KR100754914B1 - Thermoplastic resin composition and molded articles - Google Patents

Abstract

The thermoplastic resin composition of the present invention comprises 100% by weight of the total of the following components (A), (B) and (C), and is excellent in flame retardancy, impact resistance, and molded article surface appearance:

(A) Rubber modified styrene resin 5-98 which is a graft polymer which consists of 3-40 weight% of rubbery polymers (a), and the vinyl monomer (b) 60-97 weight% which consists of an aromatic vinyl compound and a vinyl cyan compound as desired. Weight%, (B) The vinyl monomer which consists of an aromatic vinyl compound and a vinyl cyan compound as needed, and a hydroxyl group containing unsaturated compound, a carboxyl group containing unsaturated compound, an acid anhydride group containing unsaturated compound, an epoxy group containing unsaturated compound, and an oxazoline group containing unsaturated compound 1-74 weight% of modified styrene resins which consist of a vinyl monomer selected from among, and (C) 1-21 weight% of polyorganosiloxane.

Thermoplastic resin composition, rubbery polymer, vinyl compound, graft polymer, styrene resin, polyorganosiloxane

Description

Thermoplastic composition and molded article {THERMOPLASTIC RESIN COMPOSITION AND MOLDED ARTICLES}

The present invention relates to a thermoplastic resin composition excellent in flame retardancy, molded article surface appearance and impact resistance, and a molded article made of the present thermoplastic resin composition.

Rubber-modified styrene-based resins represented by ABS resins and HIPS, and flame-retardant resin compositions obtained by flame retarding a composition of these and polycarbonate resins are excellent in mechanical properties, physical properties, and electrical properties. It is widely used in electronics, 0A, home appliances, vehicles, and hygiene.

The flame retardant represented by a halogen type flame retardant (for example, refer patent document 1), an organophosphorus flame retardant (for example, refer patent document 2, patent document 3), etc. is used for flame retardation of these resin.

In these flame retardant resin compositions, when a halogen flame retardant is used, there is a problem of causing metal corrosion such as a processing machine. In addition, when phosphorus-based flame retardants such as phosphate compounds are used, the flame retardant acts as a plasticizer of the resin, resulting in poor mechanical strength, heat resistance, and the like.

[Patent Document 1] Japanese Patent No. 3198485

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-87337

[Patent Document 3] Japanese Unexamined Patent Publication No. 10-120853

An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, molded article surface appearance and impact resistance, and a molded article made of such a thermoplastic resin composition.

According to this invention, the thermoplastic resin composition and molded article of the following structure are provided and the said objective of this invention is achieved.

That is, according to one aspect of the present invention, there is provided a thermoplastic resin composition (hereinafter referred to as "thermoplastic resin composition 1") consisting of a total of 100% by weight of the following components (A), (B) and (C): do:

(A) Rubber modified styrene resin 5-3 which is a graft polymer consisting of 3-40 weight% of rubbery polymers (a) and 60-97 weight% of vinyl monomers (b) which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound. 98% by weight,

(B) 30-99 weight% of vinyl monomers which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound, and a hydroxyl group containing unsaturated compound, a carboxyl group containing unsaturated compound, an acid anhydride group containing unsaturated compound, an epoxy group containing unsaturated compound, and an oxazoline group 1-74 weight% of modified styrene resins which consist of 1-70 weight% of at least 1 sort (s) of vinyl monomers chosen from containing unsaturated compound,

(C) 1 to 21% by weight of polyorganosiloxane.

Moreover, according to another aspect of the present invention, the thermoplastic resin composition (hereinafter referred to as "thermoplastic resin composition 2") is composed of a total of 100% by weight of the following components (A), (B), (C) and (D). Is provided:

(A) Rubber modified styrene resin 5-3 which is a graft polymer consisting of 3-40 weight% of rubbery polymers (a) and 60-97 weight% of vinyl monomers (b) which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound. 94% by weight,

(B) 30-99 weight% of vinyl monomers which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound, and a hydroxyl group containing unsaturated compound, a carboxyl group containing unsaturated compound, an acid anhydride group containing unsaturated compound, an epoxy group containing unsaturated compound, and an oxazoline group 1 to 90% by weight of a modified styrene resin composed of 1 to 70% by weight of at least one vinyl monomer selected from the group containing unsaturated compounds,

(C) 1 to 21% by weight of polyorganosiloxane,

(D) 4 to 93% by weight of at least one selected from aromatic polycarbonate resins, thermoplastic polyester resins, and polyarylene sulfides.

Moreover, according to another aspect of this invention, the molded article which consists of said thermoplastic resin composition is provided.

Embodiment of the Invention                     

(A) component of this invention is 3-40 weight% of rubbery polymers (a), 60-97 weight% of vinyl monomers (b) which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound, and said (b) as needed It is a rubber modified styrene resin which is a graft polymer which consists of other vinyl monomers copolymerizable with a) component.

As the rubbery polymer (a) used here, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene-acryl copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer Diene-based (co) polymers such as isobutylene-isoprene copolymer, hydrogenated products of these diene-based (co) polymers, ethylene-propylene- (nonconjugated diene) copolymers, ethylene-butene-1- (nonconjugated dienes) ) Copolymers, polyurethane rubbers, acrylic rubbers, silicone rubbers, and the like.

Among them, polybutadiene, butadiene-styrene copolymer, styrene-butadiene-styrene block copolymer and hydrogenated products of these butadiene moieties, ethylene-propylene- (nonconjugated diene) copolymer, acrylic rubber and silicone rubber are preferred and these are 1 It can be used individually by 1 type or in combination of 2 or more types.

The amount of the rubbery polymer (a) in the component (A) of the present invention is 3 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight, and the amount used is less than 3% by weight. Impact resistance is inferior and flame retardancy is inferior when it exceeds 40 weight%.

As an aromatic vinyl compound of (b) component, styrene, (alpha) -methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, methyl- (alpha) -methylstyrene, brominated styrene, hydroxy styrene, etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, styrene and α-methylstyrene are preferable.

As a vinyl cyan compound of (b) component, an acrylonitrile, methacrylonitrile, etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.

The amount of the vinyl monomer (b) in the component (A) of the present invention is 60 to 97% by weight, preferably 70 to 95% by weight, more preferably 80 to 95% by weight, and if the amount of use exceeds 97% by weight, Impact resistance is inferior and flame retardance is inferior when it is less than 60 weight%.

Moreover, as another vinyl monomer copolymerizable with the said (b) component, For example, (meth) acrylic acid ester, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate, maleimide And maleimide compounds such as N-methyl maleimide, N-butyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide. These can be used individually by 1 type or in combination of 2 or more types. Moreover, this maleimide compound can also be introduce | transduced by the method of imidating, after copolymerizing maleic anhydride.

The range of 0-50 weight% of the use ratio in (A) component of another monomer like the said (meth) acrylic acid ester and a maleimide compound is preferable.

A preferable use ratio of the said aromatic vinyl compound and a vinyl cyan compound is the range of aromatic vinyl compound / vinyl cyan compound = 60-85 / 40-15 weight%.

Component (A) of the present invention may be a graft polymer obtained by graft polymerization of a vinyl monomer (b) in the presence of a rubbery polymer (a), or a polymer obtained by polymerizing a vinyl monomer (b) in the absence of a rubbery polymer (a). A mixture with the graft polymer may be used, or any of them can be used.

The component (A) of the present invention can be polymerized by an emulsion polymerization, a bulk polymerization, a solution polymerization, a suspension polymerization and a polymerization method in which these are known polymerization methods. Particularly preferred for achieving the object of the present invention is obtained by emulsion polymerization.

When prepared by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier and water are used. These can use all well-known things. In addition, the rubbery polymer (a) and vinyl monomer (b) to be used may be polymerized by collectively adding the vinyl monomer (b) in the presence of the whole amount of the rubbery polymer (a), or may be polymerized by being split or continuously added. have. Moreover, it can also superpose | polymerize by the method of combining these. Moreover, you may superpose | polymerize by adding all or part of the said rubbery polymer (a) in the middle of superposition | polymerization.

As a polymerization initiator, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxy laurate, t-butyl peroxy monocarbonate, etc. are mentioned.

As a chain transfer agent, it is octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, tetraethyl thiuram sulfide, acrolein, methacrolein, allyl alcohol, 2- Ethyl hexyl thioglycol etc. are mentioned.

As an emulsifier used at the time of emulsion polymerization, For example, aliphatic sulfonates, such as sulfate ester of a higher alcohol, alkylbenzene sulfonate of sodium dodecylbenzene sulfonate, and sodium lauryl sulfate, higher aliphatic carboxylate, rosin, phosphate Anionic surfactant, such as these, and also well-known nonionic surfactant can also be used.

In emulsion polymerization, the powder of rubber-modified styrene resin is obtained by drying after washing with water the powder obtained by coagulation | solidification with a coagulant normally. As a coagulant at this time, inorganic salts, such as calcium chloride, magnesium sulfate, and magnesium chloride, or acids, such as a sulfuric acid, hydrochloric acid, an acetic acid, can be used. Particularly preferred coagulant in the present invention is sulfuric acid.

Moreover, in block polymerization, solution polymerization, suspension polymerization, although various solvents, a suspension agent, a polymerization initiator, a chain transfer agent, etc. are used, all the well-known thing is used.

The average rubber particle diameter dispersed in the component (A) of the present invention is preferably in the range of 500 kPa to 30000 kPa, more preferably 1000 kPa to 20000 kPa, and particularly preferably 1500 kPa to 8000 kPa.

When obtaining (A) component of this invention by emulsion polymerization, the rubbery polymer obtained by emulsion polymerization is often used, In that case, the gel content in a rubbery polymer is 98 weight% or less normally, and it is preferable that it is 40-98 weight%. More preferably, it is 50 to 95 weight%, Especially preferably, it is 60 to 90 weight%. When the gel content is 40 to 98% by weight, a thermoplastic resin composition can be obtained that gives a molded article exhibiting particularly excellent flame resistance, impact resistance, and molded article surface appearance.

In addition, the gel content is 1g of rubbery polymer to toluene 100m1, and after standing at room temperature for 48 hours, filtered through 100 mesh wire mesh (weight W ₁ ) by vacuum drying the toluene insolubles and wire mesh at 80 ℃ for 6 hours to weigh Weight W ₂ ), and the value calculated by the following equation.

Gel content (%) = [{W ₂ (g) -W _l (g)} / 1 (g)] × 10 O

The gel content can be adjusted by appropriately setting the type and amount of the molecular weight modifier, the polymerization time, the polymerization temperature, the polymerization conversion rate and the like at the time of producing the rubbery polymer.

The graft ratio of the component (A) of the present invention is preferably 20 to 200% by weight, more preferably 30 to 150% by weight, particularly preferably 40 to 120% by weight. This graft rate (%) is required by the following equation.

Graft Rate (%) = {(T-S) / S} × 100

In the above formula, T is added to 1 g of a rubber-modified styrene-based resin in acetone 20m1, shaken by shaking for 2 hours, and then centrifuged for 60 minutes with a centrifuge (rotation speed; 23000rpm) and an insoluble component obtained by separating insoluble and soluble components. Is the weight (g), and S is the weight (g) of the rubbery polymer contained in 1 g of the rubber-modified styrene resin.

The intrinsic viscosity [η] of the acetone soluble component of the rubber-modified styrene resin (measured at 30 ° C. using methyl ethyl ketone as the solvent) is preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 1 Dl / g, particularly preferably 0.3 to 0.8 dl / g.

Component (B) of the present invention contains 30 to 99% by weight of a vinyl monomer comprising an aromatic vinyl compound or an aromatic vinyl compound and a vinyl cyan compound, and a hydroxyl group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an epoxy group-containing compound. It is a modified styrene resin which consists of 1 to 70 weight% of at least 1 sort (s) of vinyl monomers chosen from the group of the functional group containing unsaturated compound which consists of an unsaturated compound and an oxazoline group containing unsaturated compound.

As an aromatic vinyl compound and a vinyl cyan compound used here, all of said things can be used, The usage-amount of these vinyl monomers in (B) component of this invention is 30-99 weight%, Preferably it is 40-97 weight%, More Preferably it is 50 to 95 weight%, Especially preferably, it is 60 to 95 weight%. Outside this range, flame retardancy, impact resistance and molded article surface appearance are poor.

The hydroxyl group-containing unsaturated compound is 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy Hydroxy-2-methyl-1-propene, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide, and the like, and the like can be used alone or in combination of two or more thereof. .

Acrylic acid, methacrylic acid, etc. are mentioned as a carboxyl group-containing unsaturated compound, These can be used individually or in combination of 2 or more types.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, and citraconic anhydride, and these can be used alone or in combination of two or more thereof.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether, and these may be used alone or in combination of two or more thereof.

Vinyl oxazoline etc. are mentioned as an oxazoline group containing unsaturated compound, These can be used individually or in combination of 2 or more types.

The functional group-containing unsaturated compound may be used alone or in combination of two or more, and preferred are hydroxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, and carboxyl group-containing unsaturated compounds. Moreover, the other copolymerizable monomer enumerated as said (A) component can be used together as needed. The amount of the functional group-containing unsaturated compound in the component (B) of the present invention is 1 to 70% by weight, preferably 3 to 60% by weight, more preferably 5 to 50% by weight, particularly preferably 5 to 40%. Weight percent. Outside of the above range, flame retardancy, impact resistance and molded article surface appearance are inferior. The use ratio of the other copolymerizable monomer which can be used as needed is 0 to 50 weight% normally in (B) component, In order to acquire a use effect, Preferably it is 1 to 30 weight%.

The component (B) of the present invention improves the affinity between the component (A) and the component (C) to improve flame retardancy, impact resistance and the appearance of the molded article, but preferred combinations include styrene / 2-hydroxyethyl methacrylate. , Styrene / acrylonitrile / 2-hydroxyethyl methacrylate, styrene / methacrylic acid, styrene / acrylonitrile / methacrylic acid, styrene / glycidyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate Rate and the like.

The component (B) of the present invention can be produced by an emulsion polymerization, a bulk polymerization, a solution polymerization, a suspension polymerization or a polymerization method in which these are known polymerization methods.                     

About the manufacturing method in the case of manufacturing by emulsion polymerization, the method described by the said (A) component can be used.

The solvent used in solution polymerization is an inert polymerization solvent used in normal radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene, toluene, ketones such as methyl ethyl ketone, acetone, dichloromethylene, carbon tetrachloride, and the like. Halogenated hydrocarbons, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like. 80-140 degreeC of polymerization temperature is preferable, More preferably, it is 85-130 degreeC, Especially preferably, it is the range of 90-120 degreeC.

In the case of superposition | polymerization, you may superpose | polymerize by thermal polymerization, without using a polymerization initiator, and you may superpose | polymerize using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide and the like are preferably used. As a chain transfer agent, mercaptans, (alpha) -methylstyrene dimer, etc. can be used, for example.

In block polymerization, all the polymerization initiators, chain transfer agents, etc. which were described in solution polymerization can be used.

The intrinsic viscosity (measured at 30 ° C using methyl ethyl ketone as a solvent) of component (B) of the present invention is preferably 0.2 to 1.0 dl / g, more preferably 0.25 to 0.8 dl / g.

It is preferable that the amount of monomer finally remaining in (A) component and (B) component of this invention is 10000 ppm or less. More preferably, it is 5000 ppm or less.                     

The polyorganosiloxane of the component (C) of the present invention preferably has a polydimethylsiloxane as a basic structure, and the degree of polymerization of the polyorganosiloxane to be used, that is, the viscosity is preferably 10 to 5 million cSt at 25 ° C, more preferably. Preferably, 100 to 4 million cSt, particularly preferably 100,000 to 3 million cSt, and (C) component of 30 to 30% by weight or more, 30 to 30% by weight of 20 to 1000 cSt It is especially preferable to contain more than%.

Moreover, as (C) component of this invention, a part of substituents of Si of polyorganosiloxane, for example, 0.1 mol%-80 mol% of all the methyl groups of polydimethylsiloxane are alkoxy group, hydrogen, a phenyl group, a vinyl group, etc. Substituted with an unsaturated group and a hydroxyl group can also be used, and by constructing the entire amount of 1% by weight of the component (C) with these substituted polydimethylsiloxanes, a composition having more excellent flame retardancy, impact resistance, and molded article surface appearance can be obtained. have. Preferred substituents among the above are hydrogen, alkoxy group, unsaturated group and phenyl group.

Moreover, as (C) component of this invention, the side chain, one terminal, a side end, side chain / terminal of an amino group, an epoxy group, a carboxy group, a carbinol group, a methacryl group, a hydroxyl group, a mercapto group, You may use what modified | denatured by at least 1 sort (s) chosen from a phenol group.

(D) component of this invention is at least 1 sort (s) chosen from aromatic polycarbonate resin, thermoplastic polyester resin, and polyarylene sulfide.

As an aromatic polycarbonate resin used here, what is obtained by the interfacial polycondensation of various hydroxyaryl compounds and phosgene, or the transesterification reaction of carbonate compounds, such as a dihydroxy aryl compound and diphenyl carbonate (melt polycondensation) Although all obtained by the well-known polymerization method, such as the thing obtained by), can be used, What was obtained by the melt polymerization method from the viewpoint of welding strength is preferable. As dihydroxyaryl compound which becomes a raw material of aromatic polycarbonate resin, bis (4-hydroxyphenyl) methane, 1, 1-bis (4-hydroxyphenyl) ethane, 2, 2-bis (4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 '-Dihydroxydiphenylether, 4,4'-dihydroxy-3,3'-dimethyldiphenylether, 4,4'-dihydroxyphenylsulfide, 4,4'-dihydroxy-3, 3'-dimethylphenylsulfide, 4,4'-dihydroxyphenylsulfide, 4,4'-dihydroxy-3,3'-dimethylphenylsulfide De, 4,4'-dihydroxyphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethylphenylsulfoxide, 4,4'-dihydroxyphenylsulfone, 4,4'-di Hydroxy-3,3'-dimethyldiphenylsulfone, hydroquinone, resorcin, and the like, and these are used alone or in combination of two or more thereof. Especially preferred is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The said aromatic polycarbonate can be used individually by 1 type or in combination of 2 or more types of various polycarbonates obtained from the said raw material.

As for the viscosity average molecular weight of the said aromatic polycarbonate resin used by this invention, 13000-32000 are preferable, More preferably, it is 17000-31000, Especially preferably, it is 18000-30000. The viscosity average molecular weight and a different aromatic polyester carbonate may be used in combination, particularly a viscosity-average molecular weight 13000~19000 (D ₁₎ that is to be the _{20000~32000 (D 2) (D 1} ) / (D 2) = 10 / When it uses together at the ratio of 90-50 / 50 weight%, the thing excellent in the balance of impact resistance and fluidity is obtained.

In addition, the viscosity average molecular weight of aromatic polycarbonate resin can be computed by inserting the specific viscosity ((eta) _sp ) measured at 20 degreeC and the concentration [0.7g / 100ml (methylene chloride)] using methylene chloride as a solvent, in following Formula. .

Viscosity Average Molecular ^Weight = ([η] × 8130) ^1.205

(In the above formula, [η] = [(η _sp × 1.12 + 1) ^1/2 −1] /0.56C. In addition, C represents a concentration.)

In the aromatic polycarbonate resin used in the present invention, one obtained by interfacial polycondensation may contain various chlorine compounds. Since this chlorine compound may adversely affect the thermal stability of the thermoplastic resin composition of this invention, it is preferable that content of the chlorine compound of aromatic polycarbonate resin is 300 ppm or less as a chlorine atom, More preferably, it is 100 ppm or less.

As a thermoplastic polyester resin, the thing obtained by polycondensing dicarboxylic acid or its ester or ester forming derivative, and diol component by a well-known method, etc. are mentioned.

Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, heptalene-2,6-dicarboxylic acid, and the like, and these ester forming derivatives can also be used as components of the thermoplastic polyester resin of the present invention. have. Moreover, p-hydroxybenzoic acid can also be used individually or in combination with a diol component and a dicarboxylic acid component.

Examples of the diol component include polymethylene glycol having 2 to 6 carbon atoms (for example, ethylene glycol, 1,4-butanediol, 1,6-hexanediol), 1,4-cyclohexanediol, bisphenol A, hydroquinone and These ester formation derivatives etc. are mentioned, The said dicarboxylic acid component, the said diol component, etc. can be used individually by 1 type or in combination of 2 or more types.

Preferred thermoplastic polyester resins are polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate and the like, and more preferably polyethylene terephthalate and polybutylene terephthalate.

The intrinsic viscosity of the thermoplastic polyester resin used in the present invention is not particularly limited, and all known ones can be used, but in the case of polyethylene terephthalate, the intrinsic viscosity measured at 25 ° C. in an equivalent mixed solvent of tetrachloroethane / phenol [ (eta)] (unit dl / g), Preferably it is 0.5-2 dl / g, More preferably, it is the range of 0.5-1.5 dl / g. In the case of polybutylene terephthalate, it is the range of 0.4-2.0 preferably as intrinsic viscosity [(eta) / (g / g) measured at 25 degreeC in the solvent which consists of O-chlorophenol.                     

The polyarylene sulfide of this invention is a polymer which consists essentially of arylene groups couple | bonded with each other by the sulfide group, and is represented by the following general formula.

(-Ar-S-) n

(In the above formula, Ar is a substituted or unsubstituted arylene group, preferably a phenyl group, and n is preferably a number greater than 50.)

The polyarylene sulfide used in the present invention may be linear, branched or crosslinked.

Preferred starting compounds and methods for preparing polyarylene sulfides are described, for example, in US Pat. No. 3,354,129 and US Pat. No. 3,919,177. In its preparation, polyhalogenated aromatic compounds are obtained by reacting with sulfur-containing compounds in the presence of a catalyst in a polar solvent.

Preferred polyhalogenated aromatic compounds include, for example, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 2,5-dichlorotoluene, 1,4-dibromobenzene, 2, 5-dibromoaniline and mixtures thereof. In the preparation of branched polyarylene sulfides, at least 0.05 mol% of the polyhalogenated aromatic compounds are selected from aromatic trihalogen or tetrahalogen compounds such as 1,2,4-trichlorobenzene, 1,3,5- Preference is given to trichlorobenzene or 1,2,4,5-tetrachlorobenzene.

Preferred sulfur-containing compounds are alkali metal sulfides such as sodium sulfide, and potassium. Hydrates of these alkali metal sulfides are particularly preferred. The alkali metal sulfide can be produced from hydrogen sulfide using an alkali hydroxide such as lithium hydroxide and sodium hydroxide.

Preferred polar solvents are, for example, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, N-ethylcaprolactam and 1,3-dimethylimidazonone.

Moreover, as a suitable catalyst, substances, such as an alkali fluoride, an alkali phosphate, or an alkali carboxylate, are mentioned, for example, It is preferable to use in the quantity of 0.02-1.0 mol per mol of alkali metal sulfides.

It is preferable to use a compatibilizer for the purpose of improving the affinity of the (A) component and (D) component of this invention. As a compatibilizer, a copolymer of ethylene and an epoxy group-containing unsaturated compound (such as a styrene / (acrylonitrile) copolymer block and a polymer comprising the (meth) acrylic acid ester polymer block and an ethylene-glycidyl methacrylate copolymer) The copolymerization amount of the epoxy group-containing unsaturated compound is preferably in the range of 3 to 50% by weight.) In addition, the aromatic vinyl compound, the vinyl cyan compound, the aromatic vinyl compound and the ( Meta) acrylic acid ester compound or a polymer obtained by graft polymerization of the above-mentioned (meth) acrylic acid ester compound, and a carboxylic acid and / or an acid anhydride-modified ethylene polymer, and the like, and these may be used alone or in combination of two or more thereof. Can be.

It is preferable to use the said compatibilizer in 1-40 weight part with respect to a total of 100 weight part of said (A) and (D) component.

As an organometallic compound which is (E) component of this invention, the metal salt of carboxylic acid and / or the metal salt of sulfonic acid is mentioned. Examples of the metal include Li, Na, K, Mg, Ca, Ba, Zn, Al, Sn, Pb, Co, Sr, Cd, Fe, and the like, and carboxylic acid compounds include formic acid, acetic acid, propionic acid, lauric acid, stearic acid, Palmitic acid, olefinic acid, linoleic acid, montanic acid, maleic acid, rosin acid, phthalic acid and the like are exemplified. Moreover, as a sulfonic acid compound, the alkyl sulfonic acid, alkyl ether sulfonic acid, polyoxyethylene alkyl ether sulfonic acid, the dialkyl sulfosuccinic acid, the alkylamide ether sulfonic acid which have a C4-C18 alkyl group, and di2-ethylhexyl fosuccinic acid, C4-C18 Alkylbenzene sulfonic acid which has a substituted alkyl group to the aromatic ring of 18, sulfonic acids, such as diphenylsulfonic acid, etc. are illustrated. (E) component of this invention is 0.1-15 with respect to a total of 100 weight part of (A), (B) and (C) component of this invention or (A), (B), (C) and (D) component. Parts by weight, preferably 0.5 to 12 parts by weight, more preferably 1 to 10 parts by weight, particularly preferably 1 to 8 parts by weight. If the amount is less than 0.1 part by weight, there is no effect of improving flame retardancy, and if it exceeds 15 parts by weight, impact resistance is inferior.

As a flame retardant which is (F) component of this invention, what is necessary is just a compound which can provide sufficient flame retardance, when added to resin, A well-known flame retardant and a flame retardant adjuvant can be used. For example, an organic halogen flame retardant, an organic phosphorus flame retardant, and inorganic flame retardants, such as red phosphorus, calcium borate, magnesium hydroxide, and alumina, etc. are mentioned, These can be used individually or in combination of 2 or more types.

As the organic halogen flame retardant, a compound containing bromine and / or chlorine is preferable, and as the organophosphorus flame retardant, a phosphate compound and / or a phosphazene compound is preferable because it can increase the flame retardant performance when added to the resin.                     

As the organic halogen flame retardant, it is preferable to use at least one compound selected from the group consisting of halogenated bisphenol compounds, halogenated epoxy compounds, and halogenated triazine compounds. These flame retardants are most preferable because they have high flame retardant performance and exhibit the maximum effect of the present invention.

The halogenated bisphenol compound is a halide of bisphenol, and examples thereof include tetrabromobisphenol A, dibromobisphenol A, tetrachlorobisphenol A, dichlorobisphenol A, tetrabromobisphenol F, dibromobisphenol F and tetrachlorobisphenol F, dichlorobisphenol F, tetrabromobisphenol S, dibromobisphenol S, tetrachlorobisphenol S, dichlorobisphenol S, etc. are mentioned. These may be one kind or a mixture of two or more kinds.

A halogenated epoxy compound is a reaction product of a halogenated bisphenol compound and epihalohydrin or a halogenated bisphenol compound and diglycidyl ether, and is represented by the following general formula.

{Wherein n represents an integer of 0 or more, X represents bromine or chlorine, a, b, c and d represent an integer of 1 to 4, R ₁ represents an isopropylidene group, methylene group or sulfone group , R ₂ , R ₃ each represent a 2,3-epoxypropylene group or a CH ₂ CH (OH) CH ₂ OR group (R is an alkyl or allyl group which may be substituted with bromine or chlorine).}

As a specific example of the halogenated bisphenol compound used as a raw material of a halogenated epoxy compound, the thing illustrated above is mentioned similarly. The polymerization degree n of a halogenated epoxy compound is an integer of 0 or more, More preferably, it is an integer of 0-15, You may use together two or more things from which polymerization degree n differs.

An epoxy group may be sufficient as the terminal of a halogenated epoxy compound, and the epoxy group may be sealed by the allyl group, an alkyl group, etc. The allyl group and alkyl group which seal the terminal may be modified with halogen elements, such as chlorine and a bromine, as needed. Specific examples of the terminal sealing group include alkyl groups such as unsubstituted allyl groups such as phenyl group and naphthyl group, tribromophenyl group, pentabromophenyl group, halogenated allyl groups such as trichlorophenyl group and pentachlorophenyl group and stearyl group have. The terminal of the halogenated epoxy compound used in the present invention is not limited as long as it is within the above range, and the structure of one terminal and the other terminal may be the same or different.

A halogenated triazine compound is an organic halogen compound which has a triazine skeleton, and is represented by the following general formula.                     

(Wherein Y represents an -O- group or an -NH- group, R ₄ represents a brominated or chlorinated allyl group and / or an alkyl group, or a hydrogen atom, respectively.)

Such compounds are generally obtained by reacting triazine skeleton-containing compounds such as cyanuric acid and melamine with hydroxyl group-containing compounds such as brominated or chlorinated phenols and alcohols and amine compounds.

As an organophosphorus flame retardant, what is represented by following General formula (3), (4), etc. are mentioned.

Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are an alkyl group, a phenyl group or a xylyl group, and may be the same or different, respectively. X is a divalent resorcinol residue, hydro Quinone residue or bisphenol A residue, where n is 0 to 5 on average.)

(Wherein R ⁹ and R ¹⁰ are a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹¹ is a hydrogen atom, a phenyl group or a group represented by the following formula:

The phenyl group may be substituted with at least one selected from a halogen atom, a hydroxyl group or a lower alkyl group. x is an integer of 1-4. R ⁹ and R ¹⁰ may be the same or may be different.)

Specific examples of the flame retardant represented by the general formula (4) include ones represented by the following formulas (5) to (8).                     

Among them, those represented by the following formulas (5) and (6) are preferable.                     

The organophosphorus flame retardant may be used alone or in combination of two or more.

As a component (F) of this invention, a flame retardant adjuvant can be mix | blended further. Flame retardant adjuvant includes antimony compounds such as antimony trioxide, antimony tetraoxide, antimony pentoxide, polydetrafluoroethylene (PTFE) and the like. The flame retardant adjuvant in the case of using a halogen flame retardant is preferably an antimony compound, and in the case of using a phosphorus flame retardant, PTFE is preferable.

The PTFE has the effect of preventing dripping (melting drop) during combustion and achieving a higher combustion level. The weight average molecular weight of PTFE is 500,000 or more normally, Preferably it is 1 million or more. The average particle diameter of PTFE at the time of kneading with another component is 90-600 micrometers, Preferably it is 100-500 micrometers, More preferably, it is 120-400 micrometers. After kneading with the other components, PTFE is dispersed as a particulate matter having a mean particle diameter of 0.1 to 10 탆 or a finer fibrous substance. The specific gravity of PTFE is usually 1.5 to 2.5, preferably 2.1 to 2.3, and the bulk density is usually 0.5 to 1 g / ml, preferably 0.6 to 0.9 g / ml. PTFE may also be used as a dispersion type PTFE dispersed with a lubricant in a medium such as water. Examples of the lubricant include organic metal salts such as polyethylene wax, organic acids, and magnesium stearate.

Examples of the use of representative flame retardants include, for example, use of organic halogen flame retardants alone, combinations of organic halogen flame retardants with at least one selected from antimony oxide, zinc borate, zinc stannate, and iron oxide, use of organophosphorus flame retardants alone, and organophosphorus flame retardants And inorganic compounds such as magnesium compounds, inorganic compounds such as red phosphorus alone, combinations of organopolysiloxanes and organometallic compounds, hindered amine flame retardants alone, and inorganic flame retardants such as magnesium hydroxide, alumina, calcium borate, and low melting point glass. May be used alone or in combination.

(F) component of this invention combined the said flame retardant and the said flame retardant adjuvant, (F) component of this invention is (A), (B) and (C) component, or (A), (B), (C 1 to 40 parts by weight, preferably 1 to 35 parts by weight, more preferably 2 to 30 parts by weight, particularly preferably 2 to 25 parts by weight, based on 100 parts by weight of the total of the components (D) and (D). If the amount is less than 1 part by weight, the effect of improving flame retardancy is not obtained. If the amount is more than 40 parts by weight, the impact resistance and the appearance of the molded article are inferior.

Inorganic fillers of component (G) used in the present invention include glass fibers, glass powders, glass flakes, glass beads, hollow glass beads, carbon fibers, talc, wollastonite alumina such as wollastonite, mica, kaolin, montmorillonite, potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, plate-shaped alumina, acicular alumina, silica, smectite ), And these may be used alone or in combination of two or more thereof. Moreover, the inorganic filler which intercalated polyhydric alcohols, such as dimethylammonium chloride, trimethylammonium chloride, pentaerythritol, etc. can also be used between layers of plate-like compounds, such as mica, montmorillonite, smectite, and alumina.

Moreover, a well-known coupling agent can be used for the purpose of improving the dispersibility of the said inorganic filler of this invention. Known coupling agents include silane coupling agents, titanate coupling agents and the like.

(G) component of this invention is a component (A), (B) and (C) of this invention, (A), (B), (C) and (D) component, (A), (B), ( It is 1-100 weight part with respect to a total of 100 weight part of C), (D) and (E) component, or (A), (B), (C), (D), (E), and (F) component. . These fillers also have the effect of improving the flame retardancy in addition to the effect of improving the rigidity and heat resistance of the thermoplastic resin composition of the present invention.

In the thermoplastic resin composition 1, the usage-amount of (A) component is 5-98 weight%, Preferably it is 35-95 weight%, More preferably, it is 58-92 weight%, Especially preferably, it is 65-92 weight% . If the amount is less than 5% by weight, the impact resistance is inferior, and if it exceeds 98% by weight, the flame retardancy is not expressed. The usage-amount of (B) component is 1-74 weight%, Preferably it is 3-50 weight%, More preferably, it is 5-30 weight%, Especially preferably, it is 5-25 weight%. If the amount is less than 1% by weight, the impact resistance, flame retardancy and the appearance of the molded article are inferior, and if it exceeds 74% by weight, the impact resistance and the appearance of the molded article are inferior. The usage-amount of (C) component is 1 to 21 weight%, Preferably it is 2-15 weight%, More preferably, it is 3-12 weight%, Especially preferably, it is 3-10 weight%. If the amount is less than 1% by weight, flame retardancy is not expressed. If the amount is more than 21% by weight, the impact resistance and the appearance of the molded article are inferior.

In the thermoplastic resin composition 2, the usage-amount of (A) component is 5-94 weight%, Preferably it is 5-94 weight%, More preferably, it is 17-90 weight%, Especially preferably, it is 22-90 weight% . If the amount is less than 5% by weight, the impact resistance is inferior. If the amount is more than 94% by weight, flame retardancy is not expressed. The usage-amount of (B) component is 1 to 90 weight%, Preferably it is 3 to 70 weight%, More preferably, it is 5 to 50 weight%, Especially preferably, it is 5 to 30 weight%. If the amount is less than 1% by weight, impact resistance, flame retardancy and molded article surface appearance are inferior. If it exceeds 90% by weight, the impact resistance and the appearance of the molded article are degraded. The usage-amount of (C) component is 1 to 21 weight%, Preferably it is 2-15 weight%, More preferably, it is 3-12 weight%, Especially preferably, it is 3-10 weight%. If the amount is less than 1% by weight, flame retardancy is not expressed. If the amount is more than 21% by weight, the impact resistance and the appearance of the molded article are inferior. The usage-amount of (D) component is 4-93 weight%, Preferably it is 4-85 weight%, More preferably, it is 4-75 weight%, Especially preferably, it is 4-70 weight%. If the amount is less than 4% by weight, the flammability cannot be improved. If the amount is more than 93% by weight, the surface appearance of the molded product is inferior.

The thermoplastic resin composition of this invention can obtain a molded article by well-known shaping | molding methods, such as injection molding, press molding, sheet extrusion, vacuum molding, mold release extrusion molding, and foam molding.

The following can be illustrated as a molded article obtained by these molding methods.                     

Gears, Cases, Sensors, LEP Lamps, Connectors, Sockets, Resistors, Relay Cases, Switches, Coil Bobbins, Condensers, Barrier Cases, Optical Pickups, Oscillators, Various Terminal Boards, Transformers, Plugs, Printed Wiring Boards, Tuners Speakers, microphones, headphones, small motors, magnetic headbases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and other computer-related components Electrical and electronic components.

Home and office electrical appliances represented by VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, sound parts, audio machine parts such as audio / laser discs and compact discs, lighting parts, refrigerator parts, air conditioner parts, etc. Product parts.

Office computer parts, phone parts, fax parts, copier parts, cleaning jig parts.

Sanitary parts such as toilet seats, tank covers, casings, kitchen parts, vanity parts and bathroom parts.

Parts related to houses and housing facilities such as window frames, furniture, flooring and wall materials.

Parts related to optical and precision instruments such as microscopes, binoculars, cameras, and watches.

Various valves such as alternator terminals, alternator connectors, IC regulators, exhaust valves, fuel-related valves, exhaust systems, intake valves, air intake nozzles, intake manifolds, fuel pumps, engine coolant joints, carburetor bodies, carburettors Spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake component wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump Impellers, turbine vanes, wiper motor parts, distributors, starter switches, starter relays, wiper harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, connectors for fuses, horn terminals, electrical components insulation plates, Step motor roller, lamp socket, lamp reflector, ram Housing, brake piston, solenoid bobbin, engine oil filter, ignition device case.

Housings of storage devices such as personal computers, printers, displays, CRT displays, notebook personal computers, mobile phones, PHS, DVD drives, PD drives, flexible disk drives, chassis, relays, switches, case members, transformer members, coil bobbins, etc. Electrical and electronic device parts, automotive parts, and other applications.

The thermoplastic resin composition of this invention can mix | blend a weatherproof agent (lightfaster), an antistatic agent, antioxidant, a lubricating agent, a plasticizer, a coloring agent, a dye, an antibacterial agent suitably.

In addition, other polymers such as polyamide resin, polyamide elastomer, polyester elastomer, polyethylene, polypropylene, polyphenylene ether, P0M (polyacetal), phenol resin, epoxy resin, LCP (liquid crystal polymer), etc. may be used in combination. Can be.

The thermoplastic resin composition of this invention can be prepared by melt-kneading each component with various extruders, Banbury mixers, stirrers, rolls, feeder ruders, etc. Preferred recipes are those using an extruder or Banbury mixer.

In addition, in kneading each component, these components may be kneaded collectively, or may be kneaded by dividing into multiple stages by an extruder or a Banbury mixer.

Moreover, after kneading with a Banbury mixer, a stirrer, etc., it can also pelletize with an extruder.

EXAMPLE

Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited at all by the following example.

In addition, the part and% in an Example are a basis of weight unless there is particular notice. In addition, the various evaluations in an Example are measured as follows.

(1) Evaluation method

(1-1) limit oxygen index (L0I)

LOI was measured according to ASTM D-2863. The higher the value, the more difficult the combustion was, and the index was regarded as flame retardancy.

(1-2) impact resistance

Based on ISO test method 179, Charpy impact strength (KJ / m <2>) with a notch was measured.

(1-3) Molded product surface appearance

The flat plate was molded and the molded article surface appearance was visually evaluated according to the following evaluation criteria.

○: appearance is good,

X: inferior.                     

(1-4) Average particle diameter of rubbery polymer

The average particle diameter of the rubbery polymer dispersed particles was confirmed by electron microscopy that the diameter of the latex particles synthesized in the emulsified state was shown as the particle diameter of the dispersed particles in the resin as it was, and the particle diameter of the dispersed particles in the latex was measured by the light scattering method. . As a measuring instrument, LPA-3100 manufactured by Otsuka Denshi Co., Ltd. was used, and the particle diameter was measured by the cumulant method by 70 cumulative calculations.

(1-5) Graft ratio of (A) component (rubber modified styrene resin)

It carried out by the method of the said description.

(1-6) Intrinsic viscosity of acetone soluble part of (A) component and (B) component [η]

It measured by the method of the said description.

(1-7) Viscosity Average Molecular Weight of Aromatic Polycarbonate Resin

It measured by the method of the said description.

(1-8) Intrinsic viscosity of polyethylene terephthalate [η]

It measured by the method of the said description.

(2) Components of the Thermoplastic Resin Composition

(2-1) (A) Rubber modified styrene resin

Preparation Example A-1

In a 7-liter glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 parts of potassium rosinate, 0.1 parts of t-dodecyl mercaptan, polybutadiene latex (average particle diameter; 3500 kPa, gel content) in a nitrogen stream %) 40 parts (solid content), 15 parts of styrene, and 5 parts of acrylonitrile were added, and the temperature was raised stirring. When internal temperature reached 45 degreeC, the solution which melt | dissolved 0.2 parts of sodium pyrolate, 0.01 parts of ferrous sulfate hydrates, and 0.2 parts of glucose in 20 parts of ion-exchange water was added. Thereafter, 0.07 parts of cumene hydroperoxide was added, polymerization was initiated and polymerized for 1 hour, followed by 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, and t-dodecyl mercaptan 0.05 Part and cumene hydroperoxide 0.01 part were continuously added over 3 hours, and further polymerized for 1 hour, and 0.2 parts of 2,2-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. did. The reaction product latex was solidified with an aqueous sulfuric acid solution, washed with water, and dried to obtain a rubber-modified styrene resin A-1. The graft ratio of this rubber modified styrene resin A-1 was 72%, and the intrinsic viscosity [eta] of the acetone soluble part was 0.47 dl / g.

Preparation Example A-2

After connecting two jacketed polymerization reactors equipped with an internal volume 30 L ribbon impeller and replacing them with nitrogen, 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.1 part of t-dodecyl mercaptan and 5 parts of toluene was supplied as a molecular weight regulator, and a solution of 0.1 parts of 1, l'-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene was continuously supplied as a polymerization initiator. Supplied. The polymerization temperature of the first reactor was controlled to 110 ° C, the average residence time was 2.0 hours, and the polymerization conversion rate was 60%. The obtained polymer solution was continuously taken out in the same amount as the feed amount by a pump provided outside the first reaction vessel and supplied to the second reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., average residence time 2.0 hours, and polymerization conversion ratio 80%. In the copolymer solution obtained in the second reaction vessel, the unreacted monomer and the solvent were directly devolatilized using a twin screw three-stage vented extruder to obtain styrene resin A-2. Intrinsic viscosity [η] of this was 0.48 dl / g.

(2-2) (B) modified styrene resin

Preparation Example B-1

In a 7-liter glass flask equipped with a stirrer, 100 parts of ion-exchanged water, 1 part of dodecylbenzenesulfonic acid Na, 0.15 part of t-dodecyl mercaptan, 34 parts of styrene, and 11 parts of acrylonitrile in a nitrogen stream -5 parts of hydroxyethyl methacrylate and 0.15 part of t-dodecyl mercaptan were added, and the temperature was raised while stirring. When the internal temperature became 45 degreeC, the solution which melt | dissolved 0.2 parts of sodium pyrrolate, 0.01 parts of ferrous sulfate hydrates, and 0.2 parts of glucose in 20 parts of ion-exchange water was added. Thereafter, 0.12 parts of cumene hydroperoxide was added to initiate polymerization and polymerized for 1.5 hours, followed by 17 parts of styrene, 5.5 parts of acrylonitrile, 2.5 parts of 2-hydroxyethyl methacrylate, 0.1 part of t-dodecyl mercaptan, 40 parts of ion-exchanged water and 0.06 parts of cumene hydroperoxide were added and reacted for 1 hour. Thereafter, 17 parts of styrene, 5.5 parts of acrylonitrile, 2.5 parts of 2-hydroxyethyl methacrylate, 0.1 part of t-dodecyl mercaptan, 40 parts of ion-exchanged water, and 0.06 part of cumene hydroperoxide were added thereto, and for 1 hour. After the polymerization reaction, 0.2 part of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) was added to complete the polymerization. The reaction product latex was coagulated with an aqueous magnesium sulfate solution, washed with water and dehydrated, and then dried to obtain Polymer B-1. The intrinsic viscosity [η] of this product was 0.45 dl / g.

Preparation Example B-2

In Production Example B-1, the polymer B- was polymerized under the same conditions as in Production Example B-1 except that the following components and amounts were used as the first-stage monomer component, the second-stage monomer component, and the third-stage monomer component. 2 was obtained. The intrinsic viscosity [η] of this product was 0.46 dl / g.

 1st stage  2nd step  3rd stage   Styrene (part)  36.5  18.25  18.25   Acrylonitrile (part)  11  5.5  5.5   Glycidyl methacrylate (part)  2.5  1.25  1.25

(2-3) (C) component

C-1; Shin-Etsu Chemical Co., Ltd. KF96H-300,000 cSt was used.

C-2; Shin-Etsu Chemical Co., Ltd. KF96H-100 million cSt was used.

C-3; Shin-Etsu Chemical Co., Ltd. KE76BS (3 million cSt) was used.

C-4; Shin-Etsu Chemical Co., Ltd. KF9901 (20 cSt) was used.

C-5; Shin-Etsu Chemical Co., Ltd. KR-511 (methylphenyl polysiloxane, 100 cSt) was used.

C-6; Shin-Etsu Chemical Co., Ltd. KF105 (epoxy modified product, 15 cSt) was used.

C-7; Shin-Etsu Chemical Co., Ltd. X-22-173DX (epoxy modified product, 65 cSt) was used.

(2-4) (D) component

D-1; As the polyarylene sulfide, LR-01G made from toprene was used.

D-2; An aromatic polycarbonate having a viscosity average molecular weight of 23000 obtained by thermal melt polymerization of bisphenol A and diphenyl carbonate was used.

D-3; The pulverized product (IV = 0.73 dl / g) of the blow bottle of polyethylene terephthalate was used.

(2-5) (E) component

E-1; Barium stearate was used.

E-2; Lithium stearate was used.

E-3; Zinc acetate was used.

E-4; Potassium diphenyl sulfonate was used.

E-5; Zinc stearate

(2-6) (F) component

F-1; As a phosphorus flame retardant, PX-200 1,3-phenylene-bis (dixylenyl phosphate) manufactured by Daihachi Chemical Co., Ltd. was used.

F-2; As the polydetrafluoroethylene, Dikinon Co., Ltd. Difreon F 201L was used.

(2-7) (G) Component

G-1; Nippel Gel CY-200 manufactured by Nippon Silica Co., Ltd. was used as silica.

G-2; Somasif MEE manufactured by Kope Chemical Co., Ltd. was used as a mica in which organic matter was intercalated between layers.

G-3; Nippon Taruk P-3 (average particle diameter: 5.1 micrometers) was used.

(2-8) Other Ingredients

As a silane coupling agent, NUC silane coupling agent A-186 made by Nippon Unicars was used.

(2-9) Examples 1-23, Comparative Examples 1-4                     

The components (other than D component) shown in Table 1 or Table 2 were mixed by the Henschel mixer in the blending ratios shown in Table 1 or Table 2, and then melt kneaded using a Banbury mixer (resin temperature 200 to 230 ° C). It was made into a sheet using a roll, pelletized with a sheet cutter, and dried.

The test piece for evaluation was shape | molded by the injection molding machine set to the cylinder temperature of 220 degreeC that D component is not mix | blended.

The composition to which the D component was mix | blended was melt-kneaded and pelletized by the twin screw extruder (280 degreeC), after mixing the said pellet and D component, and it dried. And the test piece for evaluation was shape | molded with the injection molding machine set to the cylinder temperature of 285 degreeC.

Using each said molded article, flame retardance (limit oxygen index), impact resistance, and the molded article surface appearance were evaluated by the said method. The evaluation results are shown in Table 1 and Table 2.                     

Comparative Example 1 is an example in which the amount of the component (B) of the present invention is less than the range of the invention, and the flame retardancy, impact resistance and the appearance of the molded article are poor.

Comparative Example 2 is an example in which the amount of the component (C) of the present invention is less than the scope of the present invention, and is inferior in flame retardancy.

Comparative Example 3 is an example in which the amount of rubber in the component (A) of the present invention is less than the range of the present invention, and the impact resistance is inferior.

Comparative Example 4 is an example in which the amount of the component (C) of the present invention is used out of the range of the invention, and the impact resistance and the appearance of the molded article are poor

ADVANTAGE OF THE INVENTION According to this invention, a thermoplastic resin composition excellent in flame retardancy, impact resistance, and the molded article surface appearance is obtained by mix | blending appropriate amount of the styrene resin which has a specific functional group with the composition which consists of styrene rubber reinforced resin and polyorganosiloxane.

Claims (12)

(A) Rubber modified styrene resin 5-3 which is a graft polymer consisting of 3-40 weight% of rubbery polymers (a) and 60-97 weight% of vinyl monomers (b) which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound. 98% by weight, (B) 30-99 weight% of vinyl monomers which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound, and a hydroxyl group containing unsaturated compound, a carboxyl group containing unsaturated compound, an acid anhydride group containing unsaturated compound, an epoxy group containing unsaturated compound, and an oxazoline group 1 to 74% by weight of a modified styrene resin composed of 1 to 70% by weight of one or more vinyl monomers selected from the group consisting of unsaturated compounds, and (C) 3 to 10% by weight of polyorganosiloxane To 100 parts by weight of the resin composition, wherein the sum of the components (A), (B) and (C) is 100% by weight. (E) 0.1-15 weight part of organometallic compounds A thermoplastic resin composition formed by blending. (A) Rubber-modified styrene resin 5 to 3 which is a graft polymer which consists of 3-40 weight% of rubbery polymers (a) and 60-97 weight% of vinyl monomers (b) which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound. 94% by weight, (B) 30-99 weight% of vinyl monomers which consist of an aromatic vinyl compound or an aromatic vinyl compound, and a vinyl cyan compound, and a hydroxyl group containing unsaturated compound, a carboxyl group containing unsaturated compound, an acid anhydride group containing unsaturated compound, an epoxy group containing unsaturated compound, and an oxazoline group 1 to 90% by weight of a modified styrene resin composed of 1 to 70% by weight of one or more vinyl monomers selected from the group consisting of unsaturated compounds, (C) 3 to 10% by weight of polyorganosiloxane, and (D) aromatic polycarbonate resins, thermoplastic polyester resins and polyarylene sulfides It consists of 4 or 93 weight% of 1 or more types chosen from the group which consists of, and with respect to 100 weight part of resin compositions whose sum total of the said (A), (B), (C) and (D) component is 100 weight%. (E) 0.1-15 weight part of organometallic compounds A thermoplastic resin composition formed by blending. The method of claim 1, With respect to 100 weight part of resin compositions whose sum total of the said (A), (B) and (C) component is 100 weight%, (F) 1 to 40 parts by weight of flame retardant Thermoplastic resin composition which is mix | blended further. The method of claim 2, With respect to 100 weight part of resin compositions whose sum total of the said (A), (B), (C) and (D) component is 100 weight%, (F) 1 to 40 parts by weight of flame retardant Thermoplastic resin composition which is mix | blended further. The method of claim 1, To 100 parts by weight of the total of the components (A), (B), (C) and (E), (G) 1 to 100 parts by weight of inorganic filler Thermoplastic resin composition which is mix | blended further. The method of claim 2, To 100 parts by weight of the total of the components (A), (B), (C), (D) and (E), (G) 1 to 100 parts by weight of inorganic filler Thermoplastic resin composition which is mix | blended further. The method of claim 3, To 100 parts by weight of the total of the components (A), (B), (C), (E) and (F), (G) 1 to 100 parts by weight of inorganic filler Thermoplastic resin composition which is mix | blended further. The method of claim 4, wherein To 100 parts by weight of the total of the components (A), (B), (C), (D), (E) and (F), (G) 1 to 100 parts by weight of inorganic filler Thermoplastic resin composition which is mix | blended further. The method according to any one of claims 1 to 8, The thermoplastic resin composition in which the polyorganosiloxane which is the said (C) component contains 30 weight% or more of polydimethylsiloxane whose viscosity in 25 degreeC is 100,000-3 million cSt. The method according to any one of claims 1 to 8, A part of the substituents of Si in the polyorganosiloxane of the said (C) component is 1 or more types chosen from the group which consists of a hydrogen, an alkoxy group, an unsaturated group, and a phenyl group. The method according to any one of claims 1 to 8, The thermoplastic resin composition of the polyorganosiloxane of the component (C) is modified with at least one selected from the group consisting of amino, epoxy, carboxyl, carbinol, methacryl, hydroxy, mercapto and phenol groups. The molded article which consists of a thermoplastic resin composition of any one of Claims 1-8.