JPH10120931A - Organic pigment for coloring syndiotactic styrene-based polymer (sps), coloring material for coloring sps and styrene-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment capable of exhibiting excellent processing stability and service stability by including a specific organic pigment. SOLUTION: This pigment comprises at least one selected from among (A) a metal-containing azo pigment, (B) a copper phthalocyanine-based pigment, (C) a perylene based pigment, (D) a indanthrene-based pigment and (E) a quinacridone-based pigment. The pigment or a mixture of the pigment with an inorganic pigment can be used as a coloring material for coloring syndiotactic styrene-based polymer (SPS). This resin composition can be obtained by compounding 100 pts.wt. SPS compound comprising 20-100wt.% SPS and 80-0wt.% at least one among a rubber-based elastomer, a thermoplastic resin other than SPS and an inorganic filler with 0.001-200 pts.wt. coloring material for coloring SPS compound. The resin composition does not cause pollution of mold due to bleeding in molding and is excellent in processing stability and quality stability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coloring material used for a styrenic polymer having a syndiotactic structure (hereinafter sometimes abbreviated as "SPS") and SP.
The present invention relates to a styrene-based resin composition comprising a mixture of S and a certain component, and the coloring material. More specifically, the present invention relates to an SPS coloring material and a styrene-based resin composition that do not cause contamination of a mold due to bleeding of the coloring material during molding.

[0002]

2. Description of the Related Art Since SPS has extremely excellent properties such as heat resistance, chemical resistance, electrical properties, and water absorption dimensional stability, it has been conventionally used as an engineering plastic for various applications. However, colored ones are sometimes required depending on the application, for example, when it is necessary to identify a relay connector or a color.

[0003] Usually, various dyes and pigments are used for coloring a resin. When coloring a certain resin, when selecting a coloring material, sharpness, coloring power, dispersibility, and heat resistance are considered. Investigations have been made from every angle, including weather resistance, color transfer, water resistance, solvent resistance, chemical resistance, and toxicity. For example, dyes that are generally referred to as oil-soluble dyes are used. However, bleeding and migration (migration) of resins such as soft vinyl chloride, polyethylene, and polypropylene are intense except in special cases. Although they cannot be used, they are widely used in styrene resins such as polymethyl methacrylate, polystyrene and ABS resins because of their good dispersibility, transparency and sharpness.

On the other hand, pigments are roughly classified into inorganic pigments and organic pigments, and each is classified according to its structure.
Organic pigments are selected from the viewpoint of transparency, clarity, and coloring, and inorganic pigments are selected from the viewpoint of hiding power, heat resistance, and weather resistance. By the way, when coloring SPS, general dyes and pigments used for ordinary resins cannot always be applied as they are due to the excellent properties of SPS itself as a resin. In other words, SPS, which is particularly excellent in heat resistance, requires a high temperature for crystallization at the time of molding, so the mold temperature must be increased, so that general dyes used in ordinary resins cause bleeding, It cannot be used because it causes mold contamination. Further, for example, even if a pigment is used for a resin that requires a high temperature for molding, such as a polycarbonate, it is not necessarily applicable to the SPS.

[0005] As described above, no knowledge has been obtained about the coloring material for SPS, and an appropriate coloring material has been awaited at present.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an organic pigment for coloring SPS, a coloring material for coloring SPS, and an SPS having excellent processing stability and service stability. It is another object of the present invention to provide a styrene-based resin composition comprising a compound containing certain components as necessary and the coloring material.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific organic pigment is extremely effective for coloring SPS. It has been found that inorganic pigments can be used as coloring materials for coloring SPS. The present invention has been completed based on such findings.

That is, the present invention provides (a) a metal-containing azo pigment,
(b) Copper phthalocyanine pigment, (c) Perylene pigment, (d)
An object of the present invention is to provide at least one kind of SPS coloring organic pigment (1) selected from a sullen pigment and (e) a quinacridone pigment, and to provide an SPS coloring material (2) using the organic pigment. And an SPS coloring material (3) comprising an inorganic pigment and the organic pigment. (A) (a) SPS 20 to 100% by weight
And (b) a rubber-like elastic material, (c) a thermoplastic resin other than a styrene-based polymer having a syndiotactic structure, and (d) at least one 80% by weight selected from inorganic fillers. 100 parts by weight of the composition and the above (2)
Or the colorant for SPS coloring described in (3) 0.001 to 200
It is intended to provide a styrene resin composition comprising parts by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION 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 below. 1. Organic pigments for SPS coloring (a) Metal-containing azo pigments Metal-containing azo pigments are azo pigments having a hydrophilic group or a substituent containing a hydrophilic group, which are water-soluble or poorly water-soluble. For example, it refers to an azo lake pigment which is made insoluble (lake) by forming a salt with aluminum, calcium, barium, strontium, manganese, iron, lead, tin, nickel or the like. Here, the hydrophilic group is, for example, -S
_{O 3 H, -SO 3 M,} -OSO 3 H, -OSO 3 M, -CO
OM, -NR ₃ X (M is an alkali metal or -NH _4, R
Represents an alkyl group, and X represents a halogen. ) Or a group generated by condensation of these groups (for example, —SO ₃ NH ₂ CO— or the like). An azo pigment is generally obtained by a coupling reaction of a diazonium salt obtained by diazotizing an aromatic amine with a phenol or naphthol, usually in the presence of an alkali, and includes an azo group (-N = N-). Here, examples of the metal salt used for insolubilizing (raking) the water-soluble or poorly water-soluble azo pigment include aluminum sulfate, barium chloride, tin chloride, strontium chloride, calcium chloride, manganese chloride, iron chloride, and acetic acid. Lead and the like.

As the metal-containing azo pigment, specifically,
Pigment Yellow 150, Pigment Yellow 18
3, Lake Red C, Brilliant Carmine 6B, Watching Red, Lisor Red, Brilliant Scarlet G, Lake Red D, and the like. (b) Copper phthalocyanine pigment The copper phthalocyanine pigment is a copper phthalocyanine having a structure represented by the following general formula (I) which is converted into a pigment (for example,
The crude product is dissolved in concentrated sulfuric acid, and then the concentration of sulfuric acid is reduced to obtain fine crystals by precipitation, etc.), and further provided as a coloring material through a drying step and the like.

[0011]

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[0012] Since copper phthalocyanine has various crystal forms, there is a possibility that coloring power may be reduced or a hue may change due to crystal transition. Therefore, generally, several halogen atoms on the benzene ring of the copper phthalocyanine molecule,
Preferably, a method of preventing crystal transition or crystal growth by introducing chlorine is used, but this halogenated 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 it 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, and Pigment Green 7. (c) Perylene pigment The perylene pigment is represented by the following general formula (II) in the chemical structure:
Refers to those having the structure represented by

[0014]

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(Where X is H, -R, -Ph, -Ph
_{-R, -Ph-R 2, -Ph} -OR, -COR, -Ph
-N = N-Ph, -Ph-HC = CH-Ph (where,
R represents an alkyl group having 1 to 10 carbon atoms, and Ph represents a phenyl group. ). Preferably, -Ph-OC
_{H 3, -Ph-OC 2 H} 5, -Ph- (CH 3) 2, -C
_{H 3, H, -Ph-N} = N-Ph, a -COCH ₃ shows. Specific examples of perylene pigments include Pigment Red 1
78, perylene red (pigment red 190), perylene vermillion (pigment red 123), perylene scarlet (pigment red 149), perylene maroon (pigment red 179), perylene brown (pigment brown 26) and the like. (d) Slen-based pigment Slen-based pigment is represented by the following general formula (III) in its chemical structure:
And having an anthraquinone structure or an anthraquinone derivative.

[0016]

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Specific examples of the slen pigment include dianthraquinolyl red (pigment red 177), indanthrone blue (pigment blue 60), pigment yellow 147, anthrapyrimidine yellow (pigment yellow 108), and acylamide yellow (pigment yellow). 99), flavantron yellow (pigment yellow 24), pyranthrone orange (pigment orange 40), anthantrone orange (pigment red 168), isobiolanthrone blue (pigment violet 31), pigment red 216
Pigment Violet 33, Pigment Blue 22,
Pigment Blue 21, Pigment 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.

[0018]

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(Where X is H, -R (R is carbon number 1 to
Represents 10 alkyl groups. Preferably -CH _3), halogen (preferably shows a -Cl). Specific examples of quinacridone pigments include quinacridone red (pigment violet 19), quinacridone magenta (pigment red 122), quinacridone scarlet (pigment red 207), quinacridone red (pigment red 209), quinacridone maroon (pigment red 206), Pigment Red 20
2 and the like. 2. SPS Coloring Material The above-mentioned specific organic pigment or a combination of the organic pigment and the inorganic pigment is used as the SPS coloring material.

The inorganic pigment is not particularly limited.
For example, titanium oxides such as titanium white and titanium yellow, iron oxides such as red iron oxide and iron oxide yellow, oxides such as zinc white and chromium green, and chromic acids such as graphite and chromium vermillion Molybdenum-based,
Cadmium selenide such as cadmium yellow and cadmium red; mercury sulfide such as mercury red; ferrocyanide such as navy blue; aluminum silicate such as ultramarine blue; aluminum powder and bronze powder; Examples include metal powder, carbon black, and pearl mica. 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 together,
Coloring and coloring are improved, and so-called color vividness is increased. In addition, pigment dispersants such as metal soaps, mineral oils, low-molecular-weight thermoplastic resins, monoamides and bisamides can be added to improve the color development. 3. Styrene-based resin composition (A) 20 to 100% by weight of SPS (a), at least one kind 80 selected from (b) rubbery elastic body, (c) thermoplastic resin other than SPS, and (d) inorganic filler 100 parts by weight of an SPS formulation consisting of:
It is composed of 0.001 to 200 parts by weight of a coloring material for PS coloring. (1) (A) SPS compound As the SPS compound to which the SPS coloring material is added,
Although SPS can be used alone, it can be specifically used as the following compound.

(A) a blend of 20 to 99% by weight of SPS and (b) a blend of 80 to 1% by weight of a rubber-like elastic material, (a) 20 to 99% by weight of SPS and (c) a thermoplastic resin other than SPS 1% by weight, (a) 20 to 99% by weight of SPS, and (d) inorganic filler 80
(A) 20 to 99% by weight of SPS, (b) a rubbery elastic body and (c) 80 to 1% by weight of a thermoplastic resin other than SPS, (a) A blend of 20 to 99% by weight of SPS, (b) a rubber-like elastic material and (d) 80 to 1% by weight of an inorganic filler, (a) 20 to 99% by weight of SPS and (c) a thermoplastic resin other than SPS, (d) a compound comprising 80 to 1% by weight of an inorganic filler, (a) 20 to 99% by weight of SPS and (b) a rubbery elastic body,
(c) thermoplastic resin other than SPS and (d) inorganic filler 80
(1) Next, each component in the composition will be described in detail. (a) Styrene-based polymer having syndiotactic structure (SPS) Styrene-based polymer having syndiotactic structure (SPS)
The syndiotactic structure in PS) means that the steric structure is a syndiotactic structure, that is, phenyl groups and substituted phenyl groups which are side chains with respect to the main chain formed from carbon-carbon bonds are alternately located in opposite directions. It has a three-dimensional structure, and its tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon.
Tacticity measured by ¹³ C-NMR method is
The abundance ratio of a plurality of continuous structural units, for example, dyad for two, triad for three, and pentad for five, styrene having a syndiotactic structure referred to in the present invention. The term “polymer” means usually 75% or more in racemic diad, preferably 85% or more, or 30% or more in racemic pentad,
Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinylbenzoic ester), preferably having a syndiotacticity of 50% or more, And a mixture thereof, or a copolymer containing these as a main component. In addition, here, as poly (alkyl styrene),
Poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary-butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), poly (vinylstyrene), etc.
Examples of poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

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

The styrene polymer may be used alone or in combination of two or more. Although the molecular weight of the styrene polymer is not particularly limited, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. Furthermore, 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 10,000, the thermal properties and mechanical properties of the resulting composition or molded article may be undesirably reduced.

The styrenic polymer having such a syndiotactic structure is prepared, for example, in an inert hydrocarbon solvent,
Or by producing a styrene-based monomer (a monomer corresponding to the styrene-based polymer) using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in the absence of a solvent. (Japanese Unexamined Patent Publication No. Sho 62)
187708). The 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-1-178505.

In the composition of the present invention, the (a) styrene-based polymer having a syndiotactic structure is contained in an amount of 20.
It is contained in the range of １００100% by weight. If the SPS is less than 20% by weight, the excellent characteristics of the SPS are not exhibited, which is not preferable. (b) Rubber-like elastic body Examples of the rubber-like elastic body include natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene- Butadiene block copolymer (SB
R), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-
Styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS),
Hydrogenated styrene-isoprene-styrene block copolymer (SEPS), ethylene propylene rubber (EP
R), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (ABS), methyl methacrylate-butadiene-styrene-core-shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core-shell rubber (MAS) Octyl acrylate-butadiene-styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (ABS), butadiene-styrene-core-shell rubber (SBR), methyl methacrylate-
Core-shell type particle-like elastic bodies such as siloxane-containing core-shell rubbers such as butyl acrylate siloxane, and rubbers obtained by modifying these.

Among these, in particular, SBR, SEB, S
BS, SEBS, SIR, SEP, SIS, SEPS,
Core-shell rubber, EPM, EPDM, or rubber modified from these are preferably used. In addition, these rubber-like elastic bodies can be used alone or in combination of two or more. (c) Thermoplastic resin other than SPS The thermoplastic resin can be arbitrarily selected from conventionally known ones as long as it is a resin other than the above-mentioned SPS. Low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, cyclic polyolefin, polyolefins including poly-4-methylpentene Resin, polystyrene, HIPS, ABS, AS
And polystyrene resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polyamide 6, polyamide 6, and 6, polyphenylene ether, and polyphenylene sulfide. In addition, only one kind of the thermoplastic resin may be used alone, or two or more kinds may 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, whisker, and the like. As the shape of the fibrous inorganic filler, there are a whisker itself in addition to a cross shape, a mat shape, a bundle cut shape, a short fiber shape, and the like. In the case of the bundle cut shape,
Those having a length of 0.05 to 50 mm and a fiber diameter of 5 to 20 μm are preferred.

On the other hand, as the material of the granular or powdery inorganic filler, for example, talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate,
Calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate,
Examples include tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads. Among such inorganic fillers, in particular, glass fillers such as glass powder, glass flake,
Glass beads, glass filaments, glass fibers, glass lobing, and glass mats are preferred.

As the inorganic filler, those which have been subjected to a surface treatment with a coupling agent or the like in order to improve the adhesion to the resin are preferably used. As the coupling agent, a silane coupling agent, a titanium coupling agent, or any conventionally known coupling agent can be arbitrarily selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Aminosilanes such as silane, epoxysilane, and isopropyl tri (N-amidoethyl, aminoethyl) titanate are preferred.

Further, a film-forming substance (film former) can be used in combination with the above-mentioned coupling agent. As the film-forming substance, conventionally known substances can be used without any particular limitation. System, epoxy system, polyether system and the like are preferably used. Such an inorganic filler may be used alone, but may be used in combination of two or more if necessary. (3) In the above-mentioned SPS compound, the method of mixing the respective components is not particularly limited, and conditions such as the order of addition and the mixing method can be arbitrarily set. The mixture also includes those obtained by mixing and then kneading the components. The method of melt-kneading is not particularly limited, and a conventionally known method can be used. (4) The styrenic resin composition may contain various additional components such as an antioxidant, a nucleating agent, a plasticizer, a release agent, a flame retardant, a flame retardant auxiliary, and a charge as long as the object of the present invention is not impaired. Additives such as inhibitors can be included.

As a nucleating agent, aluminum di (pt-
Butyl benzoate), metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate, talc, phthalocyanine derivatives, and the like. Can be selected and used. These nucleating agents can be used alone or in combination of two or more.

The plasticizer can be arbitrarily selected from known ones such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalate ester, polystyrene oligomer, polyethylene wax, mineral oil and silicone oil. . These plasticizers can be used alone or in combination of two or more.

As the release agent, polyethylene wax,
Any known materials such as silicone oil, long-chain carboxylic acid, and long-chain carboxylate can be used. These release agents may be used alone or in combination of two or more. As the antioxidant, any of known antioxidants such as phosphorus-based, phenol-based, and sulfur-based can be used. These antioxidants can be used alone or in combination of two or more.

Known flame retardants include brominated polymers such as brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether, and brominated aromatic compounds such as brominated diphenylalkane and brominated diphenyl ether. Can be arbitrarily selected and used. In addition, as the flame retardant auxiliary, antimony compounds such as antimony trioxide, and others can be arbitrarily selected and used, respectively, one type alone may be used alone, or two or more types may be used in combination. Can also be used. (5) Production method of styrene resin composition Production of styrene resin composition comprising SPS compound and SPS coloring material (that is, the above-mentioned specific organic pigment, or the organic pigment and the inorganic pigment) There is no particular limitation on the method. For example, it can be manufactured by the following method. A method in which the components constituting the SPS compound and the SPS coloring material are simultaneously mixed and then melt-kneaded to form pellets. In this case, the ratio of the SPS compound to the SPS coloring material is as follows. 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight of the SPS coloring material with respect to parts by weight.
Parts by weight. A method in which the components constituting the SPS compound are first mixed, melt-kneaded to produce pellets, then mixed with the SPS coloring material, and melt-kneaded again to form pellets. Also in this case, the ratio of the SPS compound to the SPS coloring material is the same as described above. A high-concentration colored pellet (masterbatch) obtained by simultaneously mixing and melting and kneading each component constituting the SPS compound and the SPS coloring material, and mixing and melt-kneading each component constituting the SPS compound. A method of blending with the pellets obtained in a ratio according to the application.

The ratio of the SPS compound to the SPS coloring material in the preparation of the master batch is such that the SPS coloring material is 0.1 to 200 parts by weight based on 100 parts by weight of the SPS compound.
Parts by weight, preferably 0.5 to 150 parts by weight. The pellets or a blend thereof obtained by these methods are provided as a raw material for molding such as injection molding, depending on the required use.

[0037]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. [Production Example 1] An organometallic compound (hereinafter referred to as a catalyst system) comprising triisobutylaluminum as component (c), methylaluminoxane as component (b) and pentamethylcyclopentadienyltitanium trimethoxide as component (a). , X), and styrene (hereinafter abbreviated as SM) was polymerized (conversion rate = 21%). At this time, each component is represented by SM: X:
Component (c): Component (b): Component (a) = 350000:
Mix at a molar ratio of 25: 25: 75: 1 and polymerize at 70 ° C.
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 methyl ethyl ketone as a solvent, the insoluble content was 97%. Its weight average molecular weight was 730,000. [Production Example 2] Triisobutylaluminum as component (c), dimethylanilinium tetra (pentafluorophenyl) borate as component (b), and pentamethylcyclopentadienyltitanium trimethoxide as component (a). Triethylaluminum was added to the catalyst system as an organometallic compound (hereinafter abbreviated as X) to polymerize styrene (hereinafter abbreviated as SM) (conversion rate = 35).
%). At this time, each component is represented by SM: X: (c) component: (b)
Component: (a) component = 350,000: 25: 20: 1: 1
And the polymerization was carried out at 70 ° C. for 1 hour. After finely pulverizing the polymer, the polymer was sufficiently washed with methanol and dried under reduced pressure. The polymer obtained was subjected to Soxhlet extraction for 6 hours using methyl ethyl ketone as a solvent.
8%. Its weight average molecular weight was 390,000. [Production Example 3] First, 90 μmol of pentamethylcyclopentadienyltitanium trimethoxide, 90 μmol of dimethylanilinium tetra (pentafluorophenyl) borate, 29.1 mmol of toluene, and 1.8 mmol of triisobutylaluminum were mixed. A premixed catalyst was prepared. Next, 1.0 liter of purified styrene and 1 mmol of triethylaluminum were added to a reaction vessel having an internal volume of 2 liters, and the mixture was heated to 75 ° C.
Milliliter 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 and found to be 263,500.

[Production Example 4] Polymerization was carried out in exactly the same manner as in Production Example 2 except that the amount of the organometallic compound, triethylaluminum, was changed to 200 times the amount of the component (a). The conversion was 25%. The weight average molecular weight was 130,000. [Evaluation Test] The following tests were performed using the injection molding raw materials obtained in Examples and Comparative Examples. (1) Retention heat stability test A test sheet piece (90 mm × 40 mm × 3 mm) obtained by injection-molding the injection molding material at 290 ° C. was injection-molded at 290 ° C. And a test sheet piece (90 mm ×
(40 mm x 1 mm), the degree of discoloration was examined.
In the CIE1976 L ^* a ^* b ^* color space and display (ΔEab ^* ) using the color difference equation, the following evaluation was performed.
When ΔEab ^* was less than 2 (that is, there was almost no discoloration), ◎ was given, and when ΔEab ^* was 2 or more and less than 5 (that is, a little discoloration was seen), ΔEab ^* was 5 or more. (I.e., those which are so discolorable that they cannot be used practically) are marked as x.

(2) Color material transfer test A white vinyl chloride sheet (30 mm x 30 mm x 2 mm) was added to a test sheet piece (90 mm x 40 mm x 3 mm) obtained by injection molding the injection molding material at 290 ° C. Were adhered for 2 hours and peeled off. The color difference before and after close contact of the white vinyl chloride sheet with the test sheet piece was measured. A sample having ΔEab ^* of less than 2 (that is, a sample having almost no discoloration) was evaluated as ◎, and no color migration was observed. ΔEab
^* Is 2 or more (that is, one in which discoloration was slightly observed) was evaluated as x, and color transferability was determined.

[Examples 1-4, Comparative Examples 1-2] Production Example 1
In 100 parts by weight of the SPS obtained in the above, 0.01 part by weight of the inorganic pigment, 0.055 parts by weight of the organic pigment, and 0.055 parts by weight of the dye shown in Table 1 as shown in Table 1 The pellets were blended and melt-kneaded at 290 ° C. using a biaxial kneader to produce pellets. This pellet was used as a raw material for injection molding.
The results are shown in Table 1.

[0041]

[Table 1]

Examples 5 to 8, Comparative Examples 3 and 4 Production Example 2
45 parts by weight of nylon [manufactured by Ube Industries, Ltd .; trade name 2020U] are blended with 55 parts by weight of the SPS obtained in the above, and the mixture is melt-kneaded at 290 ° C. using a twin-screw kneader to prepare a pellet (A). . On the other hand, the SPS obtained in Production Example 2
55 parts by weight and 45 parts by weight of nylon
As shown in Table 1, 3 parts by weight of an inorganic pigment, 0.3 parts by weight of an organic pigment, and 0.2 parts by weight of a dye were blended as shown in Table 1, and the mixture was heated to 290 ° C. using a twin-screw kneader. The mixture was melt-kneaded to produce a high-concentration colored pellet (master batch) (B).
A blend of the pellet (A) and the pellet (B) at a ratio of 29: 1 was used as a raw material for injection molding. The results are shown in Table 1.

[Examples 9 to 12, Comparative Examples 5 to 6] Production Example 3
Glass fiber [manufactured by Asahi Fiber Glass Co., Ltd .; trade name 03JA FT712] 2
5 parts by weight were blended, and the inorganic pigment shown in Table 1 was added to 1.0 part.
Parts by weight, 0.1 part by weight of an organic pigment and 0.11 part by weight of a dye were blended as shown in Table 1 and melt-kneaded at 290 ° C. using a twin-screw kneader 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] Production Example 4
Glass fiber [manufactured by Asahi Fiberglass Co., Ltd .; trade name 03JA FT712] 3
5 parts by weight, rubber [manufactured by Kuraray Co., Ltd .; trade name: Septon 80
06] 20 parts by weight, bromo flame retardant [manufactured by Ferro Corporation;
17 parts by weight of trade name Pyrocheck 68PBC] were blended and melt-kneaded at 290 ° C. using a biaxial kneader to prepare a pellet (A). On the other hand, the SP obtained in Production Example 4
For 50 parts by weight of S, 30 parts by weight of rubber, and 20 parts by weight of bromo-based flame retardant, 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 used. As shown in Table 1, each was blended and melt-kneaded at 290 ° C. using a twin-screw kneader to prepare a high-concentration colored pellet (master batch) (B). A blend of the pellet (A) and the pellet (B) at a ratio of 49: 1 was used as a raw material for injection molding. The results are shown in Table 1.

[0045]

As described above, the organic colorant for coloring of SPS of the present invention, the coloring material for coloring of SPS, and a mixture of SPS with a certain component as required, and the coloring material for coloring. The styrenic resin composition retains the excellent properties of SPS such as heat resistance, bleeds at the time of molding, does not cause mold contamination, and has excellent processing stability. It has excellent quality stability without migration. Therefore, the styrenic resin composition of the present invention is expected to be effectively used for applications requiring different colors such as connectors.

Claims (4)

[Claims] 1. At least one kind of syndye selected from (a) a metal-containing azo pigment, (b) a copper phthalocyanine pigment, (c) a perylene pigment, (d) a sulene pigment and (e) a quinacridone pigment. Organic pigments for coloring styrenic polymers (SPS) with tactic structure 2. At least one organic compound selected from the group consisting of (a) a metal-containing azo pigment, (b) a copper phthalocyanine pigment, (c) a perylene pigment, (d) a sullen pigment and (e) a quinacridone pigment. Colorant for coloring styrenic polymer (SPS) with syndiotactic structure using fluorinated pigment 3. An inorganic pigment and at least one selected from (a) a metal-containing azo pigment, (b) a copper phthalocyanine pigment, (c) a perylene pigment, (d) a sulene pigment, and (e) a quinacridone pigment. Styrene-based polymer (SPS) coloring material having one type of organic pigment and having a syndiotactic structure (A) (a) 20 to 100% by weight of a styrenic polymer (SPS) having a syndiotactic structure
And (b) a rubber-like elastic material, (c) a thermoplastic resin other than a styrene-based polymer having a syndiotactic structure, and (d) at least one 80% by weight selected from inorganic fillers. 100 parts by weight of the blend, and (B) the colorant for SPS coloring according to claim 2 or 3, 0.001 to 200.
Styrene resin composition consisting of parts by weight