JP2625919B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to impact resistance, moldability, slidability, abrasion resistance, weather resistance, cold resistance, heat stability, heat resistance, and chemical resistance. The present invention relates to a thermoplastic resin composition having excellent weld strength and exhibiting a high-gloss molded appearance.

[Conventional technology]

Conventionally, polyamide resins such as nylon 6, nylon 6,6, nylon 4,6, and nylon 12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, vinyl chloride resins, olefin resins, polyacetal resins, and polyphenylene sulfide Resins, polyarylate resins, and polyphenylene ether resins have various excellent properties, and are utilized in many fields such as plastic products and films by utilizing these properties.

However, polyamide resin, polyester resin, vinyl chloride resin, polyacetal resin, polyphenylene sulfide resin, polyarylate resin,
Alternatively, the polyphenylene ether-based resin has a disadvantage that the impact resistance is not so excellent, and particularly the impact resistance when a notch is formed is low.

In addition, polycarbonate resin has poor chemical resistance,
In addition, it has the disadvantage that the impact resistance is sensitive to the notch sensitivity.

Due to these drawbacks, the above-mentioned materials have not always been satisfactory for a wider application.

Therefore, in order to improve the impact resistance, many methods of blending rubber and rubber-reinforced resin have been reported. However, depending on these methods, the impact resistance of a polyamide resin or a polyester resin is sufficiently improved. It is not sufficient in terms of weld strength and molding appearance. The impact resistance of a polycarbonate-based resin is also improved by the above method, but the chemical resistance and the weld strength are not sufficiently improved. Further, in this case, various types of rubbers such as butadiene rubber and ethylene-propylene rubber can be considered, but the selection of these rubbers is important because the characteristics of the rubber used are reflected in the characteristics of the resin blended therewith. It is.

Therefore, when considering polyorganosiloxane (hereinafter sometimes referred to as “silicone rubber”) having excellent functions such as weather resistance, heat resistance, and cold resistance as a rubber component,
Simply blending a silicone rubber and a thermoplastic resin will result in poor impact resistance of the resulting blend due to poor compatibility between these components. Therefore, some modification technique is required for silicone rubber.

Several methods have been disclosed for these modification techniques. For example, a method of graft-polymerizing a vinyl monomer to a silicone rubber containing a vinyl group or an allyl group (Japanese Patent Application Laid-Open No. 50-109282), a method of graft-polymerizing a vinyl monomer to a silicone rubber containing a mercapto group ( JP-A-52-130885) or a method in which a vinyl monomer is graft-polymerized to a silicone rubber containing an acryl group or a methacryl group (JP-A-60-2526).
No. 13).

Further, a graft copolymer of these silicone rubbers (hereinafter, sometimes simply referred to as a “graft copolymer”)
Several types of blends of a resin and a thermoplastic resin are also disclosed. For example, a method of adding a small amount of a graft copolymer to nylon 6 (JP-A-61-235462), a blend of a graft copolymer and a polyester resin (JP-A-61-235462).
JP-A-62-121752) or a blend of a graft copolymer and a polycarbonate resin (JP-A-62-297352, JP-A-62-77968).

[Problems to be solved by the invention]

However, when a silicone rubber containing a vinyl group, an allyl group or a mercapto group is used as a modification technique, the apparent graft ratio calculated from the amount of gel formation, That is, the ratio of the vinyl polymer grafted to the silicone rubber is small. Therefore, the effect of improving the compatibility between the components is poor.

In addition, when a silicone rubber containing an acryl group or a methacryl group is used, the graft ratio is improved, but the functional group is an ester bond. There is a problem in the stability of bonding, and the thermal stability, chemical resistance, appearance, etc. are insufficient.

Further, regarding the blend of the graft copolymer and the thermoplastic resin, the thermoplastic resin blended with the vinyl polymer grafted on the silicone rubber, that is, a polyamide resin, a vinyl chloride resin, an olefin resin, a polyacetal resin, a polyphenylene Insufficient compatibility with sulfide resin, polyarylate resin, or polyphenylene ether resin could not sufficiently improve impact resistance, weld strength, molded appearance, and chemical resistance.

The present invention has been made in view of the problems of the prior art described above, and uses a specific modified polyorganosiloxane capable of efficiently graft-polymerizing a vinyl monomer to a silicone rubber, and further comprises a polyamide resin, a polyester resin, and a polycarbonate resin. By graft polymerizing a specific vinyl monomer to silicone rubber that significantly improves compatibility with thermoplastic resins such as resins, impact resistance, weld strength, molded appearance, chemical resistance are improved, and further, slidability, An object of the present invention is to provide a thermoplastic resin composition having excellent wear resistance, weather resistance, cold resistance, moldability, heat stability, and heat resistance.

[Means for solving the problem]

The present invention relates to (A) 5 to 90% by weight of a polyorganosiloxane-based polymer obtained by cocondensing 0.1 to 50% by weight of at least one kind of a graft crosslinking agent selected from the following groups (a) to (d):
A graft copolymer (hereinafter sometimes referred to as a "graft copolymer (A)") obtained by graft-polymerizing a carboxyl group-containing vinyl monomer and another vinyl monomer at 95 to 10% by weight. weight%, (Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and a graft crosslinking agent having both an alkoxysilyl group and an unsaturated group.

(B) R ³ _p SiO _{(3-p) / 2} (wherein, R ³ represents a vinyl group or an allyl group, and p represents an integer of 0 to 2.) (c) HSR ⁴ SiR ⁵ _q O _{(3- q) / 2} (wherein, R ⁴ represents a divalent or trivalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ⁵ represents a monovalent monovalent group containing no aliphatic unsaturated group having 1 to 6 carbon atoms. A hydrocarbon group, and q represents an integer of 0 to 2.) (In the formula, R ⁶ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group, r is an integer of 1 to 6, and s is an integer of 0 to 2.) (B) The polyorganosiloxane-based polymer A graft copolymer (hereinafter, referred to as "graft copolymer (B)") obtained by graft-polymerizing 95 to 10% by weight of another vinyl monomer excluding the carboxyl group-containing vinyl monomer to 5 to 90% by weight of the copolymer. (C) styrene resin (hereinafter referred to as “styrene resin (C)”)
(D) a polyamide resin, a polyester resin, a polycarbonate resin, a vinyl chloride resin, an olefin resin, a polyacetal resin, a polyphenylene sulfide resin, a polyarylate resin, And a thermoplastic resin containing 10 to 90% by weight of at least one thermoplastic resin selected from polyphenylene ether-based resins (hereinafter sometimes referred to as “thermoplastic resin (D)”).

Further, in this thermoplastic resin composition, the following requirements (a) to (c) are preferable.

(A) The content of the carboxyl group-containing vinyl monomer in the component (A) is 0.1 to 8% by weight, and the content of the carboxyl group-containing vinyl monomer in the whole composition is 0.02 to 4% by weight. The content of the polyorganosiloxane polymer in the composition is 5 to 40% by weight, and (c) the graft ratio to the polyorganosiloxane polymer in the components (A) and (B) is 30% by weight or more. And the intrinsic viscosity (30 ° C., in methyl ethyl ketone) of the matrix component in the component (A), the component (B) and the component (C) is 0.35 dl / g or more.

The polyorganosiloxane-based polymer used in the graft copolymers (A) and (B) of the present invention is obtained by co-condensing an organosiloxane (I) and a graft-linking agent (II).

Here, as the organosiloxane (I), for example, the general formula R ¹ _n SiO _{(4-n) / 2} (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and n is 0 to 0) 3) which has a structural unit represented by the following formula:
Although it has a branched or cyclic structure, it is preferably an organosiloxane having a cyclic structure.

Examples of the substituted or unsubstituted monovalent hydrocarbon group possessed by the organosiloxane (I) include a methyl group, an ethyl group, a propyl group, a vinyl group, a phenyl group, and a substituted or unsubstituted halogen atom or cyano group. Examples include a hydrocarbon group.

In the average composition formula, the value of n is an integer of 0 to 3.

Specific examples of the organosiloxane (I) include, in addition to cyclic compounds such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and trimethyltriphenylcyclotrisiloxane, A chain or branched organosiloxane can be mentioned.

The organosiloxane (I) may be a polyorganosiloxane precondensed, for example, having a polystyrene equivalent weight average molecular weight of about 500 to 10,000.

When the organosiloxane (I) is a polyorganosiloxane, its molecular chain ends are blocked with, for example, a hydroxyl group, an alkoxy group, a trimethylsilyl group, a dimethylvinylsilyl group, a methylphenylvinylsilyl group, a methyldiphenylsilyl group, or the like. May be.

Next, the graft crosslinking agent (II) used in the present invention comprises:
It is at least one selected from the following groups (a) to (d).

(Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and a graft crosslinking agent having both an alkoxysilyl group and an unsaturated group.

(B) R ³ _p SiO _{(3-p) / 2} (wherein, R ³ is a vinyl group or an allyl group, and p is an integer of 0 to 2) Specific examples: vinylmethyldimethoxysilane, tetravinyltetramethyl Cyclosiloxane, allylmethyldimethoxysilane.

(C) HSR ⁴ SiR ⁵ _q O _{(3-q) / 2} (wherein R ⁴ has 1 to 1 carbon atoms ₎
18 divalent or trivalent saturated aliphatic hydrocarbon group, R ⁵ is a monovalent hydrocarbon group containing no aliphatic unsaturated group having 1 to 6 carbon atoms, and q represents an integer of 0 to 2 . Specific examples: γ-mercaptopropylmethyldimethoxysilane.

(In the formula, R ⁶ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a phenyl group, r is an integer of 1 to 6, and s is an integer of 0 to 2.) Specific examples: γ-methacryloxypropylmethyl Dimethoxysilane.

Among these grafting agents (II), compounds having both the unsaturated group represented by (a) and an alkoxysilyl group are particularly preferred.

This (a) graft-crosslinking agent will be described in more detail. In the general formula, R ² is a hydrogen atom or a carbon atom having 1 carbon atom.
6 to 6, but a hydrogen atom or a carbon atom having 1 to 6
2 alkyl groups are preferred, and more preferably a hydrogen atom or a methyl group.

Specific examples of these (a) graft-crosslinking agents include p-vinylphenylmethyldimethoxysilane and 1- (m
-Vinylphenyl) methyldimethylisopropoxysilane, 2- (p-vinylphenyl) ethylenemethyldimethoxysilane, 3- (p-vinylphenoxy) propylmethyldiethoxysilane, 3- (p-vinylbenzoyloxy) propylmethyldimethoxy Silane, 1- (o-vinylphenyl) -1,1,2-trimethyl-2,2-dimethoxydisilane, 1- (p-vinylphenyl) -1,1-diphenyl-3-ethyl-3,3-di Ethoxydisiloxane, m-
Examples thereof include vinylphenyl- [3- (triethoxysilyl) propyl] diphenylsilane, [3- (p-isopropenylbenzoylamino) propyl] phenyldipropoxysilane, and mixtures thereof.
(A) The graft-crosslinking agent is preferably p-vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, or 3- (p-vinylbenzoyloxy) propylmethyldimethoxysilane. Preferably, it is p-vinylphenylmethyldimethoxysilane. By using this (a) graft-crossing agent, one having a high grafting ratio can be obtained, and therefore, a more excellent composition aimed at by the present invention can be obtained.

The use ratio of the above grafting agent (II) is 0.2 to 50% by weight, preferably 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the components (I) and (II). If it is less than 0.2% by weight, a high graft ratio cannot be obtained in the graft polymerization of the resulting polyorganosiloxane polymer and vinyl monomer, and as a result, the interfacial adhesion between the polyorganosiloxane polymer and vinyl polymer decreases. However, delamination occurs, and sufficient impact strength cannot be obtained for the graft copolymer.

On the other hand, when the proportion of the graft-linking agent (II) exceeds 50% by weight, the graft ratio increases, but the polymerization of the grafted vinyl polymer decreases with the increase of the graft-linking agent (II). Molecular weight, and as a result, a sufficient impact strength cannot be obtained.

The polyorganosiloxane-based polymer is produced by subjecting the organosiloxane (I) and the graft-linking agent (II) to shear mixing using a homomixer or the like in the presence of an emulsifier such as alkylbenzene sulfonic acid and condensing the mixture. can do. This emulsifier acts as an emulsifier for the organosiloxane (I) and also serves as a condensation initiator.

The amount of the emulsifier to be used is generally 0.1 to 5% by weight, preferably 0.1 to 5% by weight, based on the total amount of the components (I) and (II).
It is about 0.3 to 3% by weight.

The amount of water used at this time depends on the components (I) and (I)
The amount is usually 100 to 500 parts by weight, preferably 200 to 400 parts by weight, per 100 parts by weight of the component (I).

 The condensation temperature is usually 5 to 100C.

In the production of the polyorganosiloxane polymer, a crosslinking agent may be added as a third component in order to improve the impact resistance of the obtained resin. Examples of the crosslinking agent include methyltrimethoxysilane, phenyltrimethoxysilane, and ethyltriethoxysilane.
Examples of the functional crosslinking agent include tetrafunctional crosslinking agents such as tetraethoxysilane. The amount of the crosslinking agent is usually about 10% by weight or less, preferably about 5% by weight or less, based on the total amount of the organosiloxane (I) and the grafting agent (II).

The polyorganosiloxane-based polymer thus obtained has a polystyrene-equivalent weight average molecular weight of usually 10,000 to 1,000,000, preferably about 50,000 to 500,000.

The graft copolymer (A) used in the present invention is a copolymer obtained by graft-polymerizing a carboxyl group-containing vinyl monomer and another vinyl monomer in the presence of the polyorganosiloxane-based polymer thus obtained. It is a polymer.

Here, examples of the carboxyl group-containing unsaturated vinyl monomer include acid anhydrides such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, and maleic anhydride. Acid, methacrylic acid.

Further, as other vinyl monomers, styrene, α-
Methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, p-butylstyrene, ethylstyrene, vinylnaphthalene, o-methylstyrene, p-methylstyrene, dimethylstyrene, sodium styrenesulfonate, etc. Aromatic alkenyl compounds; methacrylates such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, butyl methacrylate, allyl methacrylate; methyl acrylate,
Acrylates such as ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate; acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile; olefins such as ethylene and propylene; conjugated diolefins such as butadiene, isoprene and chloroprene; and vinyl acetate, vinyl chloride, vinylidene chloride, triallyl isocyanurate, N-phenylmaleimide, and N-methyl Maleimides such as maleimide, N-ethylmaleimide, No-chlorophenylmaleimide, and N-cyclohexylmaleimide are used, and these are used alone or in combination.

When a carboxyl group-containing vinyl monomer is copolymerized, (1) a graft layer of a graft copolymer or (2) a non-graft polymer may be mentioned as a portion to be copolymerized, but preferably (1). .

The charged composition at the time of graft-polymerizing a carboxyl group-containing vinyl monomer and another vinyl monomer to the polyorganosiloxane-based polymer is 5 to 90% by weight, preferably 10 to 70% by weight of the polyorganosiloxane-based polymer. Preferably, the total amount of the vinyl monomer is 95 to 10% by weight, preferably 90 to 30% by weight, more preferably 80 to 40% by weight based on 20 to 60% by weight.

If the polyorganosiloxane polymer is less than 5% by weight, sufficient impact strength cannot be obtained, while if it exceeds 90% by weight, sufficient interfacial adhesion between the polyorganosiloxane polymer and the vinyl polymer cannot be obtained. As a result, the resulting composition has poor appearance and a reduced impact strength.

The proportion of the graft copolymer (A) in the composition of the present invention is 5 to 90% by weight, preferably 10 to 90% by weight, more preferably 10 to 80% by weight. The resulting composition is poor in impact resistance and weld strength, while when it exceeds 90% by weight, the molded appearance and the formability are deteriorated.

Next, the graft copolymer (B) used in the present invention
Is a copolymer obtained by graft-polymerizing another vinyl monomer other than the carboxyl group-containing vinyl monomer (hereinafter referred to as "other vinyl monomer") in the presence of the polyorganosiloxane-based polymer obtained as described above. It is united.

Here, as the other vinyl monomer, one or more of the other vinyl monomers used in the graft copolymer (A) can be used.

The charge composition at the time of graft-polymerizing another vinyl monomer to the polyorganosiloxane polymer is preferably 5 to 90% by weight, more preferably 5 to 90% by weight, for the same reason as in the case of the graft copolymer (A). Is 10 to 70% by weight, more preferably 20 to 60% by weight, and the other vinyl monomer is 95 to 10% by weight, preferably 90 to 30% by weight,
More preferably, it is 80 to 40% by weight.

The proportion of the graft copolymer (B) in the composition of the present invention is 5 to 80% by weight. In the composition of the present invention, it is preferable to add the component (B) in order to adjust the balance of physical properties such as molding appearance and moldability, but if the proportion exceeds 80% by weight in the composition, the composition is resistant. Impact strength and weld strength are undesirably deteriorated.

The graft ratio of the graft copolymer (A) or (B) thus obtained is usually about 30% by weight or more, preferably about 50% by weight or more, and more preferably about 100% by weight or more.

As described above, when the graft ratio of the graft copolymer (A) or (B) is high, the interfacial adhesion between the graft copolymer and the vinyl polymer that has not been directly grafted increases. The polyorganosiloxane-based polymer is uniformly dispersed in the thermoplastic resin composition, and a thermoplastic resin composition having good appearance and excellent impact strength can be obtained.

When producing the graft copolymer (A) or (B) used in the present invention, a carboxyl group-containing vinyl monomer or another vinyl monomer (hereinafter, collectively referred to as " Vinyl monomer ") by the usual radical polymerization to form a graft copolymer (A) or (B).
Is obtained as a composition containing

Here, depending on the type of the radical polymerization initiator, it is necessary to neutralize the latex of the polyorganosiloxane-based polymer acidified by the alkylbenzenesulfonic acid as described above with an alkali. As the alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethanolamine, triethylamine and the like are used.

Examples of the radical polymerization initiator include, for example, an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, and a sulfoxylate formulation. Redox initiators in combination with reducing agents such as a mixture of sugar-containing iron pyrophosphate formulation / sulfoxylate formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl- 2,2'-
Examples include azo compounds such as azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide and lauroyl peroxide; and the above-mentioned redox initiators are preferred.

The amount of the radical polymerization initiator to be used is generally about 0.05 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of the vinyl monomer used.

The radical polymerization at this time is preferably carried out by emulsion polymerization or solution polymerization.

In the emulsion polymerization, a known emulsifier, the above-mentioned radical initiator, a chain transfer agent and the like are used.

Here, as the emulsifier, anionic emulsifiers such as sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium diphenylether disulfonate, sodium succinate dialkali ester sulfonate,
Alternatively, one or more nonionic emulsifiers such as polyoxyethylene alkyl ester and polyoxyethylene alkyl allyl ether can be used.

The amount of the emulsifier used is usually
It is about 0.5 to 5% by weight.

Examples of the chain transfer agent include t-dodecyl mercaptan, octyl mercaptan, n-tetradecyl mercaptan,
Mercaptans such as n-hexyl mercaptan; halogen compounds such as carbon tetrachloride and ethylene bromide are usually used in an amount of 0.02 to 1% by weight based on the vinyl monomer.

In the emulsion polymerization, a radical polymerization initiator, an emulsifier,
In addition to chain transfer agents, various electrolytes and pH
In combination with a modifier, for 100 parts by weight of the vinyl monomer, usually, 100 to 500 parts by weight of water, the radical polymerization initiator, an emulsifier, a chain transfer agent and the like in an amount within the above range, Emulsion polymerization is carried out under the conditions of a polymerization temperature of 5 to 100 ° C, preferably 50 to 90 ° C, and a polymerization time of 0.1 to 10 hours.

In the case of emulsion polymerization, the organosiloxane (I)
And a graft crossing agent (II). It can also be carried out by adding a vinyl monomer and a radical initiator to a latex containing a polyorganosiloxane-based polymer).

On the other hand, in the case of solution polymerization, a polyorganosiloxane-based polymer and a vinyl monomer are dissolved in an organic solvent, and a radical initiator, a chain transfer agent as needed, and various additives are added thereto to perform radical polymerization.

Examples of the organic medium used in the solution polymerization include toluene, n-hexane, cyclohexane, chloroform, tetrahydrofuran and the like.

At the time of solution polymerization, a radical polymerization initiator, optionally using a chain transfer agent and the like, based on 100 parts by weight of the vinyl monomer, usually 80 to 500 parts by weight of an organic solvent, the radical polymerization initiator, A chain transfer agent or the like is used in an amount within the above range, and the polymerization temperature is 5 to 150 ° C, preferably 50 to 130 ° C.
Solution polymerization is carried out at a temperature of 1 ° C. for a polymerization time of 1 to 10 hours.

In the case of this solution polymerization, impurities can be significantly reduced as compared with the case of emulsion polymerization.

When the graft copolymer (A) or (B) used in the present invention is produced by emulsion polymerization, it is purified by coagulation by a usual salt coagulation method, washing the obtained powder with water, and then drying it. You.

In the case of solution polymerization, after unreacted monomers and a solvent are distilled off by steam distillation, the resulting resin mass is finely crushed and dried to be purified.

Next, the (C) styrene resin used in the present invention is:
In the presence or absence of the rubbery polymer, an aromatic vinyl compound is an essential component, and at least one selected from a maleimide compound, a vinyl cyanide compound, and another copolymerizable vinyl monomer as necessary. It is a resin obtained by polymerizing a resin component composed of a monomer.

The rubbery polymer, aromatic vinyl compound, maleimide compound, and other vinyl monomers copolymerizable therewith are the same as those described for the components (A) and (B).

In addition, as another vinyl monomer to be graft-polymerized to the components (A) to (C), a vinyl monomer may be selected such that the components (A) to (C) are compatible with each other. Preferably, particularly preferably, (A) to
The component (C) and the other vinyl monomers may be substantially similar.

(C) Styrene-based resin is a resin that polymerizes a monomer of a resin component in the presence of a rubbery polymer, and a resin that is obtained by polymerizing a monomer of a resin component in the absence of a rubbery polymer. May be used.

More specifically, the styrene resin (C) is acrylonitrile-butadiene rubber-styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-
Styrene resin (AES resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABSM resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin), high-impact polystyrene ( HIPS), acrylonitrile-n-butyl acrylate rubber-styrene resin (AAS resin) and the like.

The proportion of the styrene resin as the component (C) in the composition of the present invention is 3 to 80% by weight, and if it exceeds 80% by weight, the weld strength is deteriorated.

When a polyamide resin is selected as the component (D),
The preferred range of the component (C) is 10 to 80% by weight, and a thermoplastic resin composition having excellent impact resistance and molded appearance can be obtained.

The graft ratio of the monomer to the rubber component in the component (C) of the present invention is usually 30% by weight or more, preferably 40% by weight or more, and more preferably 50 to 150% by weight.
When the amount is less than the weight percentage, the appearance of the molded article is affected by the molding temperature, and the gloss is reduced.

Next, the polyamide resin used as the component (D) of the present invention is not particularly limited, and ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- and
Aliphatics such as 2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) methane, m-xylylenediamine and p-xylenediamine Polyamide derived from an alicyclic or aromatic diamine and an aliphatic, alicyclic or aromatic dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid; ε Polyamides obtained by ring-opening polymerization of lactams such as caprolactam and ω-dodecalactam; polyamides derived from 6-aminocaproic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, and the like; Nylon, which is a polymerized polyamide or a mixed polyamide, and is industrially produced in large quantities at low cost 6 (polycaproamide), nylon 6,6 (polyhexamethylene adipamide), nylon 12 (poly dodeca amide), nylon 6,10
(Polyhexamethylene sebacamide), nylon 4,6, and copolymers or mixtures thereof are useful.

The degree of polymerization of the polyamide resin used herein is not particularly limited, and usually, the relative viscosity (1 g of the polymer is dissolved in 98 ml of 98% by weight sulfuric acid and measured at 25 ° C.) is within the range of 1.8 to 6.0. Resin can be used arbitrarily,
When a material having a range of 2 to 5 is used, a material having an excellent balance between impact resistance and moldability can be obtained.

There is no restriction on the molecular structure of the polyamide resin,
Either a linear polyamide or a branched polyamide may be used.

The polyester resin used as the component (D) is not particularly limited, but is obtained by a polycondensation product of a diol and a derivative such as a dicarboxylic acid or an alkyl ester of the dicarboxylic acid.

Of the constituent components of the polyester resin, 70 to 100 mol% of the portion composed of dicarboxylic acid is introduced by terephthalic acid, and 30 to 0 mol% is isophthalic acid, terephthalenedicarboxylic acid, adipic acid. , And sebacic acid. The portion constituted by glycol is introduced by ethanediol, propanediol, butanediol, pentanediol, or hexanediol, and may be constituted by two or more of these.

Further, there may be a portion introduced by oxybenzoic acid and bisphenol A, and a mixed polyester resin obtained by mixing one or more of these polyester resins is also included in the scope of the present invention.

Such polyester-based resins include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and copolymers or mixtures thereof.

The polycarbonate resin used as the component (D) is obtained by reacting a bisphenol with a phosgene or a carbonate precursor such as diaryl carbonate.

As the bisphenols, bis (hydroxyaryl) alkanes are preferable. For example, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dibromophenyl) propane, 2 , 2'-bis (4-hydroxy-3,5-dichlorophenyl) propane and the like. These bisphenols are used alone or as a mixture.

The degree of polymerization of the polycarbonate resin used here is not particularly limited, and is usually limited to an intrinsic viscosity (solvent: methylene chloride, 20
0.3 to 1.0 dl / g can be used arbitrarily. If 0.35 to 0.75 dl / g is used, a product having a high level of balance between impact resistance and moldability can be obtained. Can be

The vinyl chloride resin used as the component (D) includes at least a vinyl chloride homopolymer and at least a double bond capable of copolymerizing with vinyl chloride at most 50% by weight (preferably 45% by weight or less). It is a compound having one compound, preferably a copolymer with another vinyl monomer.

Representative examples of the compound having at least one double bond include vinylidene chloride, ethylene, propylene, vinyl acetate, acrylic acid, and methacrylic acid, and their esters, maleic acid and its esters, and acrylonitrile. These vinyl chloride resins are obtained by homopolymerizing or copolymerizing vinyl chloride alone or vinyl chloride and the other vinyl monomer in the presence of a free radical catalyst.

The polymerization degree of this vinyl chloride resin is usually 400 to 4,500
And particularly preferably 400 to 1,500.

The olefin-based resin used as the component (D) is typified by polyethylene and polypropylene, and these may be copolymers with a compound having at least one double bond capable of copolymerization. Often, the compounds include acrylic acid and methacrylic acid and their esters, maleic acid and its esters, maleic anhydride and the like. These compounds are preferably copolymerized with polyethylene or polypropylene at a ratio of 10% by weight or less.

The degree of polymerization of the above polyolefin resin is 300 to 6,000
It is preferred that

The polyacetal resin used as the component (D) is a resin obtained by stabilizing a polyoxymethylene having a polyether bond, and is a homopolymer type having only an oxymethylene group in the main chain, or an oxymethylene group and an oxyethylene group. Of the copolymer type.

The polyphenylene sulfide-based resin used as the component (D) has the following repeating structural unit; And a polymer having a degree of polymerization of 100 to 300 is preferred. This polyphenylene sulfide-based resin can be generally polymerized using p-dichlorobenzene and sodium sulfide as starting materials under an appropriate catalyst.

The polyarylate resin used as the component (D) is a polymer synthesized from an aromatic dicarboxylic acid and a dihydric phenol, and the main raw materials are terephthalic acid chloride or isophthalic acid chloride and bisphenol A, As a reaction solvent, methylene chloride or the like is used.

The repeating structural unit of the polyarylate resin when terephthalic acid chloride and bisphenol A are used is as follows:
It is as follows.

The polyphenylene ether resin used as the component (D) has a general formula (Wherein, X is a hydrogen atom, or a chlorine atom, a bromine atom or an iodine atom, R ⁷ is a hydrocarbon group, a hydrocarbonoxy group,
And a monovalent substituent selected from a halogenated hydrocarbon group having at least two carbon atoms between a halogen atom and a phenol nucleus and a halogenated hydrocarbonoxy group, R ⁸ is the same as R ⁷ , or A halogen atom, R ⁹ and
R ¹⁰ is the same as R ⁸ or a hydrogen atom.
However, all of R ^{7 to} R ¹⁰ have no tertiary carbon atom. Or a phenol compound obtained by oxidative coupling polymerization of one or more phenol compounds represented by the formula (I) in the presence of a known catalyst, or a product obtained by further modifying this with maleic anhydride.

Among the phenol compounds, particularly preferred are:
General formula (Wherein R ⁷ ′ and R ⁸ ′ are each a monovalent substituent selected from a hydrocarbon group having 1 to 8 carbon atoms, and R ⁹ ′ and R ⁸ ′
¹⁰ 'is a monovalent substituent or a hydrogen atom selected from hydrocarbon groups having 1 to 8 carbon atoms. The most preferred phenol compounds include 2,6-dimethylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, and 2-methyl-6-allyl. Phenol,
2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-dibutylphenol, 2-methyl-6-propylphenol, 2,3,6-trimethylphenol, 2,3-dimethyl-6-ethyl Phenol, 2,3,6-
Examples include triethylphenol, 2,3,6-tripropylphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-propylphenol, and the like.

Specific examples of the most preferred polyphenylene ether-based resin include polyphenylene ether and 2,6-dimethylphenol obtained from 2,6-dimethylphenol.
Polyphenylene ether obtained by copolymerization of 2,3,6-trimethylphenol. In particular, copolymerized polyphenylene ether obtained from 2,3,6-trimethylphenol and 2,6-dimethylphenol has heat resistance, impact resistance, surface gloss of molded products, moldability, solvent resistance, and thermal stability. Good.

The intrinsic viscosity [η] (measured in chloroform at 30 ° C.) of the polyphenylene ether used in the present invention is not particularly limited, but is preferably 0.2 to 1 dl / g, more preferably 0.25 to 0.7 dl / g. g.

These components (D) are used singly or as a mixture, and the proportion in the composition is 10 to 90% by weight, preferably 20 to 80% by weight.

When the component (D) in the composition is a polyamide resin, the suitable range is 10 to 90% by weight, particularly preferably 10 to 80% by weight, and when less than 10% by weight, the moldability and chemical resistance are poor. On the other hand, if it exceeds 90% by weight, the impact resistance, weld strength, and appearance of the molded product deteriorate.

The component (D) is a polyester resin alone, or a polyester resin and a polycarbonate resin and / or
Or, in the case of a mixture with a polyamide resin, the suitable range is 10 to 90% by weight, and if it is less than 10% by weight, moldability and chemical resistance are poor. Deterioration of strength and molding appearance.

Further, the component (D) is a polycarbonate resin alone,
Alternatively, in the case of mixing a polycarbonate resin with a polyamide resin and / or a polyester resin, the suitable range is 10 to 90% by weight, and if it is less than 10% by weight, the impact resistance is poor. Impact strength and weld strength deteriorate.

Further, when the component (D) is a vinyl chloride resin, an olefin resin, a polyacetal resin, a polyphenylene sulfide resin, a polyarylate resin, or a polyphenylene ether resin, the suitable range is 10 to 90% by weight, preferably Is from 10 to 80% by weight, and if it is less than 10% by weight, moldability and chemical resistance are poor, while if it exceeds 90% by weight, impact resistance is deteriorated.

As described above, the thermoplastic resin composition of the present invention contains the components (A) to (D), but needs to further satisfy the requirements (A) to (C).

That is, the carboxyl group-containing vinyl monomer in the graft copolymer (A) is usually 0.1 to 8% by weight,
It is preferably 0.2 to 7% by weight, more preferably 0.3 to 7% by weight. If it is less than 0.1% by weight, the impact resistance and weld strength are low.
Weld strength and molding appearance deteriorate.

The content of the carboxyl group-containing vinyl monomer in the whole composition is usually 0.02 to 4% by weight, preferably 0.05 to 4% by weight.
To 3.5% by weight, more preferably 0.1 to 3% by weight,
If the content is less than 0.02% by weight, impact resistance and weld strength are low, and 4
If the content is more than 10% by weight, impact resistance, weld strength, and appearance of the molded product deteriorate.

Further, the content of the polyorganosiloxane-based polymer in the whole composition is usually 5 to 40% by weight, preferably 7 to 35%.
%, More preferably 7 to 30% by weight. If it is less than 5% by weight, impact strength and weld strength are low, while if it exceeds 40% by weight, moldability deteriorates.

Furthermore, the intrinsic viscosity (30 ° C., in methyl ethyl ketone) of the matrix component (that is, the methyl ethyl ketone soluble portion in the components (A) to (C)) in the components (A) to (C) is usually 0.35 dl / g or more, preferably 0.4 to 1.0 dl / g
If it is less than 0.35 dl / g, the impact resistance and weld strength will be low.

In order to obtain the composition of the present invention, the components (A) to (D) are mixed with, for example, a mixer, and then melt-kneaded at 200 to 300 ° C. with an extruder to form pellets. Furthermore, each component can be simply melt-kneaded and molded in a molding machine.

The compositions of the present invention include an antioxidant, such as 2,6-di-
t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), tris (di-nonyl) Phenyl) phosphite; UV absorber, for example, pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4-m-octoxyphenyl) benzotriazole; lubricant For example, paraffin wax, stearic acid, hydrogenated oil, stearamide, methylene bis stearamide, n-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, boric acid Zinc, tricresyl phosphate, tris (di (Loropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agent, for example, stearoamidopropyldimethyl-β-hydroxyethyl, ammonium tolate; anti-coloring agent, for example, titanium oxide, carbon black Fillers such as calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers; pigments and the like can be added as needed.

The thermoplastic resin composition thus pelletized is processed and molded by ordinary means such as compression molding and injection molding.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified.

 In the examples, various measurement items were as follows.

The graft ratio was determined by the following method. Ie 1g of material
20 cc of acetone was added thereto, shaken for 10 hours, and then separated into soluble and insoluble using a centrifuge at 20,000 rpm, and the insoluble was removed by a vacuum dryer. After drying, an insoluble matter (X) was obtained. On the other hand, the amount of rubber (R) in the insoluble matter (X) was calculated from the polymerization composition and the polymerization conversion, and the graft ratio was determined by the following equation.

Izod impact strength was measured at 23 ° C with ASTM-D256, 1/4 "notch, and -30 ° C with 1/4" notch.

The melt flow rate (MFR) was measured at 240 ° C. and 10 kg according to JIS K7210.

The glossiness was measured at 45 ° C. according to ASTM D523.

Chemical resistance was measured by applying a constant strain of 1% to a test piece (1/8 "x 1/2" x 5 "), applying dioctyl phthalate (DOP) and brake fluid to the flexure, The time until breakage after standing at ℃ was measured and used as an index of chemical resistance.

○ indicates that there was no breakage and no crack for 100 hours or more.

Weld strength retention was measured by measuring the tensile strength (Tw) using a test piece molded using a mold with a weld line at the center of the ASTM No. 1 dumbbell, and then using a mold without a weld line. Measure the tensile strength (To) using
Weld strength retention was determined by Tw / To × 100%.

 The sliding characteristics were determined as follows.

That is, in the friction and wear test, a Suzuki type sliding tester was used, and the same material or steel (S45C) was used as a mating material. The test piece used was a hollow cylindrical one having an outer diameter of 25.6 mm and an inner diameter of 20.8 mm, and the mating member was also of the same shape.

The measurement conditions of the dynamic friction coefficient were a load of 5 kg and a running speed of 3.75 cm / sec in an atmosphere at room temperature of 23 ° C. and humidity of 50%.

 The dynamic friction coefficient is calculated by the following equation.

(Where μ is the dynamic friction coefficient, F is the force applied to the load cell,
P is the load, R is the arm length to the load cell, r ₁ is the inner diameter,
r ₂ represents the outer diameter. The conditions for measuring the wear coefficient are as follows: In the atmosphere of room temperature 23 ° C and humidity 50%, when the same material is used, load 5kg, running speed 3.75cm / sec, 12,6
00 revolutions (running speed 0.24km)
In the case of C), the measurement was performed at a load of 10 kg, a traveling speed of 15 cm / sec, and 80,000 revolutions (a traveling speed of 6 km).

 The friction coefficient is calculated by the following equation.

(Where A is the coefficient of friction, ΔW is the weight change of the sample, P
Is the load, l is the running distance, and α is the density of the sample. The weather resistance test was performed using a sunshine weather meter (manufactured by Toyo Rika Co., Ltd., WE-USN-HC type), and after exposure for 200 hours (at 63 ° C., with rain), the Izod impact strength was measured.

Reference Example 1 [Polyorganosiloxane-based polymer (R-1 to R-1)
Production of 3)] p-Vinylphenylmethyldimethoxysilane and octamethylcyclotetrasiloxane were mixed at the ratio shown in Table 1, and the mixture was placed in 300 parts of distilled water in which 2.0 parts of dodecylbenzenesulfonic acid was dissolved. The mixture was stirred for 3 minutes by a mixer to emulsify and disperse.

The mixture was transferred to a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, heated at 90 ° C. for 6 hours while stirring and mixing, and cooled at 5 ° C. for 24 hours to complete the condensation.

The condensation rate of octamethylcyclotetrasiloxane in the obtained polyorganosiloxane-based polymer was 92.8%.

This polyorganosiloxane polymer latex was neutralized to pH 7 with an aqueous sodium carbonate solution.

Reference Example 2 (Production of Graft Copolymer A-1 to 8, Graft Copolymer B-1 to 7, and Styrene Resin C-1 to 3) In a glass flask having an inner volume of 7 equipped with a stirrer, 100 parts of ion-exchanged water, 0.5 part of sodium dodecylbenzenesulfonate, 0.01 part of potassium hydroxide, 0.1 part of t-dodecylmercaptan and 0.1 parts of t-dodecylmercaptan were mixed with the polyorganosiloxane-based polymer latex of Table 1 in various proportions. A batch polymerization component consisting of a body was added, and the temperature was raised while stirring. When the temperature reached 45 ° C., an activator aqueous solution consisting of 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water, and diisopropylbenzene 0.1 part of hydroperoxide was added and the reaction continued for 1 hour.

Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.02 part of potassium hydroxide, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropylbenzene hydroperoxide and the various monomers in the proportions shown in Table 2 The resulting mixture of incremental polymerization components was added continuously over 3 hours and the reaction continued.

After completion of the addition, the reaction was continued for 1 hour with further stirring.
-Butylphenol) was added and the reaction product was taken out of the flask.

Next, the product was coagulated using 2 parts of potassium chloride, dehydrated, washed with water, and dried to recover a powdery polymer.

Table 2 shows the monomer polymerization conversion, the graft ratio, and the intrinsic viscosity [η] measured by the method described above.

Examples 1 to 21 and Comparative Examples 1 to 17 The components (A) to (D) shown in Table 3 were melt-kneaded with an extruder having an inner diameter of 40 mm in a temperature range of 250 to 320 ° C. to produce pellets.

These pellets are injected into a 5 _oz injection molding machine (Toshiba Corporation, IS
Using -80A), a test piece was prepared by molding at a molding temperature of 260 to 300 ° C, and its physical properties were evaluated. The results are shown in Table 3.

In addition, in an Example and a comparative example, as a (D) component,
The following were used:

Nylon 6; Toray Industries, Ltd., Amilan CM1017 Nylon 4,6; DSM, stanyl KS300 PBT (polybutylene terephthalate); Polyplastics, Duranex XD499 PC (polycarbonate); Idemitsu Petrochemical Co., Ltd. A-
2200 PVC (polyvinyl chloride); Alon TS700 MPP (maleic anhydride-modified polypropylene) manufactured by Toa Gosei Chemical Co., Ltd .; MODIC P-10B POM (polyoxymethylene) manufactured by Mitsubishi Yuka Co., Ltd .; Polyplastics Co., Ltd. )
Manufactured by Duracon M90 PPS (polyphenylene sulfide); manufactured by Topren Co., Ltd .; toprene T-4 polyarylate; manufactured by Unitika Ltd .; U Polymer U-80
Regarding PPE (polyphenylene ether), a polymer was obtained by the following method.

Production of PPE1 (polyphenylene ether) 2,6-xylenol is used as a catalyst for cupric bromide, di-
The polymerization reaction was carried out using n-butyleneamine in a toluene solution at 30 ° C. while blowing oxygen.

After the polymerization was completed, an aqueous solution of trisodium ethylenediaminetetraacetate was added to remove the catalyst.

The polymer solution phase was removed from the resulting product mixture by centrifugation. While vigorously stirring the polymer solution, methanol was gradually added to form a slurry. After separating the solid content, the polymer was sufficiently washed with methanol and dried to obtain a polymer (PPE1). (Η) of polymer PPE1 measured at 30 ° C. using chloroform as a solvent is 0.40 dl
/ g.

Production of PPE2 (maleic anhydride-modified polyphenylene ether) 2 parts of maleic anhydride and 1 part of 2,5-dimethyl-2,5-di (t-butyleneperoxy) hexane were added to 100 parts by weight of the polymer PPE1. After dry blending at room temperature, using a twin-screw extruder with a vent in the same direction, melt kneading at a cylinder temperature of 300 ° C and a screw rotation speed of 150 rpm to pelletize the polymer, An acid-modified polyphenylene ether (PPE2) was obtained.

As is clear from Table 3, according to Examples 1-26,
The thermoplastic resin composition intended for the present invention has been obtained.

On the other hand, in Comparative Examples 1 to 17, the effects intended by the present invention cannot be obtained.

That is, in Comparative Examples 1 to 8, the component (D) was nylon 6
The amount of the polyorganosiloxane-based polymer and the amount of the graft-crosslinking agent of the component (A) or the amount of the polyorganosiloxane-based polymer and the amount of the graft-crosslinking agent of the component (B) of the present invention is the polyamide composition of the present invention. It is out of the range, and the Izod impact strength, glossiness and weld strength are inferior.

Comparative Examples 9 and 10 are polyamide compositions in which the component (D) is nylon 6, and the amount of the nylon 6 as the component (D) is out of the range of the present invention.
Poor chemical resistance, gloss and weld strength.

Further, Comparative Examples 11 and 12 are polyester compositions in which the component (D) is polybutylene terephthalate (PBT), and the PBT amount of the component (D) is out of the range of the present invention.
Poor Izod impact strength, chemical resistance, glossiness, and weld strength.

Further, Comparative Examples 13 and 14 are PC compositions in which the component (D) is polycarbonate (PC), and
The amount is outside the range of the present invention, and the Izod impact strength, chemical resistance, glossiness, and weld strength are poor.

Further, Comparative Examples 15 to 17 used compositions composed of two types of mixtures as the component (D), but none of the components contained the component (A), and had Izod impact strength, glossiness, Poor weld strength.

[Effects of the Invention] The thermoplastic resin composition of the present invention has a high balance of impact resistance, moldability, chemical resistance, and weld strength. Further, the composition of the present invention is a conventional polyamide resin, polyester resin, polycarbonate resin, vinyl chloride resin, olefin resin, polyacetal resin, polyphenylene sulfide resin, polyarylate resin, polyphenylene ether resin And eliminated the disadvantages of these compositions, and succeeded in imparting the properties of silicone rubber such as weather resistance, cold resistance, sliding properties, and abrasion resistance. A new thermoplastic resin having excellent characteristics that cannot be obtained is obtained. Therefore, the thermoplastic resin composition of the present invention is a molding material that satisfies the requirements of the molding and processing industry, and is applicable to new application fields such as sliding parts, parts for cold regions, parts for outdoor use, and the like. The significance is extremely large.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08L 71/12 LQP C08L 71/12 LQP 81/02 LRG 81/02 LRG

Claims (1)

(57) [Claims] (A) 5-90% by weight of a polyorganosiloxane-based polymer obtained by cocondensing 0.1 to 50% by weight of at least one type of graft-linking agent selected from the following groups (a) to (d):
5 to 90% by weight of a graft copolymer obtained by graft polymerization of 95 to 10% by weight of a carboxyl group-containing vinyl monomer and another vinyl monomer in total; (Wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and a graft crosslinking agent having both an alkoxysilyl group and an unsaturated group. (B) R ³ _p SiO _{(3-p) / 2} (wherein, R ³ represents a vinyl group or an allyl group, and p represents an integer of 0 to 2.) (c) HSR ⁴ SiR ⁵ _q O _{(3- q) / 2} (wherein, R ⁴ represents a divalent or trivalent saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms, and R ⁵ represents a monovalent monovalent group containing no aliphatic unsaturated group having 1 to 6 carbon atoms. A hydrocarbon group, and q represents an integer of 0 to 2.) (In the formula, R ⁶ is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a phenyl group, r is an integer of 1 to 6, and s is an integer of 0 to 2.) (B) The polyorganosiloxane-based polymer 5 to 80% by weight of a graft copolymer obtained by graft polymerization of 95 to 10% by weight of another vinyl monomer excluding the carboxyl group-containing vinyl monomer to 5 to 90% by weight of the styrene resin; 80% by weight, and (D) selected from polyamide resin, polyester resin, polycarbonate resin, vinyl chloride resin, olefin resin, polyacetal resin, polyphenylene sulfide resin, polyarylate resin, and polyphenylene ether resin 10 to 90% by weight of at least one type of thermoplastic resin (provided that (A) + (B) + (C)
+ (D) = 100% by weight].