Obtained. Comparative Example 7

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 15. Obtained. Comparative Example 8

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5 except that 300 parts of dielectric glass powder was added to 100 parts of the polymer obtained in Synthesis Example 16. Obtained. Comparative Example 9

A resin composition for forming a dielectric layer and a dielectric film were prepared in the same manner as in Example 5 except that 300 parts of dielectric glass powder was added to 100 parts of the composition obtained in Synthesis Example 17. Obtained. Comparative example 10

To 100 parts of the composition obtained in Synthesis Example 18 was added 300 parts of dielectric glass powder. A dielectric layer-forming resin composition and a dielectric film were obtained in the same manner as in Example 5 except for the above. Test example 1

Performance test (1):

With respect to the dielectric films prepared in Examples 1 to 4 and Comparative Examples 1 to 4, their adhesiveness, flexibility and appearance after firing were examined by the following methods. The results are shown in Table 1.

C Adhesion test]

The dielectric film was cut into 5 0 x 1 OO mm, roll temperature 1 0 0 ° C for heating tiger Mine one coater, roll pressure 0. 5 kgf Z cm ^2, and set the roll speed 1 0 0 0 mm / min Then, the film and a glass substrate heated to 100 ° C. were adhered with a heat-reducing unit. Next, the adhesion area was confirmed and evaluated according to the following criteria. The roll pressure of 0.5 kgf / cm ² is much lower than the normal bonding pressure.

Evaluation criteria :

Evaluation status

接着 The bonding area is 80% or more.

The bonding area is 60% or more and less than 80%.

The bonding area is less than 60%.

[Flexibility test]

The dielectric film was cut into a piece of 20 × 100 mm, and both ends were pulled at 300 mm / min with a tensile tester, and the stretch of the film was visually checked. In addition, the dielectric film is bent at 180 °, and the strength of the film is increased. The degree was checked. These conditions were combined to evaluate the flexibility according to the following criteria.

Evaluation criteria

Evaluation status

〇 The film is growing and growing.

Δ Elongation of the film is small, but it does not break when bent at 180 ° C.

X The film does not stretch and breaks when bent at 180 ° C.

[Firing test]

The dielectric film was adhered to a glass substrate, the polyester film was adhered, and the panel was baked in an electric furnace at 550 ° C. for 30 minutes. Changes in the appearance of the glass substrate (dielectric glass layer) after firing were visually confirmed and evaluated according to the following evaluation criteria.

Evaluation criteria

Evaluation status

〇 The dielectric glass layer is transparent.

Δ The dielectric glass layer is somewhat poorly transparent

X The dielectric glass layer is dark.

[Result]

Table 1 Evaluation

Dielectric film + jt ¾ mfe 1 or <Ht

Wang Singh Example 1

Example 2 Lily

Example 3 A

Example 4 〇〇 Δ

Comparative Example 1 X X 〇

Hi early father Example 2 X X 〇

Hihayabu Example 3 X Δ 〇

As shown in Table 1, the dielectric film of the present invention has adhesiveness and flexibility without practical problems, and has almost no effect on appearance even after firing. Did not give. Test example 2

performance test :

With respect to the dielectric films prepared in Examples 5 to 8 and Comparative Examples 5 to 9, the adhesiveness, flexibility and appearance after firing were examined by the same method as in Test Example 1. Further, the dispersibility of the composition was examined by the following method. Table 2 shows the results.

[Dispersibility test]

After mixing 100 parts of the polymer solution and 300 parts of the dielectric glass powder, the mixture was allowed to stand by itself, the state of sedimentation of the glass powder was observed, and the dispersibility was evaluated according to the following criteria.

Evaluation criteria : _-I

Evaluation status

Conclusion

〇 No sedimentation for 8 hours.

Δ4 Sedimentation within 8 hours

_ _ I

X 24 Sedimentation within 4 hours

Two

Evaluation

Dielectric film

Adhesiveness Flexible Appearance Dispersibility

Example 5 〇〇〇〇 Example 6 Δ 〇〇〇 Example 7 7 Δ Δ 〇〇 Example 8 〇〇 Δ 〇 Comparative Example 5 XX 〇比 Comparative Example 6 X △ 〇較 Comparative Example 7 〇〇 X 〇 Comparative Example 8 XX 〇〇 Comparative Example 9 〇〇 X 〇 Comparative Example 10 0 O OX OX

As is clear from Table 2, the dielectric film of the present invention has adhesiveness and flexibility without practical problems, and has almost no effect on appearance even after firing, and is excellent. It had dispersibility.

Claims

The scope of the claims

1. C, ~ C, ₂ Metaacrylic acid ester 80 to 100% by weight ⁰ / o and copolymerized with 0 to 20% by weight of another monomer copolymerizable therewith. The weight average molecular weight is 20,000 to 100,000, and the dielectric inorganic powder is 100 parts by weight of the self-adhesive resin having a glass transition point temperature of 15 ° C or lower. A resin composition for forming a dielectric layer, comprising 100 to 500 parts by weight.

2. C, ~ C, ₂ of main Taaku Li Le ester 8 0 ~ "! 0 0 Weight ^_0/0, mono Ma 10 having a local Bokishiru group. 5 to 1 0% by weight and copolymerizable therewith The copolymer is obtained by copolymerizing 0 to 20% by weight of other monomers, has a weight average molecular weight of 20,000 to 100,000, and has a glass transition point temperature of 15 ° C or lower. A dielectric layer-forming resin composition, wherein 100 to 500 parts by weight of a dielectric inorganic powder is added to 100 parts by weight of a self-adhesive resin.

3. The resin composition for forming a dielectric layer according to claim 1, which exhibits adhesiveness at a temperature of 3.6 ° C. or higher.

4. This to C, a ~ C _{1 2} of meta accession Li Le ester 8 0-1 0 0 wt ⁰ / o, is copolymerized 2 0 wt% other copolymerizable mono-mer 0 and Re this With respect to 100 parts by weight of self-adhesive resin having a weight average molecular weight of 20,000 to 100,000 and a glass transition temperature of 15 ° C or lower, the A composition comprising 100 to 500 parts by weight of a conductive inorganic powder, which is spread on a flexible film. Lum

5. C, ~ C i meta Accession Li Le ester 8 0-1 ₂ 0 0 wt%, mono-mer 0.5 to 1 0 wt% Oyobi copolymerizable with these other having a local Bokishiru group Is obtained by copolymerizing 0 to 20% by weight of a monomer having a weight average molecular weight of 20,000 to 100,000 and a glass transition point temperature of 15 ° C or lower. A dielectric layer is formed by adding a composition obtained by adding 100 to 500 parts by weight of a dielectric inorganic powder to 100 parts by weight of a self-adhesive resin, and spreading the composition on a flexible film. For film.

6. The film for forming a dielectric layer according to claim 4, which exhibits adhesiveness at a temperature of not less than 60 ° C.

7. The film for forming a dielectric layer according to any one of claims 4 to 6, wherein the flexible film has been subjected to a release treatment.

8. The film for forming a dielectric layer according to any one of claims 4 to 7 is attached to a substrate surface to transfer the dielectric layer containing the dielectric inorganic powder, and then fired. A method for forming a dielectric layer on a substrate, comprising:

9. The method for forming a dielectric layer on a substrate according to claim 8, wherein the substrate is a ceramic substrate. 10. The method for forming a dielectric layer on a substrate according to claim 9, wherein the ceramic substrate is a glass plate on which electrodes are formed.

The method for forming a dielectric layer on a substrate according to any one of claims 8 to 10, which is for manufacturing a plasma display panel.