JPH10316833A - Water-repellent thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin composition capable of exhibiting excellent impact resistance, water-repelling property, etc., by compounding a graft copolymer with a vinyl-based copolymer, a modified vinyl-based copolymer and a modified polyorganosiloxane at a specific ratio. SOLUTION: This resin composition comprises (A) 3-50 wt.% graft copolymer obtained by subjecting 80-20 pts.wt. mixture of (ii) 40-90 wt.% aromatic vinyl monomer with (iii) 10-60 wt.% vinyl cyanide-based monomer and (iv) 0-80 wt.% other copolymerizable vinyl-based monomer to graft copolymerization in the presence of (i) 20-80 pts.wt. rubber-based polymer, (B) 5-90 wt.% vinyl-based copolymer obtained by copolymerizing a mixture of 40-90 wt.% component (ii) with 10-60 wt.% component (iii) and 0-80 wt.% component (iv), (C) 0.1-50 wt.% modified vinyl-based copolymer having at least one kind of compounds selected from epoxy group, carboxyl group and acid anhydride group and (D) 0.1-20 wt.% modified polyorganosiloxane having at least one kind of the same reaction group as that of the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition having excellent impact resistance, water repellency, fluidity and appearance of a molded article.

[0002]

2. Description of the Related Art ABS resins have excellent mechanical properties, moldability and surface gloss, and are used in home electric appliances, OA appliances,
It is used in a wide range of fields including various parts such as automobiles. In particular, in applications where impact resistance and gloss are required, ABS resins are preferably used.

However, when an ABS resin is used for a toilet, a toilet, or a part around a bath, water repellency is often required in recent years from the viewpoint of dirt and cleanliness.

[0004] On the other hand, a resin composition in which a fluorine resin or a silicone resin is added to an ABS resin has been proposed for other purposes as disclosed in Japanese Patent Application Laid-Open No. 6-287247. Therefore, if a large amount is added to impart sufficient water repellency, there is a problem that not only the impact strength is reduced but also the appearance of the molded product is deteriorated.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a thermoplastic resin composition which is excellent in impact resistance, water repellency, fluidity, and appearance of a molded product in balance. And

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific graft copolymer, a specific vinyl copolymer, and a modified vinyl copolymer having a specific reactive group have been obtained. By blending the copolymer and the modified polyorganosiloxane having a specific reactive group in a specific ratio,
The present inventors have found that the above objects can be efficiently achieved, and have reached the present invention.

That is, the present invention relates to a rubbery polymer (a) 2
Aromatic vinyl monomer (b) in the presence of 0 to 80 parts by weight
40 to 90% by weight, vinyl cyanide monomer (c) 10
A monomer mixture of 80 to 60% by weight and 0 to 80% by weight of another copolymerizable vinyl monomer (d)
3 to 50% by weight of a graft copolymer (A) obtained by graft copolymerizing 0 part by weight of an aromatic vinyl monomer (b) 4
0 to 90% by weight, vinyl cyanide monomer (c)
5 to 90% by weight of a vinyl copolymer (B) obtained by copolymerizing a monomer mixture comprising 60% by weight and 0 to 80% by weight of another copolymerizable vinyl monomer (d), epoxy From 0.1 to 50% by weight of a modified vinyl copolymer (C) containing at least one reactive group selected from the group consisting of an epoxy group, a carboxyl group and an acid anhydride group; Modified polyorganosiloxane (D) containing at least one selected reactive group
A water-repellent thermoplastic resin composition comprising 0.1 to 20% by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

The graft copolymer (A) in the present invention
Refers to the presence of 20 to 80 parts by weight of the rubbery polymer (a)
40 to 90% by weight of an aromatic vinyl monomer (b), 10 to 60% by weight of a vinyl cyanide monomer (c) and 0 to 80% by weight of another copolymerizable vinyl monomer (d) % Of a monomer mixture of 80 to 20 parts by weight.

The term "graft copolymer" as used herein includes, in addition to a material having a structure obtained by graft copolymerization with a rubbery polymer,
It contains a non-grafted copolymer.

As the rubbery polymer (a), those having a glass transition temperature of 0 ° C. or less are suitable, and diene rubbers are preferably used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, butyl acrylate-butadiene copolymer, and acrylics such as polybutyl acrylate Rubber, polyisoprene, ethylene-propylene-diene terpolymer and the like. Among them, polybutadiene or butadiene copolymer is preferred.

Although the rubber particle diameter of the rubbery polymer (a) is not particularly limited, the weight average particle diameter of the rubber particles is 0.15 to 0.15.
0.60 μm, especially 0.20 to 0.55 μm is preferable in terms of impact resistance.

The aromatic vinyl monomer (b) used for the graft copolymer (A) and the vinyl copolymer (B) is styrene, α-methylstyrene, vinyltoluene,
Examples thereof include o-ethylstyrene and pt-butylstyrene, and styrene is particularly preferable.

The vinyl cyanide monomer (c) used for the graft copolymer (A) and the vinyl copolymer (B) includes acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and especially acrylonitrile. Is preferred in terms of impact resistance.

Other copolymerizable vinyl monomers (d) used for the graft copolymer (A) and the vinyl copolymer (B) include maleimide, N-methylmaleimide and N-phenylmaleimide. Maleimide monomers, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, itaconic acid and other α, β-unsaturated carboxylic acids and their anhydrides, methyl acrylate, butyl acrylate, α , Β-unsaturated carboxylic acid esters and acrylamide can be used, and among them, N-phenylmaleimide and methyl methacrylate are preferred from the viewpoint of moldability.

The monomer mixture used in the graft copolymer (A) is such that the aromatic vinyl monomer (b) is 40 to 9%.
0% by weight, preferably 50 to 80% by weight. If the amount of the aromatic vinyl monomer (b) is less than 40% by weight, the resulting water-repellent thermoplastic resin composition has insufficient flowability, and
If the amount is more than 10% by weight, the impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient. The content of the vinyl cyanide monomer (c) is 10 to 60% by weight, preferably 20 to 50% by weight.
% By weight. When the amount of the vinyl cyanide monomer (c) is less than 10% by weight, the impact resistance of the resulting water-repellent thermoplastic resin composition is not sufficient. When the amount exceeds 60% by weight, the obtained water-repellent thermoplastic resin is obtained. The fluidity of the composition is not sufficient. The other copolymerizable vinyl monomer (d) is 0 to
It is 80% by weight, preferably 0 to 70% by weight. When the amount of the other copolymerizable vinyl monomer (d) exceeds 80% by weight, the impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient.

The ratio of the rubbery polymer (a) to the monomer mixture when the graft copolymer (A) is obtained may be a single monomer in the presence of 20 to 80 parts by weight of the rubbery polymer (a). Body mixture 80
It is necessary to graft polymerize up to 20 parts by weight. If the amount of the rubbery polymer (a) is less than 20 parts by weight, the impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient, and if it exceeds 80 parts by weight, the flowability of the obtained water-repellent thermoplastic resin composition is increased. Sex is not enough.

The graft copolymer (A) can be obtained by a known polymerization method. For example, it is obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a latex of a rubbery polymer (a) to carry out emulsion polymerization. be able to.

The graft copolymer (A) contains an ungrafted copolymer in addition to a material having a structure grafted to the rubbery polymer (a). The graft ratio of the graft copolymer (A) is not particularly limited, but is preferably from 30 to 30 in order to obtain a resin composition having excellent impact resistance and gloss.
120% by weight is preferred. Here, the graft ratio is calculated by the following equation.

Graft ratio (%) = (amount of vinyl copolymer graft-polymerized on rubbery polymer) / (rubber content of graft copolymer) × 100

The vinyl copolymer (B) in the water-repellent thermoplastic resin composition of the present invention comprises 40 to 90% by weight of an aromatic vinyl monomer (b) and a vinyl cyanide monomer (c). It is necessary to copolymerize a monomer mixture consisting of 10 to 60% by weight and 0 to 80% by weight of another copolymerizable vinyl monomer (d). Here, the content of the aromatic vinyl monomer (b) in the monomer mixture is 40 to 90% by weight, preferably 50 to 80% by weight. If the amount of the aromatic vinyl monomer (b) is less than 40% by weight, the resulting water-repellent thermoplastic resin composition has insufficient flowability and 90% by weight.
If the ratio exceeds the above, the impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient. The content of the vinyl cyanide monomer (c) is 10 to 60% by weight, preferably 20 to 50% by weight. 10% by weight of vinyl cyanide monomer (c)
If it is less than 50%, the resulting water-repellent thermoplastic resin composition has insufficient impact resistance. If it exceeds 60% by weight, the resulting water-repellent thermoplastic resin composition has insufficient fluidity. The content of the other copolymerizable vinyl monomer (d) is 0 to 80% by weight, preferably 0 to 70% by weight. When the other copolymerizable vinyl monomer (d) exceeds 80% by weight,
The impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient.

Although the molecular weight of the vinyl copolymer (B) is not particularly limited, the reduced copolymer has a reduced viscosity of 0.30 to 0.1.
90 dl / g, particularly in the range of 0.35 to 0.85 dl / g, is preferably used in terms of excellent impact resistance and fluidity.

The method for producing the vinyl copolymer (B) is not particularly limited, and may be a known method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, or bulk-suspension polymerization. Can be manufactured.

The modified vinyl copolymer (C) used in the present invention refers to a vinyl monomer containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group and another vinyl monomer. It is a copolymer with a monomer such as glycyl methacrylate and glycyl acrylate, and a vinyl monomer containing a carboxyl group such as methacrylic acid, acrylic acid and maleic acid. And a copolymer of an acid anhydride-containing vinyl monomer such as maleic anhydride and citraconic acid with the aromatic vinyl monomer (b), vinyl cyanide monomer (c), and the like. Specifically, styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer, acrylic acid-styrene copolymer, acrylic acid-acrylonitrile-styrene copolymer, methacrylic acid-styrene copolymer Methacrylic acid-styrene-acrylonitrile copolymer, styrene-acrylonitrile-glycyl methacrylate, styrene-glycyl methacrylate, and the like. It is preferable in terms of properties.

Although the molecular weight of the modified vinyl copolymer (C) is not particularly limited, it has a reduced viscosity of 0.30 to 0.90.
dl / g, particularly in the range of 0.35 to 0.85 dl / g, is preferably used from the viewpoint of excellent impact resistance and fluidity.

The method for producing the modified vinyl copolymer (C) is not particularly limited, and includes a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method,
It can be produced by an ordinary known method such as a solution polymerization method or a bulk-suspension polymerization method.

The modified polyorganosiloxane (D) used in the present invention is a polyorganosiloxane containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group. Epoxy-modified silicone oil, carboxy-modified silicone, maleic anhydride-modified silicone, and the like can be mentioned. Among them, epoxy-modified silicone oil is preferable in terms of water repellency.

Although the viscosity of the modified polyorganosiloxane (D) is not particularly limited, it is from 1 to 30,000 cSt, especially from 10 to 30,000 cSt.
It is preferable from the viewpoint of the balance between the water repellency of the water repellent thermoplastic resin composition obtained in the range of 20,000 cSt and the appearance of the molded product.

In the water-repellent thermoplastic resin composition of the present invention, the content of the graft copolymer (A) is 3 to 50% by weight, preferably 5 to 45% by weight. If the amount of the graft copolymer (A) is less than 3% by weight, the impact resistance of the obtained water-repellent thermoplastic resin composition is not sufficient, and if it exceeds 50% by weight, the fluidity of the obtained water-repellent thermoplastic resin composition Is not enough.

The vinyl copolymer (B) has a content of 5 to 90%.
% By weight, preferably 10 to 85% by weight. If the amount of the vinyl copolymer (B) is less than 5% by weight, the resulting water-repellent thermoplastic resin composition has insufficient fluidity. If the amount exceeds 90% by weight, the resulting water-repellent thermoplastic resin composition has an insufficient resistance. Not enough impact.

The modified vinyl copolymer (C) has a content of 0.1%.
It is 1 to 50% by weight, preferably 0.5 to 45% by weight. When the content of the modified vinyl copolymer (C) is less than 0.1% by weight, the water repellency of the resulting water repellent thermoplastic resin composition is not sufficient, and when the content exceeds 50% by weight, the obtained water repellent thermoplastic resin composition Has insufficient impact resistance.

The modified polyorganosiloxane (D)
Is 0.1 to 20% by weight, preferably 0.5 to 15% by weight. If the modified polyorganosiloxane (D) is less than 0.1% by weight, the resulting water-repellent thermoplastic resin composition has insufficient water repellency, and if it exceeds 20% by weight, the molded article of the water-repellent thermoplastic resin composition obtained is obtained. Appearance is not enough.

There is no particular limitation on the method for producing the water-repellent thermoplastic resin composition of the present invention, and the graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C) and The modified polyorganosiloxane (D) can be produced by melt-kneading with a Banbury mixer, a roll, a single screw extruder, a twin screw extruder, a kneader, or the like.

The water-repellent thermoplastic resin composition of the present invention comprises
Polyethylene such as polyethylene, polypropylene, polyamide such as nylon 6, nylon 66, polyester such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethyl terephthalate, polyphenylene ether, polyglutarimide, polyphenylene sulfide, etc. The performance of the resin composition for molding can be further improved by blending the rubber composition with various elastomers.

The water-repellent thermoplastic resin composition of the present invention may contain, if necessary, an antioxidant such as a hindered phenol-based compound, a sulfur-containing compound-based compound, a phosphorus-containing organic compound-based compound, and a phenol-based or acrylate-based compound. Various stabilizers such as heat stabilizers, ultraviolet absorbers such as benzotriazoles, benzophenones, and succinates; light stabilizers such as organic nickel and hindered amines; metal salts of higher fatty acids;
Lubricants such as higher fatty acid amides, phthalates,
Plasticizers such as phosphate esters, flame retardants such as decabromobiphenyl ether, tetrabromobisphenol A, chlorinated polyethylene, brominated epoxy oligomers, brominated polycarbonates, antimony trioxide, and condensed phosphate esters, and flame retardant aids Agents, carbon black, titanium oxide, pigments, dyes and the like can also be added.

Further, the water-repellent thermoplastic resin composition of the present invention includes glass fibers, glass flakes, glass beads,
Reinforcing agents and fillers such as carbon fibers and metal fibers can also be added.

The water-repellent thermoplastic resin composition obtained as described above can be used in a conventional thermoplastic resin molding such as injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas assist molding. It can be formed by a method and is not particularly limited.

The water-repellent thermoplastic resin composition of the present invention takes advantage of the excellent properties of impact resistance, water repellency, fluidity, and appearance of a molded product, and can be used for water-borne resin parts such as toilets, toilets, and baths. Suitable for.

[0039]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In addition, the number of parts and% in an Example show a weight part and weight%, respectively. In addition, the evaluation methods and measurement methods for each physical property are as follows.

Rubber weight average particle diameter: ES chmidt, PH.Bi
Sodium alginate method described in ddison Rubber Age 88 484 (1960) (using the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate,
The particle diameter at a cumulative weight fraction of 50% is determined from the weight ratio of the cream and the cumulative weight fraction of the sodium alginate concentration).

Graft ratio: Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. Add this solution to 8
After centrifugation at 000 rpm (10,000 G) for 30 minutes, insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, and the weight (n) was measured. The graft ratio is determined by the following method.

Graft ratio = [(n)-(m) × L] /
[(M) × L] × 100 L; rubber content of graft copolymer.

Reduced viscosity ηsp / C: sample concentration 0.4 g /
The dl methyl ethyl ketone solution was measured at 30 ° C. using an Ubbelohde viscometer.

1/2 "Izod impact strength: ASTM
D256-56A MFR (Melt Flow Rate): ISO1133
(220 ° C., 10 Kg) Water repellency: The contact angle (degree) (an angle between the tangent line at the contact point between water and the resin surface and the water side formed by the resin surface) was measured and evaluated. The larger the contact angle, the better the water repellency.

Appearance of molded article: The surface of the injection-molded article was visually observed, and the case where there was no gloss and there was a feeling of roughness was evaluated as ×.
(Poor), when there is gloss and there is no roughness
(Good), and the middle was △ (medium).

Reference Example 1 Preparation of Graft Copolymer (A)
Ltd.) <A-1> polybutadiene latex (weight average particle diameter of 0.21 [mu] m, gel content 80%) 45 parts (solid basis)
55 parts of a monomer mixture consisting of 79% of styrene and 21% of acrylonitrile was emulsion-polymerized in the presence of the above. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered and dried to prepare a powdery graft copolymer (A-1). The obtained graft copolymer (A
The graft ratio of -1) was 41%.

<A-2> A monomer mixture 40 consisting of 70% styrene and 30% acrylonitrile in the presence of 60 parts (in terms of solid content) of polybutadiene latex (weight average particle diameter 0.32 μm, gel content 88%) Parts were emulsion polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (A-2). The graft ratio of the obtained graft copolymer (A-2) was 38%.

<A-3> A monomer mixture 85 composed of 70% styrene and 30% acrylonitrile in the presence of 15 parts (in terms of solid content) of 15 parts of polybutadiene latex (weight average particle size 0.10 μm, gel content 88%) Parts were emulsion polymerized. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to prepare a powdery graft copolymer (A-3). The graft ratio of the obtained graft copolymer (A-3) was 130%.

Reference Example 2 Preparation of Vinyl Copolymer (B)
Ltd. <B-1> styrene 70%, acrylonitrile 29.7
%, And a monomer mixture of t-dodecyl mercaptan 0.3% was subjected to suspension polymerization to prepare a vinyl copolymer (B-1). The reduced viscosity of the obtained vinyl copolymer (B-1) was 0.65 dl / g.

<B-2> Styrene 50%, N-phenylmaleimide 30%, acrylonitrile 19.7%, t-
Emulsion polymerization of a monomer mixture of 0.3% of dodecyl mercaptan was carried out to prepare a vinyl copolymer (B-2).

The reduced viscosity of the obtained vinyl copolymer (B-2) was 0.56 dl / g.

<B-3> A monomer mixture of 95% styrene, 4.7% acrylonitrile and 0.3% t-dodecylmercaptan is subjected to suspension polymerization to obtain a vinyl copolymer (B-3).
Was prepared. The reduced viscosity of the obtained vinyl copolymer (B-3) was 0.45 dl / g.

Reference Example 3 Modified Vinyl Copolymer (C)
Preparation) <C-1> Styrene 70%, acrylonitrile 25%,
Acrylic acid 4.9%, t-dodecyl mercaptan 0.3
% Of the monomer mixture was subjected to suspension polymerization to prepare a modified vinyl copolymer (C-1). The reduced viscosity of the resulting modified vinyl copolymer (C-1) was 0.50 dl / g.

<C-2> A monomer mixture of 70% styrene, 25% acrylonitrile, 4.8% methacrylic acid and 0.2% t-dodecylmercaptan is subjected to suspension polymerization to form a modified vinyl copolymer (C). -2) was prepared. The reduced viscosity of the resulting modified vinyl copolymer (C-2) was 0.55 dl.
/ G.

<C-3> A monomer mixture of 70% styrene, 25% acrylonitrile, 4.8% methyl methacrylate, and 0.2% t-dodecyl mercaptan is subjected to suspension polymerization to form a modified vinyl copolymer ( C-3) was prepared. The reduced viscosity of the resulting modified vinyl copolymer (C-3) is 0.5
It was 4 dl / g.

Reference Example 4 Modified polyorganosiloxane
Preparation of (D)) <D-1> Side chain alicyclic epoxy group-modified silicone oil BY16-839 manufactured by Toray Dow Corning Silicone Co., Ltd.
(Viscosity 6000 cSt) was used as the modified polyorganosiloxane (D-1).

<D-2> Side chain glycidyl group-modified silicone oil SF8 manufactured by Toray Dow Corning Silicone Co., Ltd.
411 (viscosity: 8000 cSt).

<D-3> Unmodified silicone oil SH200 (viscosity 30) manufactured by Toray Dow Corning Silicone Co., Ltd.
00cSt) was used as the polyorganosiloxane (D-3).

Examples 1 to 5 (water-repellent thermoplastic resin composition)
Production of the graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C) and modified polyorganosiloxane (D) shown in Reference Example And a resin temperature of 23 with a 40 mmφ single screw extruder with vent.
A pellet-shaped water-repellent thermoplastic resin composition was produced by melt-kneading and extrusion at 0 ° C. Then, using an injection molding machine, the cylinder temperature was 230 ° C and the mold temperature was 60.
A test piece was molded at a temperature of ° C., and the physical properties were measured under the above conditions. The obtained measurement results are shown in Table 1.

Comparative Examples 1 to 8 Graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C) and
The modified polyorganosiloxane (D) was mixed at the compounding ratio shown in Table 1, and each physical property was measured in the same manner as in the examples. The measurement results are shown in Table 1.

[0061]

[Table 1]

The following is clear from the results in Table 1.
Each of the water-repellent thermoplastic resin compositions of the present invention (Examples 1 to 5) is excellent in balance of impact resistance, water repellency, fluidity and appearance of a molded article.

On the other hand, when the blending amounts of the graft copolymer (A), vinyl copolymer (B), modified vinyl copolymer (C) and modified polyorganosiloxane (D) are out of the range of the present invention. Comparative Example 1 is inferior in water repellency, Comparative Example 2 is inferior in water repellency and molded article appearance, Comparative Example 3 is inferior in impact resistance, and Comparative Example 4 is inferior in fluidity and molded article appearance.

Further, the graft copolymer (A), the vinyl copolymer (B), the modified vinyl copolymer (C) and / or
Alternatively, when the modified polyorganosiloxane (D) is out of the range of the present invention, Comparative Examples 5.6 and 6 are inferior in water repellency and molded article appearance, Comparative Example 7 is inferior in impact resistance, and Comparative Example 8 is in impact strength and molding The product appearance is poor.

[0065]

The thermoplastic resin composition of the present invention is excellent in balance of impact resistance, water repellency, fluidity and appearance of a molded article, and is suitable for water-borne resin parts such as toilets, toilets, and baths. Useful for such things.

Claims (6)

[Claims] 1. An aromatic vinyl monomer (b) 40 to 90% by weight in the presence of 20 to 80 parts by weight of a rubbery polymer (a),
Graft copolymerization of 80 to 20 parts by weight of a monomer mixture comprising 10 to 60% by weight of a vinyl cyanide monomer (c) and 0 to 80% by weight of another copolymerizable vinyl monomer (d). 3 to 50% by weight of a graft copolymer (A), 40 to 90% by weight of an aromatic vinyl monomer (b), 10 to 60% by weight of a vinyl cyanide monomer (c) and other 5 to 90% by weight of a vinyl copolymer (B) obtained by copolymerizing a monomer mixture comprising 0 to 80% by weight of a copolymerizable vinyl monomer (d), epoxy group, carboxyl group and acid Modified vinyl copolymer (C) containing at least one reactive group selected from anhydride groups (C) 0.1 to 50
Water-repellent heat characterized by comprising 0.1 to 20% by weight of a modified polyorganosiloxane (D) containing at least one reactive group selected from an epoxy group, a carboxyl group and an acid anhydride group. Plastic resin composition. 2. The water-repellent thermoplastic resin composition according to claim 1, wherein the graft copolymer (A) is a styrene-acrylonitrile-butadiene copolymer. 3. The rubbery polymer of the graft copolymer (A) is a polybutadiene rubber having a weight average particle diameter of 0.15 to 0.6 μm, and a styrene-acrylonitrile-butadiene copolymer having a graft ratio of 30 to 120% by weight. The water-repellent thermoplastic resin composition according to claim 1, wherein the composition is a polymer. 4. The method according to claim 1, wherein the vinyl copolymer (B) is a styrene-acrylonitrile copolymer.
The water-repellent thermoplastic resin composition according to the above. 5. A modified vinyl copolymer (C) comprising styrene-
The water-repellent thermoplastic resin composition according to claim 1, which is an acrylonitrile-acrylic acid copolymer. 6. The water-repellent thermoplastic resin composition according to claim 1, wherein the modified polyorganosiloxane (D) is an epoxy-modified silicone oil.