WO1998016577A1

WO1998016577A1 - Organic pigment for coloring syndiotactic polystyrene (sps) structure, colorant for coloring sps, and styrenic resin composition

Info

Publication number: WO1998016577A1
Application number: PCT/JP1997/003680
Authority: WO
Inventors: Yutaka Azuma; Kouji Satou
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 1996-10-15
Filing date: 1997-10-14
Publication date: 1998-04-23
Also published as: JPH10120931A; DE19780989T1

Abstract

At least one organic pigment for coloring polystyrene (SPS) a syndiotactic, selected among (a) metal-containing azo pigments, (b) copper phthalocyanine pigments, (c) perylene pigments, (d) threne pigments, and (e) quinacridone pigments; a colorant for coloring SPS, comprising the above pigment; a colorant for coloring SPS, comprising the above pigment and an inorganic pigment; and a styrenic resin composition comprising a blend of SPS with at least one member selected among rubbery elastomers, thermoplastic resins other than SPS, inorganic fillers and the above colorant for coloring. The colorant for coloring SPS and the styrenic resin composition do not cause mold staining due to the bleeding of the colorant and can provide products having excellent quality stability free from migration of colors while maintaining the excellent heat resistance and other properties inherent in SPS.

Description

Satsuki Itoda

Styrene polymer having syndiotactic structure (SPS) Organic pigment for coloring, coloring material for SPS coloring, and styrene resin composition

Technical field

The present invention relates to a coloring material used for a styrene-based polymer having a syndiotactic structure (hereinafter sometimes abbreviated as “SPS”), and a blend of SPS and certain components. The present invention relates to a styrene resin composition comprising the coloring material. More specifically, the present invention relates to a coloring material for SPS coloring and a styrene resin composition which do not cause contamination of a mold due to bleeding of a coloring material during molding.

Background art

Since SPS has extremely excellent properties such as heat resistance, chemical resistance, electrical characteristics, and water absorption dimensional stability, it has been used in various applications as an engineering plastic. For some applications, colored objects were required, for example, when it was necessary to identify relay connectors or colors.

Usually, various dyes and pigments are used to color the resin. However, when coloring a certain resin, when selecting the coloring material, clarity, coloring power, dispersibility, heat resistance, and weather resistance are required. Investigations have been made from every angle, including properties, color transfer, water resistance, solvent resistance, chemical resistance, and toxicity.

For example, dyes that are generally referred to as oil-soluble dyes are used, but for resins such as soft vinyl chloride, polyethylene, and polypropylene, bridged migration (transition) ) Can not be used except in very special cases, but polymethylmethacrylate

Styrene resins such as ABS resin and ABS resin have good dispersibility, transparency, Widely used because of its sharpness.

On the other hand, pigments are roughly classified into inorganic pigments and organic pigments, each of which is classified according to its structure. In general, organic pigments are selected from the viewpoints of transparency, clarity, and coloring, and hiding power Inorganic pigments are selected from the viewpoint of heat resistance and weather resistance.

By the way, when coloring SPS, it is not always possible to apply general dyes and pigments used for ordinary resins as they are due to the excellent properties of the resin itself of SPS itself. That is, it is particularly excellent in heat resistance

Since SPS requires high temperatures for crystallization during molding, the temperature of the mold must be increased, so that general dyes used in ordinary resins generate preads and contaminate the mold. Can not be used because it causes Furthermore, for example, even pigments used for resins that require the same high temperature for molding, such as polycarbonate, are not necessarily applicable to SPS.

As mentioned above, no knowledge has been obtained yet about the coloring material for SPS, and it is currently impossible to find a suitable coloring material.

The present invention has been made in view of the above-mentioned situation, and provides an organic pigment for coloring of SPS, a coloring material for coloring of SPS, and SPS which are excellent in processing stability and service stability, as required. An object of the present invention is to provide a styrene-based resin composition comprising a compound containing the above components and the coloring material. Disclosure of the invention

The present inventors have assiduously studied and found that a specific organic pigment is extremely effective for coloring SPS, and the organic pigment, or the organic pigment and the inorganic pigment are used for coloring SPS. Can be used as a coloring material I found that.

The present invention has been completed based on such findings.

That is, the present invention is selected from (a) metal-containing azo pigments, (b) copper phthalocyanine pigments, (c) perylene pigments, (d) sulene pigments, and (e) quinacridone pigments. An object of the present invention is to provide at least one kind of organic pigment for SPS coloring (1), and to provide a coloring material for SPS coloring using the organic pigment (2), wherein an inorganic pigment and the organic pigment are used. An object of the present invention is to provide an SPS coloring material (3) comprising a pigment. In addition, (A) (a) 20 to 100% by weight of SPS, (b) a rubber-like elastic material, (c) a thermoplastic resin other than a styrene-based polymer having a syndiotactic structure, and (inorganic) 100 parts by weight of an SPS blend comprising at least 80 to 0% by weight of at least one selected from fillers, and the coloring material for SPS coloring according to the above (2) or (3)

An object of the present invention is to provide a styrenic resin composition comprising 0.001 to 200 parts by weight.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the organic pigment for SPS coloring, the coloring material for SPS coloring, and the styrene resin composition of the present invention will be specifically described.

1. Organic pigments for SPS coloring

(a) Metal-containing azo pigment

The metal-containing azo pigment is an azo pigment having a hydrophilic group or a substituent containing a hydrophilic group, which is a water-soluble or poorly water-soluble pigment that is made of a metal, for example, aluminum, canolesum, varnish. , Strontium, manganese, iron

An azo lake pigment that is made insoluble (lake) by forming a salt with, lead, tin, nickel, etc. The hydrophilic group here, for example, one S 0 ₃ H, one S 0 ₃ M, One OS 0 ₃ H, one _{OS 0 3 M, - C OO-} NR 3 X (M is alkali metal or one NH ₄ and R are alkyl groups, X is halogen You. ) Or a group formed by condensation of these groups

(Eg, —S◦ ₃ NH ₂ C 0—), which is a polar atomic group that has strong interaction with water. The azo pigment is generally obtained by subjecting a diazonium salt obtained by diazotizing an aromatic amine to a phenolic or naphthol compound, usually in the presence of alcohol, in a force-pulling reaction. And refers to a pigment having an azo group (one N = N—). Examples of metal salts used for insolubilizing (lake) water-soluble or poorly water-soluble azo pigments include, for example, aluminum sulfate, barium chloride, tin chloride, and sulfur chloride outlet. Examples include sodium, calcium chloride, manganese chloride, iron chloride, and lead acetate.

Specific examples of metal-containing azo pigments include Vigment Tiero 150, Vigment Yellow 183, Lake Red C, Brilliant Carmine 6B, and Wo Tingled, lithospheric, brilliant ska — Lett G, lakelet D, and the like.

(b) Copper phthalocyanine pigment

The copper phthalocyanine pigment is a method in which copper phthalocyanine having a structure represented by the following general formula (I) is converted into a pigment (for example, a method in which a crude product is dissolved in concentrated sulfuric acid, and then the concentration of sulfuric acid is reduced to precipitate) To obtain finer crystals), and further provided as a coloring material through a drying step or the like.

Since copper phthalocyanine has various crystal forms, there is a possibility that coloring power may be reduced or a hue change may occur due to crystal transition. Therefore, in general, a method is employed in which several halogen atoms, preferably, chlorine are introduced into the benzene ring of a copper phthalocyanine molecule to prevent crystal transition and crystal growth, and this halogenation method is used. Copper phthalocyanine can also be used. Further, a sulfone group-introduced one or a sulfonated copper phthalocyanine insoluble with a metal salt or the like may be used.

Further, the pigment may be stabilized by treating with a surfactant or the like in order to prevent aggregation of the pigments.

Specific examples of the copper phthalocyanine-based pigment include pigment blue 15: 3, pigment green 36, pigment green 7, and the like.

(c) Perylene pigment

The perylene pigment refers to a pigment having a structure represented by the following general formula (II) in the chemical structure.

(In the formula, X, H, - R, one P h, - P h- R, one _{P h- R 2, - P h} - OR, - COR, - P h - N = N - P h, one P h—HC = CH—P h (where R represents an alkyl group having 1 to 10 carbon atoms and P h represents a vinyl group), preferably — P h—OCH ₃ , one P h— 0 C ₂ H, one P h— (CH ₃ ) ₂ , one CH, H, — P h -N = N_P h, indicates -COCH.

Specific examples of perylene pigments include pigment red 178, perylene red (pigment red 190), perylene vermillion (pigment red 1). 2 3), peri-lens force (vigment thread 14 9), peri-lenmal (vigment red 1 79), perylene brown (vig-point brown 26), etc. Is mentioned.

(Melanie pigment

Slen-based pigments are those having an anthraquinone structure or an anthraquinone derivative represented by the following general formula (III) in the chemical structure.

Specific examples of the sullen pigment include Zianthraquinolyl red (VIG Mentred 1777), Indone Tromble (Big Men 60), Big Men Tiero 1 147, Anthra Pyrimimidin Yellow (Pig Men Toys 110), Asilua Midielo I (Big Men Toyer 990), Flavantrone Yellow (Big 24 I), Pyranthrone Orange (Big Orange 40), Entroin Orange (Vigmented Thread 1668), Isobiolan Tron Blue

(Vigment Violet 3 1), Pigment Red 2 16, Pigment Violet 33, Pigment Blue 22, Pigment Blue 1 2

1, Big Blue 6 and the like.

(e) Quinacridone pigment

The quinacridone pigment refers to a pigment having a structure represented by the following general formula (IV) as a basic skeleton.

(In the formula, X represents H, —R (R represents an alkyl group having 1 to 10 carbon atoms; preferably 1 CH ₃ ) and halogen (preferably 1 C 1). )

Specific examples of the quinacridone pigments include quinacridone reddish (pigmented red dye 19), quinacridone magenta (pigmented reddish 122), and quinacridone scarlet (Vigment Red 207), Kinakuri Don Red (Vigment Red 209), Kinakuri Don Red 1 (Vigment Red 206), Vigment Red 2 0 2 and the like. 2. SPS coloring material

The specific organic pigment described above or a combination of the organic pigment and the inorganic pigment is used as the coloring material for SPS coloring.

The inorganic pigments are not particularly limited. For example, titan oxides such as titanium white and titan yellow, iron oxides such as red iron oxide and iron oxide yellow, and oxides such as zinc white and chrome green can be used. , Molybdenum chromate-based materials such as graphite and chromium-million, and mercury such as force-dominated muylene, force-doped selenide such as force-dominated, and mercury-reed Examples include selenium sulfide, fluorinated compounds such as navy blue, aluminum silicates such as ultramarine blue, metal powders such as aluminum powder and bronze powder, carbon black, and pearl mai power. These may be used alone or as a mixture of two or more.

When the above-mentioned specific organic pigment and inorganic pigment are used in combination, the ratio is not particularly limited, and may be appropriately blended according to the use. By using these in combination, the colorability and color development are improved, and the so-called color vividness is increased.

Furthermore, pigment dispersants such as metal seggen, mineral oil, low molecular weight thermoplastic resin, monoamides and bisamides can be added in order to improve the color development. 3. Styrene resin composition

(A) (a) 20-100% by weight of SPS, (b) rubber-like elastic material, (c) at least one of thermoplastic resins other than SPS and (at least one selected from inorganic fillers) 100 parts by weight of an SPS blend comprising 0% by weight, and (B) 0.001 to 200 parts by weight of the above-mentioned SPS coloring material.

(1) (A) SPS compound

The SPS compound to which the SPS coloring material is added is SPS only. Although used alone, it can be specifically used as the following compound.

(1) A compound comprising (a) 20 to 99% by weight of SPS and (b) 80 to 1% by weight of a rubber-like elastic material,

(2) a compound comprising (a) 20 to 99% by weight of SPS and (c) 80 to 1% by weight of a thermoplastic resin other than SPS;

(3) a composition comprising (a) 20 to 99% by weight of SPS and (d) 80 to 1% by weight of an inorganic filler;

配合 a composition comprising (a) 20 to 99% by weight of SPS and (b) a rubbery elastic body and (c) 80 to 1% by weight of a thermoplastic resin other than SPS;

A composition comprising (a) 20 to 99% by weight of SPS and (b) a rubber-like elastic material and (d) 80 to 1% by weight of an inorganic filler;

配合 a mixture of (a) 3 to 320 to 99% by weight, (c) a thermoplastic resin other than SPS, and (d) 80 to 1% by weight of an inorganic filler,

配 A distribution consisting of (a) 8 to 82 to 99% by weight, (b) a rubber-like elastic body, (c) a thermoplastic resin other than SPS, and (d) 80 to 1% by weight of an inorganic filler. Compound

(2) Next, each component in the blend will be described in detail.

(a) Styrene-based polymer having a syndiotactic structure (SPS) The syndiotactic structure of a styrene-based polymer (SPS) having a syndiotactic structure has a three-dimensional structure. It has a three-dimensional structure in which a fluorinated group and a substituted phenyl group, which are side chains with respect to the main chain formed from carbon-carbon bonds, are alternately located in opposite directions. City one is quantified by nuclear magnetic resonance ^{(1 3} C-NMR method) by carbon isotope. ^{1 3} C—The tacticity measured by NMR is one of the In the case of styrene having a syndiotactic structure according to the present invention, the strength can be represented by, for example, a diad in the case of two, a triad in the case of three, and a pentad in the case of five. A polymer is usually 75% or more in racemic diad, preferably 85% or more, or 30% or more in racemic pentad, preferably 50% or more. % Of polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinylstyrene) Benzoic acid ester), hydrogenated polymers and mixtures thereof, or copolymers containing these as main components. Here, the poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tert-butylstyrene), and poly (vinylstyrene). ), Poly (vinylnaphthalene), poly (vinylstyrene), etc. Poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and so on. Poly (halogenated alkylstyrene) includes poly (chloromethylstyrene), and poly (alkoxystyrene) includes poly (methoxystyrene) and poly (ethoxyquin). (Styrene).

Of these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), and poly (styrene). (P-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units.

The styrenic polymer may be used alone or in combination of two or more. Can be used in combination.

The molecular weight of the styrenic polymer is not particularly limited, but the weight average molecular weight is preferably at least 1,000, more preferably at least 5,000. In addition, the molecular weight distribution is not limited in its width, and various types can be applied. Here, if the weight average molecular weight is less than 1000, the thermal properties and mechanical properties of the obtained composition or molded article may be unfavorably reduced.

Such a styrenic polymer having a syndiotactic structure is produced, for example, by using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent or in the absence of a solvent. Then, it can be produced by polymerizing a styrene-based monomer (a monomer corresponding to the styrene-based polymer) (Japanese Patent Laid-Open No. 62-187708). In addition, poly (halogenated alkylstyrene) can be obtained by the method described in JP-A-1-46912, and the hydrogenated polymer can be obtained by the method described in JP-A-1178505. .

The blend according to the present invention contains (a) the styrene-based polymer having a syndiotactic structure in the range of 20 to 100% by weight. When the content of SPS is less than 20% by weight, the excellent characteristics of SPS are not exhibited, which is not preferable. (B) Rubber-like elastic body

Examples of the rubber-like elastic material include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, atalinole rubber, urethane rubber, silicone rubber, and ebichloro hydrid rubber. Rubber, styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene Mono-butadiene-styrene block copolymer (SEBS ), Styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-block Copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), ethylene propylene rubber (EPR), ethylene propylene rubber (EPDM) ) Or butadiene acrylonitrile linoleic styrene core rubber (ABS), methyl methacrylate-butadiene styrene core rubber (MBS), methyl methacrylate Rate acrylate clear styrene-core shell rubber (MAS), octyl acrylate-butadiene-styrene-core shell rubber (MABS), alkyl acrylate-butadiene rubber Including acrylonitrile polystyrene rubber (A ABS), butadiene-styrene-core shell rubber (SBR), methyl methacrylate-butyl acrylate siloxane A core-shell type particulate elastic material such as a siloxane-containing core rubber or a rubber modified from these may be used.

Among these, SBR, SEB, SBS, SEBS, SIR, SEP. SIS, SEPS, core shell rubber, EPM, EPDM, and rubbers modified from these are preferably used. These rubber-like elastic bodies can be used alone or in combination of two or more.

(c) Thermoplastic resins other than SPS

The thermoplastic resin can be arbitrarily selected from conventionally known resins as long as it is a resin other than the above-mentioned SPS. Specifically, for example, a linear high-density polyethylene, a linear low-density polyethylene is used. Ren, high-pressure method low-density polypropylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, Random Polypropylene, Polybutene, 1, 2—Polybutadiene, cyclic polyolefin, poly_4—Polyolefin resin such as methylpentene, polystyrene, HIPS, ABS, AS Styrene resin, Polycarbonate, Polyethylene terephthalate, Polybutylene terephthalate and other polyester resins, Polyamide 6, Polyamide 6,6 And polyphenylene ether, polyvinylidene sulfide, and the like. In addition, only one kind of the thermoplastic resin can be used alone, or two or more kinds can be used in combination.

(d) Inorganic filler

Various inorganic fillers such as fibrous, granular, and powdery materials are used. For example, examples of the material type of the fibrous inorganic filler include glass fiber, carbon fiber, and whisker. Examples of the shape of the fibrous inorganic filler include a cross shape, a mat shape, a cut bundle shape, a short fiber shape, and the like. It is preferable that the length is 0.05 to 50 mm and the fiber diameter is 5 to 20 μm.

On the other hand, as the material of the granular or powdery inorganic filler, for example, talc, lime black, graphite, titanium dioxide, silica, mai power, calcium carbonate, calcium sulfate, and calcium carbonate , Magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, alumina, kaolin, gaynium carbide, metal powder, glass powder, glass flake, glass beads and the like. Among such inorganic fillers, glass fillers, such as glass powder, glass flakes, glass beads, glass filament, glass fiber, glass lobing, and glass mat, are particularly preferable.

In addition, as an inorganic filler, in order to improve the adhesiveness with a resin, Those surface-treated with a coupling agent or the like are preferably used. As the coupling agent, a silane-based coupling agent, a titanium-based coupling agent, or any conventionally known coupling agent can be arbitrarily selected and used. Above all, ferraminoprovir trimethoxysilane, N-β- (aminoethyl) -ferraminopropyl trimethoxysilane, a-glycidoxypropyl trimethoxysilane, — (3,4-epoxycyclohexyl) Amino silane such as ethyl trimethyoxy silane, epoxy silane, isopropyl tri (diamidoethyl, aminoethyl) titanate is preferred. New

In addition, a film-forming substance (film-former) can be used in combination with the above-mentioned coupling agent, and as the film-forming substance, Known ones can be used without particular limitation, and among them, urethane-based, epoxy-based, polyether-based and the like are preferably used.

Such an inorganic filler may be used alone, but may be used in combination of two or more as necessary.

(3) In the above-mentioned SPS compound, the mixing method of each compound component is not particularly limited, and conditions such as an addition order and a mixing method can be arbitrarily set. The blend includes those obtained by mixing and then kneading the components. The method of melt-kneading is not particularly limited, and a commonly known method can be used.

(4) The styrenic resin composition may contain various additives such as an antioxidant, a nucleating agent, a plasticizer, a mold release agent, a flame retardant, a flame retardant auxiliary, as long as the object of the present invention is not impaired. Additives such as antistatic agents can be added.

Examples of the nucleating agent include metal salts of carboxylic acids such as aluminum di (ρ t butyl benzoate), and methylene bis (2,4-z-t-butyl phenyl) acid phosphite sodium. To be Any known metal salt of phosphoric acid, talc, phthalocyanine derivative, or the like can be arbitrarily selected and used. In addition, these nucleating agents can be used alone or in combination of two or more.

Examples of plasticizers include polyethylene glycol, polyamido oligomer, ethylene bis stearamide, fluoric acid ester, polystyrene oligomer, polyethylene wax, and polyethylene wax. It can be arbitrarily selected from known oils such as natural oil and silicone oil. These plasticizers can be used alone or in a combination of two or more.

The release agent can be arbitrarily selected from known ones such as polyethylene wax, silicone oil, long-chain carboxylic acid and long-chain carboxylate. These release agents can be used alone or in a combination of two or more.

The antioxidant can be arbitrarily selected from known ones such as a phosphorus type, a phenol type and a zeolite type. These antioxidants can be used alone or in a combination of two or more.

Examples of the flame retardant include brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, brominated polyphenylene ether, brominated diphenylalkane, and brominated diphenylether. Any known compound such as a brominated aromatic compound can be used. Further, as the flame retardant aid, any one of antimony compounds such as antimony trioxide and others can be arbitrarily selected and used, and only one kind may be used alone. Alternatively, two or more kinds can be used in combination. (5) Method for producing styrene resin composition

There is no particular limitation on the method for producing the styrene resin composition comprising the SPS compound and the SPS coloring material (that is, the specific organic pigment, or the organic pigment and the inorganic pigment). For example, it can be manufactured by the following method.

(1) A method in which each component of the SPS compound and the coloring material for SPS coloring are simultaneously mixed and then melt-kneaded to form a pellet.

In this case, the ratio of the SPS composition to the SPS coloring material is 0.001 to 10 parts by weight, preferably 0.01 to 100 parts by weight, based on 100 parts by weight of the SPS composition. 5 parts by weight.

(2) A method in which the components of the SPS compound are first mixed, melt-kneaded to produce a pellet, and then mixed with a coloring material for SPS coloring, and then melt-kneaded again to form a pellet. Also in this case, the ratio of the SPS compound to the SPS coloring material is the same as that described in (1) above.

(3) The high-concentration colored pellets (masterbatch) obtained by simultaneously mixing and melting and kneading each component of the SPS compound with the coloring material for SPS coloring, and mixing and melting each component of the SPS compound. A method in which pellets obtained by kneading are blended at a ratio suitable for the intended use.

The ratio of the SPS compound to the SPS coloring material in the production of the master batch is 0.1 to 200 parts by weight, preferably 100 to 200 parts by weight of the SPS compound, and preferably 0.1 to 200 parts by weight. It is 0.5 to 150 parts by weight.

The pellets obtained by these methods or their blends are provided as molding materials, for example, for injection molding, depending on the required use.

【Example】

Next, the present invention will be described in detail with reference to Examples and Comparative Examples. Is not limited to these examples.

(Production Example 1)

A catalyst system comprising triisobutylaluminum (c) component, methylaluminoxane (b) component, and pentamethylcyclopenta genenyl titanate trimethoxide (a) component is used as a catalyst system.

(Hereinafter abbreviated as X), and tri-normal propylaluminum was added to polymerize styrene (hereinafter abbreviated as SM) (conversion rate = 21%). At this time, each component is mixed in a molar ratio of SM: X: (c) component: (b) component: (a) component = 3500000: 25: 25: 75: 1, and polymerized. Went at 70 for one hour. After finely pulverizing the polymer, the polymer was sufficiently washed with methanol and dried under reduced pressure. When the obtained polymer was subjected to Soxhlet extraction for 6 hours using methylethyl ketone as a solvent, the insoluble content was 97%. Its weight average molecular weight was 73,000.

(Production Example 2)

(c) component triisobutylaluminum, (b) component dimethylanilinetetra (pentafluorophenyl) borate, and (a) component pentamethylcyclopentagenenyl titanate. Triethyl aluminum as an organometallic compound (hereinafter abbreviated as X) was added to a methoxide catalyst system to polymerize styrene (hereinafter abbreviated as SM) (conversion rate: 35%). At that time, the components were mixed in a molar ratio of SM: X: (c) component: (b) component: (a) component = 3500000: 25: 20: 0: 1: 1, and the polymerization was carried out. I went for one hour at 70. After finely pulverizing the polymer, the polymer was sufficiently washed with methanol and dried under reduced pressure. When the obtained polymer was subjected to soxhlet extraction for 6 hours using methylethyl ketone as a solvent, the insoluble content was 98%. Its weight average molecular weight was 39,000 o (Production Example 3)

First, 90 mol of pentamethylcyclopentagenenyl titan trimethoxide, 90 / mol of dimethylanilinium dimethyltetra (pentafluorophenyl) borate, 29.1 mimol of toluene, and 1.8 mimol of triisobutyl valium. The mixture was mixed to prepare a premixed catalyst.

Next, 1.0 liter of purified styrene and 1 millimol of triethylaluminum were added to a reaction vessel having an internal volume of 2 liters, and the mixture was heated to 75 ° C. A little was added and polymerization was carried out at 76 ° C for 5.2 hours. After completion of the reaction, the product was repeatedly washed with methanol and dried to obtain 380 g of a polymer.

The weight average molecular weight of this polymer was measured by gel permeation chromatography at 130 ° C using 1,2,4-trichlorobenzene as a solvent. 63,500.

(Production Example 4)

The polymerization was carried out in exactly the same manner as in Production Example 2 except that the organometallic compound, triethylaluminum, was changed to 200 times the amount of the component (a). The conversion was 25%, and the weight average molecular weight was 25%. It was 13 million.

〔Evaluation test〕

The following tests were performed using the injection molding raw materials obtained in the examples and comparative examples. (1) Retention heat stability test

A test sheet (90 mm × 40 mm × 3 mm) obtained by injection molding the injection molding material at 290 ° C. and the same injection molding material at 290 ° C. The test pieces (90 mm × 40 mm × 1 mm) obtained by injection molding and holding at the same temperature for 20 minutes were examined for the degree of discoloration.

CIE 1976 L * a * b * Display by color space and color difference formula (Δ Ε ab *) and evaluated as follows.

ΔE ab * less than 2 (that is, almost no discoloration)

◎

If Eam is 2 or more and less than 5 (that is, the color is slightly discolored),

X was determined when ΔE ab was 5 or more (that is, it was so discolored that it was practically unusable).

(2) Color material transfer test

A test sheet piece (90 mm × 40 mm × 3 mm) obtained by injection molding the injection molding material at 290 ° C. was placed on a white vinyl chloride sheet (30 mm × 30 mm). X 2 mm), adhered each other for 2 hours, and peeled off. The color difference before and after the white vinyl chloride sheet was brought into contact with the test sheet piece was measured.

Those with less than 2 Eab * (i.e., those with little discoloration) were rated as ◎, indicating no color migration.

Xs having ΔE ab * of 2 or more (that is, those with some discoloration) were designated as having color migration.

(Examples 1 to 4, Comparative Examples 1 and 2)

To 100 parts by weight of the SPS obtained in Production Example 1, 0.01 parts by weight of the inorganic pigment shown in Table 1, 0.005 parts by weight of the organic pigment, and 0.005 parts by weight of the dye as shown in Table 1 Then, the mixture was melt-kneaded at 290 ° C. using a twin-screw kneader to produce pellets. This pellet was used as a raw material for injection molding. The results are shown in Table 1. [Table 1] Color material retention heat stability Color material migration test Organic pigment Inorganic pigment Dye

Example 1 Biggnunt Yellow-150 No added No added ◎ ◎ Example 2 Biggest Blue-15: 3 No added No Added ◎ ◎ Example 3 Biggnuntle '177 No added No Added ◎ ◎ Example 4 Bigtre '177 Cobalt green No addition ◎ ◎ Comparative example 1 No addition Titanium oxide' Norvent green 3 X X Comparative example 2 Biggnuntie D-93 No addition No addition X ® Example 5 Pigmentable-60 No addition No Ο ◎ Example 6 Pigmented Ret F'178 No Add No 〇 ◎ Example 7 Big Tre '149 No Add No Add ο ◎ Example 8 Big Green 36 Ultramarine Blue No Add 〇 ◎ Comparative Example 3 No addition No addition Solvent tray, G '151 ◎ X Comparative example 4 Pigment pallet? G 23 No addition No addition X ◎ Example 9 Big tonello-183 No addition and no addition 〇 ◎ Example 10 big; / Tretz F 209 No addition without addition ◎ ◎ Example 11 Bigon yellow 147 No addition No addition ◎ ◎ Example 12 Vigne D-150 Vengara No addition 〇 ◎ Comparative example 5 No addition No addition Solvent yellow-163 XX Comparative example 6 Vigmen range 13 No addition No addition X ◎ Example 13 Pigmentlet '149 Not added Not added 〇 ◎ Example 14 Pigment W 202 Not added without added ◎ ◎ Example Example green 7 Not added without added 〇 ◎ Example 16 Vigtor 'Noto' 177 Cobalt pull-Not added ◎ ◎ Comparative example 7 Not added No added / Lupentofle-94 XX Comparative example 8 Bigunun 'No F'. 180 Not added Not added X ® (Examples 5 to 8, Comparative Examples 3 to 4)

55 parts by weight of SPS obtained in Production Example 2 was blended with 55 parts by weight of Nylon (manufactured by Ube Industries, Ltd .; trade name: 200 U) 45 parts by weight using a twin-screw kneader. Pellets (A) were prepared by melt-kneading at 90 ° C. On the other hand, based on 55 parts by weight of SPS obtained in Production Example 2 and 45 parts by weight of nylon, 3 parts by weight of the inorganic pigment shown in Table 1, 0.3 parts by weight of the organic pigment, and Was blended at 0.20 parts by weight as shown in Table 1 and melt-kneaded at 290 ° C using a twin-screw kneader to produce a high-concentration colored pellet (master batch) (B). did.

Pellet (A) and pellet (B) were blended at a ratio of 29: 1 to use as raw material for injection molding. The results are shown in Table 1.

(Examples 9 to 12, Comparative Examples 5 and 6)

To 5 parts by weight of the SPS obtained in Production Example 3, 25 parts by weight of glass fiber (manufactured by Asahi Fine Barglass Co., Ltd .; trade name: 03 JA 'FT712) was blended. 1.0 part by weight of the inorganic pigment, 0.1 part by weight of the organic pigment, and 0.01 part by weight of the dye shown in Table 1 were blended as shown in Table 1, and the mixture was mixed at 290 ° C using a twin-screw kneader. The mixture was melt-kneaded at to prepare pellets. This pellet was used as a raw material for injection molding. The results are shown in Table 1.

(Examples 13 to 16, Comparative Examples 7 to 8)

To 8 parts by weight of SPS obtained in Production Example 4, 35 parts by weight of glass fiber [manufactured by Asahi Fine Bargrass Co., Ltd .; trade name: 03 JA. FT71 2], rubber [Kuraray Co., Ltd.] 20 parts by weight of septon (trade name: Septon 8006), bromide-based flame retardant [manufactured by Huguchi Co., Ltd .; trade name: pi-mouth check 68 PBC] The pellet (A) was prepared by melt-kneading at 290 ° C using a shaft kneader. On the other hand, 50 parts by weight of SPS obtained in Production Example 4, 30 parts by weight of rubber as described above, and 20 parts by weight of Then, 100 parts by weight of the inorganic pigment, 15 parts by weight of the organic pigment, and 1 part by weight of the dye shown in Table 1 were blended as shown in Table 1, and the mixture was mixed using a twin-screw kneader. The mixture was melted and kneaded at 290 ° C to produce a high-concentration colored pellet (master batch) (B).

Pellet (A) and pellet (B) were blended at a ratio of 49: 1 to use as raw material for injection molding. The results are shown in Table 1.

Industrial applicability

As described above, the organic pigment for coloring of SPS of the present invention, the coloring material for coloring of SPS, and a mixture of SPS with a certain component, if necessary, and a styrene-based coloring material comprising the coloring material for coloring. The resin composition retains the excellent properties of SPS such as heat resistance, generates bleeding during molding, has excellent processing stability without causing mold contamination, and has excellent color stability when commercialized. It has excellent quality stability without any shift.

Therefore, the styrenic resin composition of the present invention is expected to be effectively used for applications required for each color of the connector.

Claims

The scope of the requiem

1. At least one selected from (a) metal-containing azo pigments, (b) copper phthalocyanine pigments, (c) perylene pigments, (sullen pigments and (e) quinacridone pigments) Styrene-based polymer (SPS) with various syndiotactic structures Organic pigment for coloring

2. (a) metal-containing azo pigment, (b) copper phthalocyanine pigment, (c) perylene pigment, (slen pigment and (e) quinacridone pigment Styrene-based polymer (SPS) coloring material with syndiotactic structure using at least one organic pigment

3. Inorganic pigments, (a) metal-containing azo pigments, (b) copper phthalocyanine pigments, (c) perylene pigments, (d) styrene pigments, and (e) quinatari pigments. Styrene-based polymer (SPS) having a syntactic structure consisting of at least one organic pigment selected from don-based pigments

4. (A) (a) 20-100% by weight of a styrene-based polymer (SPS) having a syndiotactic structure, (b) a rubber-like elastic material, and (c) a syndiotactic structure. 100 parts by weight of an SPS compound comprising at least 80 to 0% by weight of a thermoplastic resin other than the styrenic polymer and (d) an inorganic filler, and (B). Or a styrenic resin composition composed of 0.001 to 200 parts by weight of the SPS coloring material described in 3.