JP2007161940A - Resin composition for plating and painting, and molded-article therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for plating and painting which is excellent in the adhesion of a plating layer, painting adhesion and surface impulsiveness; a plated molded-article; and a painted molded-article. <P>SOLUTION: This resin composition for plating and painting comprises adding 0.05 to 80 parts by weight of a modified vinyl-based copolymer comprising an α,β-unsaturated carboxylic acid anhydride unit having a limiting viscosity in a specified range to, a resin composition comprising 55 to 85% by weight of a styrene-based resin and 45 to 15% by weight of a polyamide resin, wherein in the central part of the resin composition, a specified phase structure is formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition comprising a styrene-based resin and a polyamide resin, which is suitable for plating treatment and coating treatment, has excellent plating adhesion and coating adhesion, has a good appearance, and further has surface impact. The present invention relates to an excellent resin composition for plating and painting, and a plated molded body and a painted molded body.

  Styrenic resins are widely used as general-purpose thermoplastic resins because they have the characteristics of high rigidity, good appearance, good dimensional stability, and low water absorption. However, the styrene-based resin has insufficient chemical resistance, wear resistance and heat resistance, and its use under severe conditions has been limited. In addition, crystalline thermoplastic resin compositions, especially polyamide resins, are widely used as engineering plastics because of their excellent chemical resistance, wear resistance, and heat resistance, but they have high water absorption, rigidity and dimensions. Stability was not enough.

  Therefore, studies have been made on resin compositions that combine the advantages of styrene resins and polyamide resins. For example, a blend composition of ABS resin and polyamide resin, which is a typical styrene resin, has been proposed. Yes. Since the resin composition comprising ABS resin and polyamide resin also has an advantage of relatively low specific gravity, its application development includes application to interior / exterior materials of automobiles, automobile parts, and housings / parts of electric / electronic devices. Application development can be mentioned. In particular, it is necessary to apply plating to automobile parts and the like from the viewpoint of imparting a high-class feeling and aesthetic appearance.

  Then, the molded object which plated the resin composition which consists of ABS resin and a polyamide resin is proposed (patent document 1, patent document 2). These plated resin moldings have relatively good plating layer adhesion. However, when used as plating resin moldings for automobile parts, etc., the plating layer adhesion is further improved and the surface is excellent. There was a demand for impact.

Also, a styrene-acrylonitrile-methacrylic acid copolymer having a specific reduced viscosity with respect to the ABS resin and the polyamide resin for the purpose of obtaining a resin composition having an ABS resin and a polyamide resin and excellent in paintability. A resin composition to which is added has been proposed (see Patent Documents 3 and 4). However, these resin compositions do not have a sufficient balance between the coating adhesion strength and the surface impact required in application development around automobile interior and exterior materials, automotive parts, and housings and parts of electrical and electronic equipment. .
JP 2003-82138 A (Claims) Japanese Patent Laying-Open No. 2005-298899 (Claims) JP 2004-131716 A (Claims) JP 2004-149791 A (Claims)

  The present invention provides a plating and coating resin composition comprising a styrene-based resin and a polyamide resin, has excellent plating adhesion and coating adhesion, has a good appearance, and has also been subjected to plating and coating treatment. The present invention provides a resin composition for plating and painting having excellent surface impact properties, and a molded article for plating and painting.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a specific modified vinyl copolymer having a specific viscosity in a specific range by blending a styrene resin and a polyamide resin with a specific composition. Addition to form a specific phase structure in the phase structure at the center of the molded body, thereby solving this problem, excellent plating adhesion and coating adhesion, good appearance, and surface impact It was found that a resin composition for plating and painting excellent in the above and a molded product of plating and painting can be obtained.

That is, the present invention
(1) Graft obtained by graft polymerization of a monomer unit comprising 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer on a rubber polymer ( (Co) polymer (A-1), vinyl (co) polymer (A-) comprising 100 to 45% by weight of aromatic vinyl monomer and 0 to 55% by weight of at least one other monomer. 2) with respect to 100 parts by weight of a thermoplastic resin composition comprising 55 to 85% by weight of a styrene resin (A) obtained by blending at least one kind and 45 to 15% by weight of a polyamide resin (B). The modified vinyl copolymer (C) comprising 0.05 to 20% by weight of β-unsaturated carboxylic acid anhydride unit and 0.5 to 60% by weight of vinyl cyanide monomer unit. Further containing 80 parts by weight, and the modified vinyl copolymer (C) A thermoplastic resin composition having an intrinsic viscosity in a range of 0.15 to 0.41 dl / g when dissolved in a tilethyl ketone solvent and measured at a temperature of 30 ° C., and further melting the thermoplastic resin composition In the molded product obtained by the molding process, when the direction perpendicular to the surface of the molded product is defined as the thickness, the phase structure is observed with an electron microscope in a region having a depth of 40 to 60% of the total thickness from the surface. A resin composition for plating, wherein the polyamide resin (B) is formed in a continuous phase part of 10% by volume or more,
(2) The intrinsic viscosity as measured in a methyl ethyl ketone solvent of the modified vinyl copolymer (C) when measured at a temperature of 30 ° C. is in the range of 0.15 to 0.30 dl / g, according to (1). Plating resin composition,
(3) The modified vinyl copolymer (C) contains 1.5 to 10% by weight of α, β-unsaturated carboxylic anhydride unit and 0.5 to 60% by weight of vinyl cyanide monomer unit. (1) or the resin composition for plating according to (2),
(4) A plated test piece obtained by plating an 80 mm × 80 mm × 3 mm thick test piece after injection molding with a thickness of 35 ± 5 μm at 23 ° C., punch tip diameter 5/8 inch, impact speed 2.5 m The resin composition for plating according to any one of (1) to (3), wherein impact energy obtained by performing a high-speed surface impact test under the conditions of / s is 20 J or more,
(5) A plating test piece obtained by plating an 80 mm × 80 mm × 3 mm thick test piece after injection molding is provided with a 1 mm square grid (10 × 10 pieces), and is defined in JIS K5400-1990. (1) to (4), wherein the remaining number of plating films when the cellophane tape peeling test is performed and the cellophane tape peeling test is performed is 70 or more Resin composition,
(6) A graft formed by graft polymerization of a monomer unit comprising 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer on a rubber polymer ( (Co) polymer (A-1), vinyl (co) polymer (A-) comprising 100 to 45% by weight of aromatic vinyl monomer and 0 to 55% by weight of at least one other monomer. 2) with respect to 100 parts by weight of a thermoplastic resin composition comprising 55 to 85% by weight of a styrene resin (A) obtained by blending at least one kind and 45 to 15% by weight of a polyamide resin (B). The modified vinyl copolymer (C) comprising 0.05 to 10% by weight of β-unsaturated carboxylic acid anhydride unit and 0.5 to 60% by weight of vinyl cyanide monomer unit. Further containing 80 parts by weight, and the modified vinyl copolymer (C) A thermoplastic resin composition having an intrinsic viscosity in a range of 0.15 to 0.41 dl / g when dissolved in a tilethyl ketone solvent and measured at a temperature of 30 ° C., and further melting the thermoplastic resin composition In the molded product obtained by the molding process, when the direction perpendicular to the surface of the molded product is defined as the thickness, the phase structure is observed with an electron microscope in a region having a depth of 40 to 60% of the total thickness from the surface. A resin composition for coating, wherein the polyamide resin (B) is formed in a continuous phase at least 10% by volume,
(7) For a test piece having a pencil hardness of H on the coating film surface obtained by coating an 80 mm × 80 mm × 3 mm thick test piece after injection molding, the tip diameter of the punch is 5/8 inch at 23 ° C. The coating resin composition according to (6), wherein the impact energy obtained by performing a high-speed surface impact test under the condition of a collision speed of 2.5 m / s is 20 J or more,
(8) A coating test piece obtained by coating a test piece of 80 mm × 80 mm × 3 mm thickness after injection molding is provided with a 1 mm square grid (10 × 10 pieces), and is defined in JIS K5400-1990. The coating resin composition according to (6) or (7), wherein the remaining number of coating films when the cellophane tape peeling test is performed is 70 or more by the cross-cut tape method,
(9) A plated molded body obtained by plating a resin molded body formed by melt molding the thermoplastic resin composition according to any one of (1) to (5),
And (10) A molded molded article obtained by coating a resin molded article obtained by melt-molding the thermoplastic resin composition according to any one of (6) to (8). .

  According to the present invention, it is possible to obtain a plating and coating resin composition, a plated molded body, and a coated molded body having excellent plating adhesion and coating adhesion, a good appearance, and excellent surface impact. The resin composition for plating and coating according to the present invention has both high adhesion strength and surface impact property of the plating layer and coating film, and further has a relatively low specific gravity and can be reduced in weight. First, it can be suitably used as an automobile part, an automobile interior / exterior material, and a housing / part surrounding material of an electric / electronic device.

  Hereinafter, the best mode for carrying out the thermoplastic resin composition of the present invention will be described.

  The styrene resin (A) used in the present invention is obtained by blending at least one of a graft (co) polymer (A-1) and a vinyl (co) polymer (A-2).

  The graft (co) polymer (A-1) is a monomer composed of 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer. The unit is formed by graft polymerization.

  Specific examples of the graft (co) polymer (A-1) include a graft copolymer containing 40% by weight or more of impact-resistant polystyrene and aromatic vinyl monomer, for example, ABS, AAS. (Acrylonitrile-acrylic rubber-styrene copolymer), AES (acrylonitrile-ethylenepropylene rubber-styrene copolymer), MBS (methyl methacrylate-butadiene rubber-styrene copolymer), and the like.

  As the rubbery polymer constituting the graft (co) polymer (A-1), those having a glass transition temperature of 0 ° C. or less are suitable. Specifically, polyene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene block copolymer such as styrene-butadiene block copolymer, and diene system such as butyl acrylate-butadiene copolymer. Rubber, acrylic rubber such as polybutyl acrylate, alkyl acrylate-acrylic allyl ester, polyisoprene, ethylene-propylene-diene terpolymer, ethylene-propylene copolymer and ethylene-propylene- (non-conjugated) Diene) copolymer ethylene-α-olefin copolymer rubber, polyorganosiloxane rubber polymer latex and other silicone rubber, butadiene polymer hydrogenated product, conjugated diene polymer block and aromatic vinyl compound Block with polymer block Examples thereof include hydrogenated rubbers of copolymers and hydrogenated rubbers such as block copolymers obtained by combining these. Among them, diene rubbers, ethylene-propylene- (non-conjugated diene) copolymers, hydrogenated diene heavy polymers, etc. Polymer, silicone rubber or acrylic rubber is preferably used, and polybutadiene or butadiene copolymer is particularly preferable. These may be used alone or in combination of two or more. As the non-conjugated diene component, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, dicyclopentadiene, and the like can be preferably used.

  The rubber particle diameter of such a rubbery polymer is not particularly limited, but those having a weight average particle diameter of the rubber particles of 0.05 to 0.7 μm, particularly 0.10 to 0.55 μm are preferable because of excellent impact resistance. In addition, a combination of a rubber having a weight average particle diameter of 0.20 to 0.25 μm and a rubber having a weight average particle diameter of 0.50 to 0.65 μm in a weight ratio of 90:10 to 60:40 is also impact resistant. It is preferably used because of its excellent resistance to falling weight impact in thin molded products. Further, as the rubbery polymer, an agglomerated one can be used.

  In addition, the weight average particle diameter of the rubber particles is creamed according to the sodium alginate method described in “Rubber Age Vol. 88 p. 484 to 490 (1960) by E. Schmidt, PH Biddison”, that is, by the concentration of sodium alginate. Utilizing the fact that the particle size of polybutadiene to be used is different, it can be measured by a method of determining the particle size of 50% cumulative weight fraction from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration.

  Examples of the aromatic vinyl monomer used as a monomer unit for graft polymerization to the graft (co) polymer (A-1) include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt -Butyl styrene, p-methyl styrene, chlorostyrene, bromostyrene and the like are mentioned, and styrene is particularly preferable, and these may be used alone or in combination of two or more.

  As at least one other monomer used as a monomer unit for graft polymerization to the graft (co) polymer (A-1), a vinyl cyanide monomer is used for the purpose of improving chemical resistance. Particularly preferably used. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile and the like, and acrylonitrile is particularly preferable. A (meth) acrylic acid ester monomer is also preferably used. Examples of the (meth) acrylic acid ester monomer include esterification products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl, isobutyl, etc., and methyl methacrylate is particularly preferable. Other monomers include unsaturated carboxylic acid monomer units such as (meth) acrylic acid and their metal salts, glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p -Glycidyl ether, p-glycidyl styrene, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, itaconic acid, itaconic anhydride, phthalic acid, 1,2-dimethylmaleic anhydride, phenylmaleic anhydride, N- Methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl (meth) acrylate, (meth) a Propylaminoethyl silylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, ( 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p- Aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy- -Butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 4-dihydroxy-2 -Butene, ethylene, propylene, vinyl chloride, vinyl acetate, isopropenyl acetate, vinyl benzoate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, or polytetramethylene glycol methacrylate can also be used. These may be used alone or in combination of two or more.

  The graft (co) polymer (A-1) in the present invention is preferably in the presence of 10 to 80 parts by weight, more preferably 40 to 80 parts by weight, and still more preferably 50 to 80 parts by weight of a rubbery polymer. Preferably 90 to 20 parts by weight, more preferably 60 to 20 parts by weight of a monomer unit composed of 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer. Part, more preferably 50 to 20 parts by weight, is obtained by graft (co) polymerization. The proportion of the rubbery polymer is not particularly limited, but if it is less than 10 parts by weight, the impact strength tends to decrease, and if it exceeds 80 parts by weight, the surface appearance tends to decrease.

  The amount of the aromatic vinyl monomer used in the graft (co) polymer (A-1) of the present invention is preferably in the range of 40 to 95% by weight, more preferably in the range of 50 to 80% by weight. More preferably, it is in the range of 60% by weight to 75% by weight.

  The amount of at least one other monomer used in the graft (co) polymer (A-1) is preferably in the range of 60 to 5% by weight, more preferably 50 to 20% by weight. %, More preferably in the range of 40% to 25% by weight.

The graft (co) polymer (A-1) is a monomer component consisting of 100 to 40% by weight of an aromatic vinyl monomer and another monomer copolymerizable with the rubber polymer. An ungrafted (co) polymer formed when 60% by weight is grafted (co) polymerized may be contained. That is, the monomer mixture of the monomer mixture may be bonded to each other and may contain an ungrafted (co) polymer, and is usually obtained as a mixture with an ungrafted (co) polymer. Can be used. The graft (co) polymer (A-1) in the present invention includes those obtained as a mixture with this non-grafted monomer. Here, the graft rate is not particularly limited, but the graft rate is preferably 10 to 150% from the viewpoint of impact strength. The graft ratio is calculated by the following formula.
Graft ratio (%) = [Amount of vinyl (co) polymer graft-polymerized to rubbery polymer] / [Rubber content of graft (co) polymer] × 100

  The intrinsic viscosity measured at 30 ° C. after dissolving the graft (co) polymer (A-1) in a methyl ethyl ketone solvent is not particularly limited, but it is 0.10 to 1 in terms of the balance between impact resistance and molding processability. The range is preferably 2 dl / g, more preferably 0.15 to 0.70 dl / g, and particularly preferably 0.15 to 0.48 dl / g.

  The method for producing the graft (co) polymer (A-1) is not particularly limited, and a combination of these polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, or bulk suspension polymerization. Is used. It is also possible to blend and use two or more of the graft (co) polymers (A-1) separately (grafted) copolymerized.

  The vinyl (co) polymer (A-2) of the present invention comprises 100 to 45% by weight of an aromatic vinyl monomer and 0 to 55% by weight of at least one other monomer.

  Specific examples of the vinyl (co) polymer (A-2) include polystyrene and an aromatic vinyl monomer that contains 45% by weight or more of the following vinyl copolymer, AS (acrylonitrile- Styrene copolymer), MS resin (methyl methacrylate-styrene copolymer), MAS resin (methyl methacrylate-acrylonitrile-styrene copolymer), maleimide monomer-containing styrene copolymer, and the like. .

  Examples of the aromatic vinyl monomer used in the vinyl (co) polymer (A-2) include styrene, α-methyl styrene, vinyl toluene, o-ethyl styrene, pt-butyl styrene, p-methyl. Examples thereof include styrene, chlorostyrene, and bromostyrene, and styrene is particularly preferable. These may be used alone or in combination of two or more.

  As at least one other monomer used in the vinyl (co) polymer (A-2), vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile are chemical resistant. It is particularly preferably used from the viewpoint of improvement, and acrylonitrile is most preferable among them. In addition to the improvement in heat resistance and flame retardancy, maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, and N-cyclohexylmaleimide are plated. N-phenylmaleimide is preferred because it is preferably used because adhesion strength and coating adhesion strength are improved. Examples of other monomers include (meth) acrylic acid ester monomers such as esterified products of acrylic acid and methacrylic acid with methyl, ethyl, propyl, n-butyl and isobutyl, and non-methacrylic (meth) acrylic acid. Saturated carboxylic acid monomers and metal salts thereof, glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, and other epoxy group-containing vinyl monomers, maleic Acid, maleic anhydride, monomethyl maleate, monoethyl maleate, itaconic acid, itaconic anhydride, phthalic acid, 1,2-dimethylmaleic anhydride, phenylmaleic anhydride, acrylamide, methacrylamide, N-methylacrylamide, butoxymethyl Acrylamide, N-propi Methacrylamide, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dibutylamino (meth) acrylate Ethyl, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, N-vinyldiethylamine, N-acetylvinyl Amino group-containing vinyl monomers such as amine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl- Oh Oxazoline group-containing vinyl monomers such as sazoline, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3- Hydroxy-2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 4-dihydroxy-2-butene, ethylene, propylene, vinyl chloride, vinyl acetate, isopropyl acetate Penyl, vinyl benzoate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol methacrylate, or the like can also be used. These may be used alone or in combination of two or more.

  The amount of the aromatic vinyl monomer used in the vinyl (co) polymer (A-2) needs to be at least 45 weight from the viewpoint of impact resistance of the resin composition of the present invention. . Preferably it is 45-95 weight%, More preferably, it is 50-95 weight%, More preferably, it is 50-80 weight%.

  The amount of at least one other monomer used for the vinyl (co) polymer (A-2) is preferably 5 to 55% by weight, more preferably 5 to 50% by weight, More preferably, it is 20 to 50% by weight.

  In the present invention, as the vinyl (co) polymer (A-2), a vinyl (co) polymer containing a maleimide monomer and a vinyl (co) polymer not containing a maleimide monomer. It is particularly preferable to use in combination from the viewpoints of improving heat resistance and flame retardancy and further improving plating adhesion strength and coating adhesion strength while maintaining surface impact.

  The intrinsic viscosity (V-2) in the present invention is dissolved in a methyl ethyl ketone solvent and the intrinsic viscosity measured at 30 ° C. is not particularly limited, but the range of 0.10 to 1.2 dl / g is impact resistance. Is more preferably used from the viewpoint of the balance between properties and moldability, more preferably in the range of 0.15 to 0.70 dl / g, and even more preferably 0.15 to 0.55 dl / g in consideration of the surface appearance. g, particularly preferably 0.15 to 0.50 dl / g.

  There are no particular restrictions on the method for producing the vinyl (co) polymer (A-2). For example, an aromatic vinyl monomer or a monomer mixture containing 50% by weight or more of an aromatic vinyl monomer is used. The (co) polymerization method is particularly preferably used, and the vinyl (co) polymer obtained by polymerization is further subjected to an appropriate reaction such as imidization in the reactor to obtain the desired vinyl (co) polymer. The method etc. which obtain a polymer (A-2) are mentioned. For the production of the vinyl (co) polymer (A-2), ordinary methods such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, or a combination of these polymerization methods such as bulk suspension polymerization are used. Is used. There is no particular limitation on the monomer charging method, and it may be added all at once, and part or all of the charged monomer is continuously charged or divided in order to prevent the formation of a copolymer composition distribution. Polymerization may be performed while charging. Moreover, it is also preferable to blend and use 2 or more types of the vinyl-type (co) polymer (A-2) polymerized separately.

  In the present invention, the styrene resin (A) is preferably composed of at least a graft (co) polymer (A-1) from the viewpoint of impact resistance, and from the viewpoint of fluidity, the styrene resin (A) is The graft (co) polymer (A-1) and the vinyl (co) polymer (A-2) are more preferable. At this time, it is preferable that content of a vinyl type (co) polymer (A-2) is 5 weight% or more in a styrene resin (A) from a fluid viewpoint. The more preferred mixing ratio of the graft (co) polymer (A-1) and the vinyl (co) polymer (A-2) is 5 to 95% by weight of the graft (co) polymer (A-1) and the vinyl The (co) polymer (A-2) is 5 to 95% by weight, more preferably 5 to 80% by weight of the graft (co) polymer (A-1) and the vinyl (co) polymer (A-2). 20 to 95% by weight, particularly preferably 40 to 80% by weight of the graft (co) polymer (A-1) and 20 to 60% by weight of the vinyl (co) polymer (A-2).

  The polyamide resin (B) used in the present invention is a polymer mainly composed of aminocarboxylic acid, lactam, or diamine and dicarboxylic acid. Typical examples of the raw material of the polyamide resin (B) used in the present invention include aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, and lactams such as ε-caprolactam and ω-laurolactam. Or tetramethylenediamine, hexamethylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4 , 4-trimethylhexamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (a) Minomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis ( 4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and other aliphatic, alicyclic, and aromatic diamines, adipic acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, 3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, Fats such as hexahydroisophthalic acid , Alicyclic, include any combination of an aromatic dicarboxylic acid.

  The polyamide resin (B) is obtained from these raw materials by commonly known polycondensation, and in the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

  Examples of preferred polyamide resin (B) include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polyhexamethylene sebaca Nylon (Nylon 610), Nylon 6/66 Copolymer, Nylon 6/66/610 Copolymer, Nylon 6/12 Copolymer, Nylon 66 / Hexamethylene Isophthalamide (6I) / 6 Copolymer, and Nylon 6/66/610/12 Examples of the copolymer include nylon 6, nylon 66, and a copolymer based on these, and particularly preferable are nylon 6 and a copolymer based on nylon 6. Nylon 6 is preferable.

The molecular weight of these polyamide resins (B) is not particularly limited, but the relative viscosity of a solution dissolved in 98% concentrated sulfuric acid at a concentration of 1 g / dl is in the range of 1.8 to 7.5 at 25 ° C. Is preferred. More preferably, it is the range of 1.8-4.0, More preferably, it is the range of 1.8-2.8, Most preferably, it is the range of 1.8-2.4, Most preferably, it is 1. It is the range of 8-2.3. When the relative viscosity exceeds 7.5, the fluidity of the resin composition of the present invention tends to decrease. When the relative viscosity is less than 1.8, the mechanical properties of the resin composition of the present invention tend to be lowered. The melting point of the polyamide resin (B) is the peak peak of crystal melting measured with a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer) in a nitrogen stream at a heating rate of 20 ° C./min. It can obtain | require by measuring and it is preferable that this melting | fusing point is 150-280 degreeC. Further, the melt viscosity of the polyamide resin (B) used in the present invention is preferably 15 to 600 Pa · s, more preferably 15 to 160 at a shear rate of 1000 seconds ⁻¹ at the temperature during melt processing. 250 Pa · s, more preferably 15 to 200 Pa · s, particularly preferably 15 to 150 Pa · s, and most preferably 15 to 100 Pa · s.

  The modified vinyl copolymer (C) in the present invention (hereinafter sometimes simply referred to as copolymer (C)) contains 0.05 to 20% by weight of α, β-unsaturated carboxylic anhydride unit. It is what.

  The α, β-unsaturated carboxylic anhydride unit contained in the copolymer (C) is in the range of 0.05 to 20% by weight. The upper limit of the content of the α, β-unsaturated carboxylic acid anhydride unit contained in the copolymer (C) is preferably 10% by weight, more preferably 7% by weight, still more preferably 5% by weight, particularly preferably. The lower limit of the content is preferably 0.1% by weight, more preferably 1.5% by weight, still more preferably 1.7% by weight, particularly preferably 2.0% by weight, and most preferably Is 2.5% by weight. When the α, β-unsaturated carboxylic acid anhydride unit is less than 0.05% by weight, the reactivity with the polyamide resin (B), or the reactivity and affinity are lowered. The surface impact property of the resin composition tends to decrease. If the α, β-unsaturated carboxylic acid anhydride unit or its derivative unit exceeds 20% by weight, the moldability and surface impact of the resin composition for plating and coating tend to be lowered.

  The copolymer (C) preferably contains vinyl cyanide monomer units, and the amount of vinyl cyanide monomer units is preferably 0.5 to 60% by weight. More preferably, it is 0.5-50 weight%, More preferably, it is 2-50 weight%. From the viewpoint of improving the surface impact of the plated and coated resin composition obtained by adding the copolymer (C) and the plated molded body obtained by coating and the coated molded body obtained by coating, vinyl cyanide The lower limit of the amount of the system monomer unit is more preferably 20% by weight or more, and the upper limit thereof is more preferably 50% by weight or less in consideration of moldability. Therefore, when these are taken into consideration, the amount of the vinyl cyanide monomer unit is preferably in the range of 20 to 50% by weight.

  There are no particular restrictions on the type of α, β-unsaturated carboxylic acid anhydride units contained in the copolymer (C). For example, maleic anhydride, fumaric anhydride, itaconic anhydride, crotonic anhydride, methyl Maleic anhydride, methyl fumaric anhydride, mesaconic anhydride, citraconic anhydride, glutaconic anhydride, tetrahydrophthalic anhydride, 1,2-dimethylmaleic anhydride, phenylmaleic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, methyl-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2, Examples include 3-dicarboxylic acid anhydride, and maleic anhydride is particularly preferable. These may be used alone or in combination of two or more.

  The copolymer (C) is an α, β-unsaturated carboxylic acid anhydride obtained by converting the α, β-unsaturated carboxylic acid anhydride contained in the copolymer (C), for example, by a reaction such as hydrolysis. A derivative unit of a product may be contained. These derivative units have chemical structures that can be converted back to α, β-unsaturated carboxylic acid anhydrides by appropriate vacuum drying or heat treatment. Derivative units of α, β-unsaturated carboxylic acid anhydrides include maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, endobicyclo -(2,2,1) -5-heptene-2,3-dicarboxylic acid, methyl-1,2,3,6-tetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene Α, β-unsaturated dicarboxylic acids such as 2,3-dicarboxylic acid, metal salts of these α, β-unsaturated dicarboxylic acids, monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate , Monoethyl itaconate, monomethyl crotonate, monoethyl crotonate, monomethyl methyl maleate, Α, β-unsaturated dicarboxylic acid monoalkyl esters such as monomethyl rufumarate, monomethyl mesaconic acid, monomethyl citraconic acid, monomethyl glutaconate, monomethyl tetrahydrophthalate or the like, metal salts thereof, α, β-unsaturated dicarboxylic acid monoalkenyl esters Alternatively, metal salts thereof, α, β-unsaturated dicarboxylic acid monoaryl esters or metal salts thereof, α, β-unsaturated dicarboxylic acid dialkyl esters, and the like can be given.

  When the vinyl cyanide monomer unit is contained in the copolymer (C), examples of the vinyl cyanide monomer unit include acrylonitrile, methacrylonitrile, ethacrylonitrile, and preferably acrylonitrile. is there.

  The copolymer (C) may contain at least one other monomer unit. As at least one other monomer unit, an aromatic vinyl monomer is preferably used. Examples of the aromatic vinyl monomer unit include styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, and the like. α-Methylstyrene is preferable, and styrene is more preferable. These may be used alone or in combination of two or more. Monomer units other than aromatic vinyl monomer units include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. N-butyl acid, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth ) 3-hydroxypropyl acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate and 2,3,4,5-tetrahydroxypentyl (meth) acrylate, acrylic acid or metal salts thereof , Methacrylic acid or its metal salt, t-butyl (meth) acrylate, aminoethyl (meth) acrylate, (meth) acrylic acid Propylaminoethyl, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, (meth ) 3-diethylaminopropyl acrylate, phenylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, allyl glycidyl ether, styrene-p-glycidyl ether, monoethyl maleate, N-methylmaleimide, N- Ethyl maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, -Acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline and 2-styryl-oxazoline . Among these, methyl (meth) acrylate, N-methylmaleimide, and N-phenylmaleimide are preferably used, and methyl acrylate, methyl methacrylate, and N-phenylmaleimide are more preferable. These may be used alone or in combination of two or more.

  The intrinsic viscosity measured by dissolving the copolymer (C) of the present invention in a methyl ethyl ketone solvent at a temperature of 30 ° C. is in the range of 0.15 to 0.41 dl / g. Preferably it is the range of 0.15-0.40 dl / g, More preferably, it is the range of 0.15-0.36 dl / g, More preferably, it is the range of 0.15-0.30 dl / g, Especially preferably, it is the range of 0.15-0.25 dl / g, Most preferably, it is the range of 0.15-0.20 dl / g. When the intrinsic viscosity exceeds 0.41 dl / g, the fluidity and surface appearance of the resin composition are lowered. On the other hand, when the intrinsic viscosity is lower than 0.15 dl / g, the surface impact properties and the surface appearance of the resin composition for plating and coating are deteriorated. Here, the intrinsic viscosity is synonymous with the intrinsic viscosity, and is an ultimate value at infinite dilution of the reduced viscosity, and can be calculated by measuring the reduced viscosity at a plurality of arbitrary concentrations. The reduced viscosity is the ratio ηr / c of the increase in relative viscosity ηr with respect to the mass concentration c of the polymer substance.

  In general, it is known that the intrinsic viscosity of a polymer substance has a certain correlation with the molecular weight, and the copolymer (C) of the present invention, which is characterized in that the intrinsic viscosity is in the above-mentioned range, also depends on the molecular weight range. Can be characterized. The molecular weight can be expressed by a number average molecular weight or a weight average molecular weight. In either case, the copolymer (C) is dissolved in tetrahydrofuran, measured using a gel permeation chromatograph (GPC), and obtained as a polystyrene equivalent value. .

  Specifically, the number average molecular weight of the copolymer (C) of the present invention having an intrinsic viscosity at 30 ° C. in a methyl ethyl ketone solution of 0.15 to 0.41 dl / g is 4000 to 20000, and the weight average molecular weight is 12000-39000. The number average molecular weight of the preferred copolymer (C) of the present invention having the same intrinsic viscosity of 0.15 to 0.40 dl / g is 4000 to 19000, and the weight average molecular weight is 12000 to 38000. The number average molecular weight of the copolymer (C) of the present invention more preferably having the same intrinsic viscosity of 0.15 to 0.36 dl / g is 4000 to 17000, and the weight average molecular weight is 12000 to 36000. The more preferred copolymer (C) of the present invention having the same intrinsic viscosity of 0.15 to 0.30 dl / g has a number average molecular weight of 4,000 to 16,000 and a weight average molecular weight of 12,000 to 34,000. The particularly preferred copolymer (C) of the present invention having the same intrinsic viscosity of 0.15 to 0.25 dl / g has a number average molecular weight of 4,000 to 14,000 and a weight average molecular weight of 12,000 to 31,000. The most preferable copolymer (C) of the present invention having the same intrinsic viscosity of 0.15 to 0.20 dl / g has a number average molecular weight of 4000 to 9000 and a weight average molecular weight of 12000 to 19000.

  The method for producing the copolymer (C) having the desired intrinsic viscosity range of the present invention is not particularly limited, but in the polymerization, the decomposition temperature and the addition amount of radical polymerization initiators such as azo compounds and peroxides. Of addition of chain transfer agents such as alkyl mercaptan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, triethylamine, etc., or controlling the amount of solvent when a solvent is used in polymerization By using this method, a copolymer (C) having a desired intrinsic viscosity range can be obtained. Among these, from the viewpoint of maintaining the polymerization stability and the polymerization rate, a method of controlling the amount of chain transfer agent added can be more preferably used. As the chain transfer agent, alkyl mercaptan is particularly preferably used. . Examples of the alkyl mercaptan used here include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and more preferably n-octyl mercaptan, t-dodecyl mercaptan and n-dodecyl mercaptan.

  The addition amount of the alkyl mercaptan in producing the copolymer (C) of the present invention depends on the desired intrinsic viscosity of the copolymer (C), the decomposition temperature and addition amount of the radical polymerization initiator, and the alkyl mercaptan species. It can be appropriately set according to the polymerization temperature, the monomer concentration and the like.

  For example, when the copolymer (C) is produced by solution polymerization, 120 parts by weight of methyl ethyl ketone is used with respect to 100 parts by weight of the total amount of the monomer mixture charged in the reaction system, When 0.3 parts by weight of 2′-azobisisobutyronitrile is used and polymerization is carried out at 80 ° C., the intrinsic viscosity at 30 ° C. is in the range of 0.15 to 0.4 dl / g in methyl ethyl ketone. To produce the copolymer (C), the amount of t-dodecyl mercaptan added is in the range of 0.1 to 0.8 parts by weight with respect to 100 parts by weight of the total amount of the monomer mixture charged in the reaction system. Control. Moreover, in order to manufacture the copolymer (C) whose intrinsic viscosity is in the range of 0.15 to 0.36 dl / g, t-dodecyl mercaptan is controlled to be in the range of 0.15 to 0.8 parts by weight. Further, to produce a copolymer (C) having an intrinsic viscosity in the range of 0.15 to 0.3 dl / g by the same solution polymerization, 0.2 to 0.8 weight of t-dodecyl mercaptan is used. Control the range of parts.

  For example, in the case of producing copolymer (C) by using 0.3 part by weight of 2,2′-azobisisobutyronitrile as an initiator and performing bulk polymerization at 80 ° C., in methyl ethyl ketone, In order to produce a copolymer (C) having an intrinsic viscosity at 30 ° C. in the range of 0.15 to 0.40 dl / g, the amount of t-dodecyl mercaptan added is the total amount of the monomer mixture charged into the reaction system. It controls to the range of 0.35-2.5 weight part with respect to 100 weight part. Further, in order to produce a copolymer (C) having an intrinsic viscosity in the range of 0.15 to 0.36 dl / g, t-dodecyl mercaptan is controlled in the range of 0.5 to 2.5 parts by weight. Furthermore, in order to produce a copolymer (C) having an intrinsic viscosity in the range of 0.15 to 0.30 dl / g, t-dodecyl mercaptan is controlled in the range of 0.75 to 2.5 parts by weight.

  The α, β-unsaturated carboxylic acid anhydride unit and vinyl cyanide monomer unit in the copolymer (C) are preferably introduced into the main chain of the copolymer by random polymerization. As for the polymerization method in this case, for example, a combination of polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, precipitation polymerization, emulsion polymerization, or bulk suspension polymerization by radical polymerization can be used. Polymerization, bulk suspension polymerization or precipitation polymerization can be used more preferably. Moreover, both a batch type and a continuous type can be used preferably. Depending on the polymerization method, the copolymer (C) may be in the form of a mixture containing a copolymer that does not contain unsaturated carboxylic anhydride monomer units. There is no particular limitation on the particle size and shape of the polymer obtained by bulk suspension polymerization or precipitation polymerization, but the particle size of the obtained polymer is preferably in the range of 0.1 μm to 8 mm, more preferably in the range of 1 μm to 5 mm. It is. When the particle size is smaller than 0.1 μm, for example, clogging occurs in the filtration step, or handling tends to be difficult in post-polymerization processing such as a drying step. On the other hand, when the particle size exceeds 8 mm, the drying efficiency in the drying process of the polymer tends to decrease, and when cleaning is performed, the cleaning efficiency tends to decrease. In addition, a particle size here means the average diameter of the polymer granule obtained by precipitation polymerization.

  In addition, the charging method of each monomer at the time of polymerization is not particularly limited, and may be added all at the beginning, and a part of the charged monomer may be used to prevent the formation of a copolymer composition distribution. Alternatively, the polymerization may be carried out while continuously or partly charging. Moreover, as a copolymer (C) to mix | blend, it is also possible to blend and use 2 or more types of the copolymer (C) polymerized separately.

  For determination of each component unit in the copolymer (C) of the present invention, an infrared spectrophotometer, a proton nuclear magnetic resonance (1H-NMR) measuring machine, gas chromatography, or the like can be used. Quantification of the α, β-unsaturated carboxylic anhydride unit in the copolymer (C) can be carried out as follows.

  (I) α, β-unsaturated carboxylic acid anhydride and vinyl cyanide monomer are mixed at various molar ratios, and infrared absorption spectrum measurement is performed to obtain α, β-unsaturated carboxylic acid anhydride and An infrared absorption spectrum calibration curve is created for the intensity ratio and molar ratio of the characteristic absorption peak with the vinyl cyanide monomer.

  (Ii) Next, the infrared absorption spectrum of the copolymer (C) is measured, and by using the prepared calibration curve, the reaction is added and the α, β-unsaturated carboxylic acid contained in the copolymer (C) is added. The molar ratio between the acid anhydride unit and the vinyl cyanide monomer is calculated.

  (Iii) Next, the other component units of the copolymer (C) are also calculated in the same manner, and the molar ratio with the vinyl cyanide monomer is calculated. Based on these results, α, β-unsaturated carboxylic acid is calculated. The content of acid anhydride units is calculated.

  Here, in preparing an infrared absorption spectrum calibration curve, α, β-unsaturated carboxylic acid anhydride has a peak of characteristic absorption due to stretching vibration of carbonyl group, and in the case of vinyl cyanide monomer unit, CN group stretching. The peak of characteristic absorption due to vibration can be used when an aromatic vinyl monomer is included, and the peak of characteristic absorption due to aromatic C = C in-plane vibration can be used.

  The resin composition for plating and coating according to the present invention can be added with other resins, if necessary, within an addition amount range that does not significantly impair the effects of the present invention. Examples of such resins include polymethyl methacrylate, polycarbonate, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyarylate, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyoxymethylene, polytetrafluoroethylene, and polylactic acid. Preferable examples include novolac epoxy phenol resin, polysulfone, polyimide, polyetherimide, polyetheretherketone, polyetheramide, and polyamideimide.

  Moreover, the resin composition for plating and coating of the present invention can greatly improve the strength, rigidity, heat resistance and the like by further containing a filler. Such fillers may be fibrous or non-fibrous, such as granules. Specific examples thereof include glass fibers, carbon fibers, metal fibers, aramid fibers, asbestos, potassium titanate whiskers, straws. Examples include stenite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.

  Since these contents differ depending on the type of filler, they cannot be specified unconditionally, but 0.05 to 150 parts by weight with respect to 100 parts by weight in total of the styrene resin (A) and the polyamide resin (B). preferable.

  Moreover, in order to provide electroconductivity, the resin composition for plating and coating of this invention can contain a conductive filler and / or a conductive polymer. The conductive filler is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin. Specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, and conductive substances. Examples thereof include coated inorganic filler, carbon powder, graphite, carbon fiber, carbon flake, scaly carbon, carbon fibril, and carbon nanotube, and these may be hollow. Specific examples of the conductive polymer include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylene vinylene. These conductive fillers and / or conductive polymers may be used in combination of two or more. Of these conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and economy.

  The content of the conductive filler and / or conductive polymer used in the present invention is appropriately determined depending on the type of the conductive filler and / or conductive polymer used, but the conductivity, fluidity, mechanical strength, etc. From the balance point, the range of 0.1 to 250 parts by weight is preferable with respect to 100 parts by weight of the thermoplastic resin composition comprising the styrene resin (A) and the polyamide resin (B), and particularly preferably 1 to 250 parts by weight. The range is 100 parts by weight.

In addition, the resin composition for plating and coating of the present invention is within the range not impairing the effects of the present invention, and further other components such as sulfur-containing compounds, acrylates, phosphorus organic compounds, copper chloride Antioxidants and heat stabilizers such as metal salt stabilizers such as cuprous iodide, copper acetate, or cerium stearate may be added.

  Other components that can be added include weathering agents, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, pigments, fluorescent pigments, dyes, fluorescent dyes, anti-coloring agents, plasticizers, antistatic agents (ion Antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, polyetheresteramide, polyamide ether, olefinic etheresteramide or olefinic etheresteramide, etc. Random or block polymers of polyamide elastomers), flame retardants (red phosphorus, metal hydroxide flame retardants, phosphorus flame retardants, silicone flame retardants, halogen flame retardants, or these halogen flame retardants and trioxide Combination with antimony), calcium carbonate, glass beads, wood flour, chaff flour Add walnut powder, waste paper, phosphorescent pigment, tungsten powder or tungsten alloy powder, antibacterial and antifungal agents such as borate glass and silver antibacterial agents, hydrotalcite represented by magnesium-aluminum hydroxyhydrate, etc. Can do.

  In the plating and coating resin composition of the present invention, the content of the copolymer (C) is 0.05 to 100 parts by weight with respect to 100 parts by weight of the resin composition comprising the styrene resin (A) and the polyamide resin (B). The amount is not particularly limited as long as it is in the range of 80 parts by weight, but is preferably in the range of 0.1 to 30 parts by weight, more preferably in the range of 0.1 to 15 parts by weight, and further preferably in the range of 0.1 to 10 parts by weight. It is a range. If the copolymer (C) is less than 0.05 parts by weight, the impact resistance of the resulting resin composition tends to decrease, and if it exceeds 80 parts by weight, the moldability of the final composition tends to decrease. .

  In the thermoplastic resin composition of the present invention, the mixing ratio of the styrene resin (A) and the polyamide resin (B) is 55 to 85% by weight of the styrene resin (A) and 45 to 15% by weight of the polyamide resin (B). Preferably, the styrene resin (A) is 60 to 80% by weight and the polyamide resin (B) is 40 to 20% by weight, and particularly preferably, the styrene resin (A) is 65 to 80% by weight and the polyamide resin (B). It is 35 to 20% by weight, and most preferably 67 to 80% by weight of the styrene resin (A) and 33 to 20% by weight of the polyamide resin (B).

  There is no particular limitation on the shape of the molded body obtained by melt molding the resin composition for plating and coating of the present invention and the phase structure of the molded body, but the surface impact of the molded body after plating and coating at normal and low temperatures The resin composition for plating and coating of the present invention, which is preferable from the viewpoint of further improving the properties, is formed from the surface when the thickness is the center of the molded body obtained by melt molding, that is, the direction perpendicular to the surface of the molded body. The polyamide resin (B) forms a continuous phase in a region having a depth of 40 to 60% with respect to the thickness. Specifically, in the phase structure at the center of the molded body, the portion where the polyamide resin (B) is a continuous phase is preferably formed in an amount of 10% by volume or more, more preferably 20% by volume or more. What is formed more than the volume% is more preferable.

  As the resin composition for plating and coating of the present invention when the polyamide resin (B) forms a continuous phase, the styrenic resin (A) is preferably 55 to 85% by weight and the polyamide resin (B) is 45 to 15% by weight. More preferably, the styrene resin (A) is 60 to 80% by weight and the polyamide resin (B) is 40 to 20% by weight, and still more preferably, the styrene resin (A) is 65 to 80% by weight and the polyamide resin (B) is 35 to 20%. % By weight, particularly preferably 67-80% by weight of styrene resin (A) and 33-20% by weight of polyamide resin (B), most preferably 70-80% by weight of styrene resin (A) and 30% of polyamide resin (B). Examples of which are -20% by weight.

  Further, a preferable resin composition for plating and coating according to the present invention has a thickness at the center of a molded product obtained by melt molding, that is, a direction perpendicular to the surface of the molded product, with respect to the total thickness from the surface. The graft (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) forms a dispersed phase in a region having a depth of 40 to 60%. Specifically, in the phase structure at the center of the molded body, the portion where the graft (co) polymer (A-1) and / or vinyl (co) polymer (A-2) is the dispersed phase is 5% by volume. More preferably, the dispersed phase is formed in an amount of 10% by volume or more, more preferably 30% by volume or more, particularly preferably 50% by volume or more, and most preferably 60% by volume or more.

  The polyamide resin (B) forms a continuous phase in the center of the molded product of the resin composition for plating and coating of the present invention, and the graft (co) polymer (A-1) and / or vinyl (co) polymer. An electron micrograph model diagram of a phase structure in which (A-2) forms a dispersed phase with respect to the polyamide resin (B) is shown in FIG.

  In FIG. 1, the portion indicated by reference numeral 1 is a polyamide resin (B) that forms a continuous phase. The portion indicated by reference numeral 2 is a vinyl (co) polymer (A-2) that forms a dispersed phase. The portion indicated by reference numeral 3 is a graft (co) polymer (A-1) that forms a dispersed phase. When the graft (co) polymer (A-1) is encapsulated in the vinyl (co) polymer (A-2), the graft (co) polymer (A-1) and the vinyl (co) polymer Both (A-2) are dispersed phases. The dispersed phase formed by the graft (co) polymer (A-1) and / or vinyl (co) polymer (A-2) is the graft (co) polymer (A-1) and / or vinyl When the (co) polymer (A-2) is observed in a specific range, it indicates that the polymer (A-2) is surrounded by the polyamide resin (B). When observed in the range of 10 μm × 10 μm in the electron micrograph, it means one surrounded by the polyamide resin (B).

  The preferred phase structure observed in the central part of the molded product of the resin composition for plating and coating of the present invention is not limited to the form shown in FIG. 1, but is a graft (co) polymer (A-1) serving as a dispersed phase. ) And / or the vinyl (co) polymer (A-2) may have a non-circular shape such as a streak shape, a polygonal shape or an elliptical shape. Further, the dispersion state of the copolymer (C) is not particularly limited, but the polyamide resin (B), the graft (co) polymer (A-1) and / or the vinyl (co) polymer ( It exists in the interface with A-2). Further, when the phase structure as shown in FIG. 1 is formed in at least a part of the central portion of the molded body, the graft (co) polymer (A-1) and / or the vinyl (co) polymer ( When A-2) is dispersed more uniformly without agglomerating in the continuous phase of the polyamide resin (B), the impact resistance at low temperatures of the molded product tends to be improved.

  The phase structure of the plating and coating resin composition of the present invention can be observed using an electron microscope. Examples of the electron microscope include TEM (transmission electron microscope) and SEM (scanning electron microscope). The ratio of the capacity of the part where the polyamide resin (B) becomes the continuous phase, or the part where the graft (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) becomes the dispersed phase is A portion in which the polyamide resin (B) becomes a continuous phase or a graft (co) polymer (A-1) and / or a vinyl-based (co) polymer (A-2) in a dispersed phase with respect to the entire area of the electron micrograph It can be calculated as the area ratio of the part.

In the resin composition for plating and coating of the present invention, in order to form such a unique phase structure, each melt viscosity of the styrene resin (A) and the polyamide resin (B) at a shear rate of 1000 sec- ¹ is related. The melt viscosity ratio defined by <melt viscosity of styrene resin (A)> / <melt viscosity of polyamide resin (B)> at a temperature during melt molding is preferably 1.5 or more. A more preferable melt viscosity ratio is 2.2 or more, and further preferably 3.2 or more.

  Examples of the method for producing the resin composition for plating and coating according to the present invention include, for example, a styrene resin (A), a polyamide resin (B), a copolymer (C), and a copolymer (D), and other if necessary. After the additive is uniformly mixed using a high-speed stirrer or the like in the form of pellets, powder, or fine pieces, it has a vent which is heated to a uniaxial or multiaxial temperature of 210 to 330 ° C. with sufficient kneading ability. A method of melt kneading with an extruder or a method of melt kneading using a Banbury mixer or a rubber roll machine can be employed. There is no particular limitation on the screw arrangement of the extruder. In addition, there is no limitation on the order of mixing and the state of the styrene resin (A), polyamide resin (B), copolymer (C), copolymer (D) and other additives as necessary. The simultaneous mixing of the above, and the method of mixing the components remaining after premixing two or more specific components can be exemplified.

  For the molded product obtained by melt molding the plating and coating resin composition of the present invention, a conventionally known molding method such as injection molding, extrusion molding, blow molding, press molding, compression molding or gas assist molding is employed. Can be obtained. The molding temperature in this case is usually selected from a temperature range of 210 to 330 ° C.

  The method for obtaining the plated molded body of the present invention is not particularly limited. For example, a conventionally known metal plating method such as chemical vapor deposition, electroplating, electroless plating, hot dipping, impact plating, vacuum plating, etc. is preferably used. In addition, it is preferable to obtain a plated molded body by performing a plating treatment after surface roughening and imparting polarity to the molded body before the plating treatment. The plating process is preferably a chemical plating catalyst application process, a chemical plating process, and an electroplating process. For example, a surface roughening process (etching process), a polarity application process, a chemical plating catalyst application process, a chemical plating process, and an electroplating process. And a drying step. The surface roughening step is a step of forming anchor holes on the surface of the molded body, and the surface roughening (etching) method is not particularly limited, and a method conventionally used in the plating treatment of plastic molded bodies is used. Can be used. As the etching agent, for example, dichromic acid, permanganic acid, dichromic acid / sulfuric acid mixed solution, chromic acid, chromic acid / sulfuric acid mixed solution, or the like is used. The treatment conditions are not particularly limited, but preferably at a temperature in the range of 40 to 90 ° C., more preferably 50 to 80 ° C., usually for 30 seconds to 60 minutes, preferably about 1 to 40 minutes. preferable. In the present invention, the styrene resin (A) and the polyamide resin (B) have a specific blending ratio and have a specific phase structure, whereby a good anchor can be obtained in the etching process, and the adhesion strength is high. A plated film can be obtained.

  The polarity imparting step is a step of treating with a compound having polarity in order to impart charge to the surface of the molded body. Examples of the treating agent include aliphatic primary amines represented by methylamine, ethylamine, propylamine, isopropylamine, butylamine and pentylamine, and aliphatic primary amines represented by dimethylamine, diethylamine, dipropylamine and diisopropylamine. Fatty acids typified by aliphatic tertiary amines typified by diamine, trimethylamine, triethylamine and tripropylamine, aliphatic unsaturated amines typified by allylamine, diallylamine and triallylamine, cyclopropylamine, cyclobutylamine and cyclopentylamine Cyclic amines, aromatic amines represented by aniline, alkyl sulfonic acids, α-olefin sulfonic acids, alkyl benzene sulfonic acids, alkyl naphthalene sulfonic acids, alkyl esters Tersulfonic acid, alkylphenyl ether sulfonic acid, alkyl diphenyl ether sulfonic acid, sulfosuccinic acid, dialkyl sulfosuccinic acid, methyl tauric acid, β-naphthalene sulfonic acid, formalin condensate, or polyacrylic acid, polyvinyl sulfonic acid, polymethacrylic acid, polystyrene sulfone Acid, polyhydroxyethyl methacrylate, polyvinyl alcohol, polyvinyl alcohol copolymer, partially saponified product of polyvinyl acetate, partially saponified product of vinyl acetate copolymer, ethyleneimine, polyethyleneimine, polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene Oxide copolymer, polyvinyl methyl ether, polyvinyl methyl ether copolymer, pyrrolidone, poly N-vinyl pyrrolidone Polyvinyl oxazoline, polyacrylamide, polyacrylamide co-critical condition, lauryl trimethylamine, aqueous solutions or salts such as EDTA and the like preferably. Among these, those having a substituted ammonium salt such as aliphatic primary amine, polyethyleneimine, lauryltrimethylamine and salts thereof are particularly suitable. These aqueous solutions may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about processing temperature, The temperature of the range of 0-80 degreeC is preferable, More preferably, it is the range of 0-60 degreeC, More preferably, it is the range of 20-60 degreeC. Although there is no restriction | limiting in particular about processing time, The range for 5 second-20 minutes is preferable, More preferably, it is the range for 10 seconds-15 minutes. If this polarity imparting step is omitted, the chemical plating catalyst is difficult to be imparted in the next step, so that a chemical plating film is difficult to form, and a desired plated molded article may not be obtained. Next, the chemical plating catalyst application step is a step for advancing chemical plating in the next step, and there is no particular limitation on the method of applying the chemical plating catalyst. Conventionally, in the plating treatment of plastic moldings, Conventional methods can be used. For example, a colloid of stannous chloride and palladium chloride having negative charges as catalyst particles is used. First, a colloidal material of tin and palladium is deposited on the surface of the molded body to which polarity is imparted by the above-mentioned process by catalyzing, and then accelerated. By removing tin and leaving only palladium, a method for applying a chemical plating catalyst (metal catalyst) or sensitizing (sensitivity imparting treatment), for example, stannous chloride solution, (2) After immersing the molded body to which polarity is imparted in the process and adsorbing reducing ionic tin to the surface of the molded body, the molded body is subjected to activation (activation treatment), for example, palladium chloride solution. A chemical plating catalyst (metal catalyst) is imparted by the treatment of immersing and precipitating palladium by the action of tin. The method can be used.

  Next, the chemical plating step is a step of forming a metal film by reducing and depositing metal ions on the surface of the molded body that has undergone the chemical plating catalyst application step. The chemical plating method is not particularly limited, and a method conventionally used in the plating treatment of plastic molded bodies can be used. For example, by immersing the molded product obtained in the chemical plating catalyst application step in a copper salt or nickel salt aqueous solution containing a reducing agent at about 10 to 50 ° C. for about 2 to 30 minutes, a copper plating film is formed on the surface. Alternatively, a nickel plating film can be formed. Further, depending on the application, an electroplating process may be performed. This process is a process for improving the adhesion strength of the plating film by electroplating the chemical plating film formed in the chemical plating process. This electroplating film may be a single metal film or a multilayer film composed of a plurality of metal films, but from the viewpoint of design, strength, life, etc., the uppermost layer is a chromium plating film. A multilayer coating is preferred. As such a multilayer film, for example, a film in which a copper plating film, a nickel plating film, and a chromium plating film are sequentially provided by electroplating can be preferably exemplified.

  There is no restriction | limiting in particular about the method of electroplating, The conventionally well-known method currently used in the plating process of a plastic molding can be used. In some applications, chemical plating is performed, but electroplating is not performed. In the present invention, a plated molded body having higher plating adhesion strength can be obtained by drying the plated molded body in the drying step. There is no restriction | limiting in particular about the method of drying, A conventionally well-known method can be used, and it is preferable to carry out for 10 second-about 60 minutes at 50-150 degreeC. As described above, a plated molded body having high plating density strength can be obtained efficiently. According to the present invention, the 90 ° peel strength, which is an index indicating the adhesion strength of plating, is not particularly limited, but is preferably 0.3 kg / cm or more, more preferably 0.5 kg / cm or more, and still more preferably 1 A plated molded body of 0.0 kg / cm or more, particularly preferably 1.5 kg / cm or more, and most preferably 2.0 kg / cm or more is obtained. Although there is no restriction | limiting in particular as an upper limit of this peel strength, It is preferable that it is 20.0 kg / cm or less, More preferably, it is 10.0 kg / cm or less.

  Further, a plated test piece obtained by plating an 80 mm × 80 mm × 3 mm thick test piece after injection molding is provided with a 1 mm square grid (10 × 10 pieces), and is defined in JIS K5400-1990. The remaining number of plating films when carrying out the cross-cut tape method and performing the cellophane tape peeling test is preferably 70 or more, more preferably 80 or more, and still more preferably 90 or more, Particularly preferred is 95 or more, and most preferred is 100.

  Further, the plating resin composition of the present invention has good surface impact even after a series of plating treatments including heat treatment and the like. A plated test piece obtained by plating a test piece of 80 mm × 80 mm × 3 mm thickness after injection molding with a thickness of 35 ± 5 μm at 23 ° C. with a punch tip diameter of 5/8 inch and a collision speed of 2.5 m / s. The impact energy obtained by performing a high-speed surface impact test under the conditions is not particularly limited, but is preferably 20 J or more, more preferably 30 J or more, still more preferably 35 J or more, and particularly preferably 45 J or more. Yes, most preferably 50 J or more. The upper limit is not particularly limited but is 150 J or less. The impact energy obtained by conducting a high-speed surface impact test on a similar plating test piece at a temperature of −30 ° C., a punch tip diameter of 5/8 inch, and a collision speed of 2.5 m / s is not particularly limited. It is preferably 5 J or more, more preferably 10 J or more, still more preferably 15 J or more, particularly preferably 20 J or more, and most preferably 30 J or more. The upper limit is not particularly limited but is 100 J or less.

  There is no particular limitation on the method for obtaining the coated molded body of the present invention, and electrostatic coating, powder coating, electrodeposition coating is applied to the surface of the molded body obtained by various conventionally known melt processing methods such as extrusion molding and injection molding. It can be obtained by a conventionally known coating method such as air spray coating or airless spray coating. Conventionally known paints can be suitably used as acrylic paints, phenolic resin paints, alkylated resin paints, aminoalkyd resin paints, vinyl chloride resin paints, silicone resin paints, fluororesin paints, unsaturated resin paints. , Epoxy resin paint, polyurethane resin paint, melamine resin paint, oil paint, powder paint, water-soluble resin paint, epoxy resin paint, acrylic urethane resin paint, acrylic melamine resin paint, polyester melamine resin paint, etc. Acrylic coating, urethane coating and melamine coating are more preferably used.

  For example, in melamine coating, a paint mainly composed of an acrylic melamine resin-based paint or a polyester melamine resin-based paint can be used. In urethane coating, a paint mainly composed of acrylic urethane resin-based paint can be used. In these coatings, conventionally known primers can be used. For example, a non-crosslinked primer mainly composed of a polyester urethane resin or a conductive primer imparted with conductivity can be used. . With regard to peel strength, which is an index indicating the adhesion strength of coating, in the present invention, a 180 ° peel strength measured by making a 10 mm wide cut in the coating film is not particularly limited, but may be 0.3 kg / cm or more. Preferably, it is 0.5 kg / cm or more, more preferably 0.9 kg / cm or more, particularly preferably 1.0 kg / cm or more, and most preferably 1.5 kg / cm or more. Although there is no restriction | limiting in particular as an upper limit of this peel strength, It is preferable that it is 20.0 kg / cm or less, More preferably, it is 10.0 kg / cm or less.

  In addition, the coating resin composition of the present invention has good surface impact even after a series of coating treatments including heat treatment and the like, and a test of 80 mm × 80 mm × 3 mm thickness after injection molding. A high-speed surface impact test was performed on a coating test piece obtained by coating the piece with a pencil hardness of H on the coating film surface at 23 ° C. under conditions of a punch tip diameter of 5/8 inch and a collision speed of 2.5 m / s. The impact energy obtained by carrying out is not particularly limited, but is preferably 20 J or more, more preferably 30 J or more, still more preferably 35 J or more, particularly preferably 45 J or more, and most preferably 50 J. That's it. The upper limit is not particularly limited, but is 150 J or less. The impact energy obtained by conducting a high-speed surface impact test on a similar coated test piece at a temperature of −30 ° C., a punch tip diameter of 5/8 inch, and a collision speed of 2.5 m / s is not particularly limited. It is preferably 5 J or more, more preferably 10 J or more, still more preferably 15 J or more, particularly preferably 20 J or more, and most preferably 30 J or more. The upper limit is not particularly limited but is 100 J or less.

  Here, the surface hardness is obtained by measuring the pencil hardness under a 1 kg load according to JIS-K-5400.

  Moreover, about the coating test piece obtained by coating the test piece of 80 mm x 80 mm x 3 mm thickness after injection molding, a 1 mm square grid (10x10 pieces) is attached, and it is prescribed | regulated to JISK5400-1990. The remaining number of the coating film when the cellophane tape peeling test is performed by a cross-cut tape method is preferably 70 or more, more preferably 80 or more, still more preferably 90 or more, particularly preferably. Is 95 or more, and most preferably 100.

  The resin composition for plating and coating of the present invention, the plated molded body and the coated molded body have excellent plating adhesion and coating adhesion, have a good appearance, and after coating, the molded body after plating has surface impact properties. Excellent. It can be used for various molded products that take advantage of these properties, especially automotive parts such as front grille, wheel caps and emblems, automotive interior and exterior materials such as bumpers and fenders, and housing and parts around electrical and electronic equipment. As useful.

  Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Prior to the description of each example, various physical property measurement methods employed in the example will be described.

(1) Plating adhesion strength About a square plate having a length of 80 mm, a width of 80 mm and a thickness of 3 mm obtained by injection molding, a chromic acid-sulfuric acid mixture (mixed liquid of chromic acid 400 g / L and sulfuric acid 400 g / L) was used. Etching was performed at a temperature of 15 ° C. for 15 minutes. After washing with water, it was then immersed for 3 minutes in a catalyst solution containing 30 g / L of palladium chloride, 20 g / L of stannous chloride and 150 g / L of hydrochloric acid at a liquid temperature of 30 ° C. Next, it was washed with water and immersed in an aqueous solution containing 10 g / L of sodium hydroxide at 40 ° C. for 2 minutes. Then, it was immersed in an electroless nickel plating solution containing 10 g / L of nickel sulfate, 10 g / L of sodium hypophosphite, 20 g / L of citric acid and 5 g / L of ammonium chloride for 10 minutes at 40 ° C. A nickel plating film was formed. Further, the test piece on which the electroless plating film was formed was subjected to electroplating treatment at a temperature of 3 A / dm ² and 25 ° C. for 120 minutes using a copper sulfate plating bath to form a copper plating film. The sample thus obtained was dried at 80 ° C. for 60 minutes. The thickness of the plated film of the sample after drying was measured by SEM (scanning electron microscope) and found to be 35 ± 5 μm. Next, a slit having a width of 10 mm was made in this plating film at room temperature, the strip-like plating film was peeled off from one end and pulled in the vertical direction, and the 90 ° peel strength was measured (JIS H8630-1987, Annex 6). Compliant).

  Further, a plating test piece obtained by plating in the same manner as described above and drying at 80 ° C. for 60 minutes is provided with a 1 mm square grid (10 × 10), and a grid defined in JIS K5400-1990. An eye tape method was performed, a cellophane tape peel test was performed, and the plating adhesion was evaluated based on the remaining number of plating films. The evaluation criteria were as follows. Remaining number of plating films 100: Evaluation score 5, Remaining number of plating films 95 to 99: Evaluation score 4, Remaining number of plating films 90 to 94: Evaluation score 3, Remaining number of plating films 80 to 89: Evaluation Score 2, plating film remaining number 70 to 79: evaluation score 1, plating film remaining number 69 or less: evaluation score 0.

(2) Coating adhesion strength A two-part curable urethane paint (Top R-263, manufactured by Nippon Bee Chemical Co., Ltd.) is formed to a thickness of 110 ± 10 μm on a square plate of 80 mm long × 80 mm wide × 3 mm thick obtained by injection molding. This was sprayed and applied, and baked at 80 ° C. for 40 minutes. Subsequently, it was dried at 80 ° C. for 60 minutes. It was H when the pencil hardness of the coating film surface of the sample obtained in this way was measured under 1 kg load using a pencil specified in JIS-S-6006 according to JIS-K-5400. With respect to this sample, a cut having a width of 10 mm was made in the coating film at room temperature, the strip-shaped coating film was peeled off from one end and pulled in the vertical direction, and 180 ° peel strength was measured.

  In addition, a similar sample obtained by applying the coating as described above and drying at 80 ° C. for 60 minutes is then subjected to a 1 mm square grid pattern by a grid pattern tape method defined in JIS K5400-1990. (10 × 10 pieces) was attached, a cellophane tape peeling test was performed, and the paintability was evaluated based on the number of remaining coating films. The evaluation criteria were as follows. Number of remaining coating films 100: Evaluation score 5, Number of remaining coating films 95 to 99: Evaluation score 4, Number of remaining coating films 90 to 94: Evaluation score 3, Number of remaining coating films 80 to 89: Evaluation Score 2, number of remaining coatings 70 to 79: evaluation score 1, number of remaining coatings 69 or less: evaluation score 0.

(3) Appearance of plating film The electroless nickel plating film sample obtained in (1) above was visually evaluated for the appearance of the plating film in accordance with JIS H8630-1987, Annex 2. The test piece was coated on the entire surface, and there was no unevenness, blistering or peeling, and excellent smoothness was marked with ◯, and the others were marked with x.

(4) Appearance of coating film Regarding the coated sample obtained in (2) above, the sample having no unevenness, blistering and peeling and having excellent smoothness was rated as “good”, and the others as “x”.

(5) Surface impact property A test piece of 80 mm × 80 mm × 3 mm thickness obtained by injection molding at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. was subjected to a thickness of 35 ± 5 μm by the same method as (1) above. A plating test piece obtained by plating, or a test piece of 80 mm × 80 mm × 3 mm thickness obtained by injection molding at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. by the same method as in (2) above. High-speed surface impact test for each of the paint specimens with a pencil hardness of H on the coating film surface obtained at the coating at 23 ° C. under conditions of a punch tip diameter of 5/8 inch and a collision speed of 2.5 m / s. The impact energy obtained by performing was measured. Here, the pencil hardness of the coating surface is obtained by measuring under a 1 kg load using a pencil specified in JIS-S-6006 in accordance with JIS-K-5400.

(6) Melt Viscosity Ratio Using a plunger type capillary rheometer (Capillograph Type 1C, manufactured by Toyo Seiki Seisakusho), a styrene resin (A) and a polyamide resin at a shear rate of 1000 seconds ^-1 at the temperature during melt molding ( Each melt viscosity (Pa · s) of B) was measured, and a melt viscosity ratio defined by <melt viscosity of styrene resin (A)> / <melt viscosity of polyamide resin (B)> was calculated.

(7) Phase structure 1 (polyamide resin (B) continuous phase)
A portion (center portion) of 1.2 to 1.8 mm from the surface in the thickness direction of ASTM No. 1 dumbbell (thickness 3 mm) was dyed with phosphotungstic acid, and a polyamide resin (B) was dyed. Next, the center part of the compact was observed using TEM (H-7100 transmission electron microscope manufactured by Hitachi, Ltd.). In the electron micrograph of the central part of the molded body thus obtained (the thickness of the photograph is uniform), any three locations (10 μm × 10 μm range) are extracted, and at each extracted location (10 μm × 10 μm range), The dyed and continuous phase portion was cut out, the total weight thereof was measured, and the ratio to the total weight (10 μm × 10 μm range) before cutting out the portion was calculated. Since this weight ratio can be regarded as a capacity ratio because the thickness of the electron micrograph is uniform, an average value obtained by performing this operation at any three locations is a polyamide resin at the center of the molded body. (B) was adopted as a capacity ratio (capacity%) of a portion that becomes a continuous phase. In the central phase structure, the evaluation score is 4 when the portion where the polyamide resin (B) is a continuous phase is formed in an amount of 30% by volume or more, and the evaluation score is when the continuous phase is 20% by volume or more and less than 30% by volume 3. Evaluation score 2 when the continuous phase is 10% by volume or more and less than 20% by volume, evaluation score 1 when the continuous phase is less than 10% by volume, evaluation score 0 when the continuous phase is not formed at all It was.

(8) Phase structure 2 (vinyl-based (co) polymer (A-2) dispersed phase)
In an electron micrograph similar to that used in the analysis of phase structure 1, three arbitrary positions were extracted, and each extracted position (10 μm × 10 μm range) was not stained with phosphotungstic acid and graft ( A portion in which the (co) polymer (A-1) and / or the vinyl-based (co) polymer (A-2) becomes a dispersed phase was cut off. Here, when the graft (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) extends outside the extracted range of 10 μm × 10 μm, any 10 μm When it was within the range of × 10 μm, this was used as a dispersed phase, and a portion existing within the range was cut off. The total weight of these cut-out portions was measured, and the ratio to the total weight (10 μm × 10 μm range) before cutting out the portions was calculated. Since this weight ratio can be regarded as a capacity ratio because the thickness of the electron micrograph is uniform, an average value obtained by performing this operation at any three locations is grafted at the center of the molded body. It was adopted as the volume ratio (volume%) of the portion where the (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) was the dispersed phase. When the proportion of the dispersed phase of the graft (co) polymer (A-1) and / or the vinyl (co) polymer (A-2) is 50% by volume or more, the evaluation score is 4, and the dispersed phase is 30 An evaluation score of 3 when the volume is greater than or equal to 50% by volume, an evaluation score of 2 when the dispersed phase is greater than or equal to 10% and less than 30%, and an evaluation score of 1 when the dispersed phase is less than 10% by volume The evaluation score was 0 when no dispersed phase was formed.

(9) Determination of α, β-unsaturated carboxylic acid anhydride unit of copolymer (C) α, β-unsaturated carboxylic acid anhydride and α, β-unsaturated contained in copolymer (C) For monomers other than carboxylic acid anhydrides, calibration curves of infrared absorption spectra were prepared, and quantification was performed by measuring infrared absorption spectra. For example, when the copolymer (C) includes an α, β-unsaturated carboxylic anhydride unit and a vinyl cyanide monomer unit, the α, β-unsaturated carboxylic anhydride and vinyl cyanide are used. Monomers are mixed at various molar ratios, and an infrared absorption spectrum is measured using a Fourier transform infrared spectrophotometer (FTIR-8100A, manufactured by Shimadzu Corporation), whereby α, β-unsaturated carboxylic acid anhydride and An infrared absorption spectrum calibration curve for the intensity ratio and molar ratio of the characteristic absorption peak with vinyl cyanide monomer was prepared. Next, the infrared absorption spectrum of the copolymer (C) is measured, and by using the prepared calibration curve, the reaction is added and the α, β-unsaturated carboxylic acid anhydride contained in the copolymer (C) is added. The molar ratio between the unit and the vinyl cyanide monomer was calculated. Next, the other component units of the copolymer (C) are also calculated in the same manner, and the molar ratio with the vinyl cyanide monomer is calculated. Based on these results, the α, β-unsaturated carboxylic acid anhydride is calculated. The unit content was calculated. In preparing an infrared absorption spectrum calibration curve, α, β-unsaturated carboxylic acid anhydride has a characteristic absorption peak (about 1780 cm ⁻¹ ) due to stretching vibration of the carbonyl group, and a vinyl cyanide monomer unit. Shows a characteristic absorption peak due to stretching vibration of CN group (about 2228 cm ⁻¹ ), and when an aromatic vinyl monomer is included, a characteristic absorption peak due to aromatic C═C in-plane vibration (about 1495 cm ⁻¹ ). Was used. These characteristic absorption peaks in copolymer (C) are about 1780 cm ⁻¹ for α, β-unsaturated carboxylic anhydride units, about 2238 cm ⁻¹ for vinyl cyanide monomer units, The aromatic vinyl monomer unit was confirmed to be about 1495 cm ⁻¹ .

(10) Weight average molecular weight 20 mg of copolymer (C) was dissolved in 10 ml of solvent tetrahydrofuran, and gel permeation chromatograph (pump: 515 type, manufactured by Waters, column: TSKgel GMHR-H (30) and TSKgel Multipore HXL-). M was measured using a direct connection manufactured by Tosoh Corporation. The column temperature was 40 ° C., and an ultraviolet detector was used as the detector. The weight average molecular weight was determined in terms of polystyrene.

<Styrene resin (A)>
Reference Example 1 Preparation of Graft Copolymer (A-1) (a-1) The following materials were charged in a polymerization vessel and heated to 65 ° C. with stirring. The polymerization was started when the internal temperature reached 65 ° C., and 40 parts by weight of a mixture comprising 71 parts by weight of styrene, 29 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours.
Polybutadiene latex (weight average particle diameter 0.2 μm): 60 parts by weight (in terms of solid content)
Potassium oleate: 0.5 parts by weight Glucose: 0.5 parts by weight Sodium pyrophosphate: 0.5 parts by weight Ferrous sulfate: 0.005 parts by weight Deionized water: 120 parts by weight

  In parallel, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a graft copolymer (a-1).

  Acetone was added to a predetermined amount (m) of this graft copolymer (a-1) and refluxed for 4 hours. The solution was centrifuged at 8800 rpm (centrifugal force 10,000 G) for 40 minutes, and then the insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 70 ° C. for 5 hours, then the weight (n) was measured, and the graft ratio = [(n) − (m) × L] / [(m) × L] × 100 was calculated. The grafting rate was 37%. Here, L is the rubber content of the graft copolymer.

  The filtrate of the acetone solution was concentrated with a rotary evaporator to obtain a precipitate (acetone soluble matter). This soluble matter was dried under reduced pressure at 70 ° C. for 5 hours, adjusted to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.39 dl / g. there were.

(Reference Example 2) Preparation of vinyl copolymer (A-2) (a-2) 80 parts by weight of acrylamide, 20 parts by weight of methyl methacrylate, 0.3 part by weight of potassium persulfate, 1500 parts by weight of ion-exchanged water The reactor was charged and the gas phase in the reactor was replaced with nitrogen gas and kept at 70 ° C. with good mixing. The reaction was continued until the monomer was completely converted to a polymer and was obtained as an aqueous solution of acrylamide and methyl methacrylate binary copolymer. Dilution with ion-exchanged water gave a solution in which 0.05 part of methyl methacrylate / acrylamide copolymer was dissolved in 165 parts of ion-exchanged water.

A solution prepared by dissolving 0.05 parts of the obtained methyl methacrylate / acrylamide copolymer in 165 parts of ion-exchanged water in a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade was stirred at 400 rpm. The inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Styrene: 71 parts by weight Acrylonitrile: 29 parts by weight t-dodecyl mercaptan: 0.2 parts by weight 2,2′-azobisisobutyronitrile: 0.4 parts by weight

  After raising the reaction temperature to 65 ° C. over 15 minutes, the temperature was raised to 90 ° C. over 2 hours and maintained at 90 ° C. for 2 hours to complete the polymerization. The reaction system was cooled, the polymer was separated, washed and dried to obtain a bead-like vinyl copolymer (a-2) containing 71% by weight of styrene units and 29% by weight of acrylonitrile units. The polymer yield was 96%. This copolymer was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured using an Ubbelohde viscometer was 0.51 dl / g.

(Reference Example 3) Preparation of vinyl copolymer (A-2) (a-3) 50 parts by weight of styrene, 49.5 parts by weight of N-phenylmaleimide, 0.5 parts by weight of maleic anhydride, t-dodecyl mercaptan 0.2 part by weight, 0.3 part by weight of 2,2′-azobisisobutyronitrile was charged into a stainless steel autoclave equipped with a baffle containing 120 parts by weight of methyl ethyl ketone and a fiddle-type stirring blade, and this solution was added at 300 rpm. The temperature was raised to 80 ° C. with stirring, and then kept at 80 ° C. for 8 hours to complete the polymerization. After cooling, the solution was poured into an excess amount of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain a vinyl copolymer (a-3). The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve was 50.0% by weight of styrene units, 49.5% by weight of N-phenylmaleimide units, and 0.5% by weight of maleic anhydride units. % Content. The vinyl copolymer (a-3) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.35 dl / g. .

<Polyamide resin (B)>
(Reference Example 4) Polyamide resin (B) (b-1): Nylon 6 having a relative viscosity of 2.3 at 25 ° C. at a concentration of 1 g / dl in 98% concentrated sulfuric acid was used.

  Reference Example 5 Polyamide resin (B) (b-2): Nylon 6 having a relative viscosity of 3.3 at 25 ° C. in a solution dissolved in 98% concentrated sulfuric acid at a concentration of 1 g / dl was used.

<Copolymer (C)>
Reference Example 6 Preparation of Copolymer (C) (c-1) 30 parts by weight of styrene, 29.9 parts by weight of acrylonitrile, 0.2 parts by weight of maleic anhydride, 0.3 part by weight of t-dodecyl mercaptan, 2 , 2′-azobisisobutyronitrile in an amount of 0.3 parts by weight was charged into a stainless steel autoclave equipped with a baffle containing 60 parts by weight of methyl ethyl ketone and a foudra-type stirring blade, and the temperature was adjusted to 80 with stirring at 300 rpm. The temperature was raised to ° C. Subsequently, a solution obtained by dissolving 37.6 parts by weight of styrene, 2.3 parts by weight of maleic anhydride, and 0.2 parts by weight of 2,2′-azobisisobutyronitrile in 60 parts by weight of methyl ethyl ketone was continuously added in 5 hours. Added. After the addition, the temperature was further maintained at 80 ° C. for 3 hours to complete the polymerization. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain a copolymer (C) (c-1). The polymer yield was 93%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 67.6% by weight of styrene units, 29.9% by weight of acrylonitrile units, and 2.5% by weight of maleic anhydride units. It was a thing. In addition, copolymer (C) (c-1) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.30 dl / g. It was. Moreover, the weight average molecular weight measured using the gel permeation chromatograph was 34000.

Reference Example 7 Preparation of Copolymer (C) (c-2) 30 parts by weight of styrene, 30 parts by weight of acrylonitrile, 0.3 part by weight of maleic anhydride, 0.6 part by weight of t-dodecyl mercaptan, 2,2 '-Azobisisobutyronitrile (0.3 parts by weight) was charged into a stainless steel autoclave equipped with a baffle containing 60 parts by weight of methyl ethyl ketone and a foudra type stirring blade, and the temperature was raised to 80 ° C. while stirring the solution at 300 rpm. The temperature rose. Subsequently, a solution prepared by dissolving 37 parts by weight of styrene, 2.7 parts by weight of maleic anhydride, and 0.2 parts by weight of 2,2′-azobisisobutyronitrile in 60 parts by weight of methyl ethyl ketone was continuously added in 5 hours. . After the addition, the temperature was further kept at 80 ° C. for 4 hours to complete the polymerization. After cooling, the solution is poured into 5 equivalents of methanol, purified by reprecipitation, vacuum dried at 80 ° C. for 15 hours to completely distill off the solvent, and copolymer (C) (c-2) is obtained. Obtained. The polymer yield was 93%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 67.0% by weight of styrene units, 30.0% by weight of acrylonitrile units, and 3.0% by weight of maleic anhydride units. It was a thing. In addition, the intrinsic viscosity of copolymer (C) (c-2) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at a temperature of 30 ° C. using an Ubbelohde viscometer is 0.25 dl / g. Moreover, the weight average molecular weight measured using the gel permeation chromatograph was 31000.

Reference Example 8 Preparation of Copolymer (C) (c-3) 33 parts by weight of styrene, 29.5 parts by weight of acrylonitrile, 1.0 part by weight of maleic anhydride, 0.75 part by weight of t-dodecyl mercaptan, 2 , 2′-azobisisobutyronitrile in an amount of 0.3 parts by weight was charged into a stainless steel autoclave equipped with a baffle containing 60 parts by weight of methyl ethyl ketone and a foudra-type stirring blade, and the temperature was adjusted to 80 with stirring at 300 rpm. The temperature was raised to ° C. Subsequently, a solution prepared by dissolving 34 parts by weight of styrene, 2.5 parts by weight of maleic anhydride and 0.2 parts by weight of 2,2′-azobisisobutyronitrile in 60 parts by weight of methyl ethyl ketone was continuously added in 5 hours. . The polymerization was completed after maintaining at 80 ° C. for 9 hours. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, vacuum-dried at 80 ° C. for 12 hours to completely remove the solvent, and copolymer (C) (c-3) was obtained. Obtained. The polymer yield was 87%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 67% by weight of styrene units, 29.5% by weight of acrylonitrile units, and 3.5% by weight of maleic anhydride units. Met. In addition, copolymer (C) (c-3) was prepared to 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured at 30 ° C. using an Ubbelohde viscometer was 0.17 dl / g. It was. Moreover, the weight average molecular weight measured using the gel permeation chromatograph was 18000.

Reference Example 9 Preparation of Copolymer (d-1) for Comparative Example 80 parts by weight of acrylamide, 20 parts by weight of methyl methacrylate, 0.3 part by weight of potassium persulfate, and 1500 parts by weight of ion-exchanged water were added to the reactor. The gas phase in the reactor was replaced with nitrogen gas and kept at 70 ° C. with good agitation. The reaction was continued until the monomer was completely converted to a polymer and was obtained as an aqueous solution of acrylamide and methyl methacrylate binary copolymer. Dilution with ion-exchanged water gave a solution in which 0.05 part of methyl methacrylate / acrylamide copolymer was dissolved in 165 parts of ion-exchanged water.

A solution prepared by dissolving 0.05 parts of the obtained methyl methacrylate / acrylamide copolymer in 165 parts of ion-exchanged water in a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade was stirred at 400 rpm. The inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate suspension polymerization.
Styrene: 70 parts by weight Acrylonitrile: 25 parts by weight Methacrylic acid: 5 parts by weight t-dodecyl mercaptan: 0.4 parts by weight 2,2′-azobisisobutyronitrile: 0.2 parts by weight

  After raising the reaction temperature to 65 ° C. over 15 minutes, the temperature was raised to 90 ° C. over 2 hours and maintained at 90 ° C. for 2 hours to complete the polymerization. The reaction system was cooled, the polymer was separated, washed, and dried to obtain a bead-shaped copolymer (d-1). The polymer yield was 96%. The composition determined by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contained 70% by weight of styrene units, 25% by weight of acrylonitrile units, and 5% by weight of methacrylic acid units. The intrinsic viscosity of the copolymer (d-1) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.59 dl / g.

Reference Example 10 Preparation of Comparative Copolymer (d-2) 120 parts of pure water and 0.3 part of potassium persulfate were charged into a polymerization vessel and heated to 65 ° C. while stirring. The polymerization was started when the internal temperature reached 65 ° C., and a mixture of 67 parts by weight of styrene, 30 parts by weight of acrylonitrile, 3 parts by weight of methacrylic acid and 1.5 parts by weight of t-dodecyl mercaptan and 2 parts of sodium dodecylbenzenesulfonate 30 parts of an emulsifier aqueous solution containing each was continuously added over 5 hours. Subsequently, the temperature of the polymerization system was raised to 70 ° C., and polymerization was performed for 3 hours to complete the polymerization. Then, copolymerization (d-2) was obtained by salting out, dehydrating and drying using calcium chloride. The polymer yield at this time was 95%. The composition obtained by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contained 67% by weight of styrene units, 30% by weight of acrylonitrile units, and 3% by weight of methacrylic acid units. The intrinsic viscosity of the copolymer (d-2) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.31 dl / g.

Reference Example 11 Preparation of Copolymer (d-3) for Comparative Example Styrene 70.0 parts by weight, acrylonitrile 28.8 parts by weight, maleic anhydride 1.2 parts by weight, t-dodecyl mercaptan 0.02 parts by weight Part, 2,2′-azobisisobutyronitrile 0.3 parts by weight was charged into a stainless steel autoclave equipped with a baffle containing 80 parts by weight of methyl ethyl ketone and a foudra-type stirring blade, and the solution was stirred at 300 rpm. The temperature was raised to 80 ° C. The polymerization was terminated by maintaining the temperature at 80 ° C. for 9 hours. After cooling, the solution was poured into 5 equivalents of methanol, purified by reprecipitation, and the solvent was completely distilled off by drying to obtain a copolymer (d-3). The polymer yield was 97%. The composition determined by infrared absorption spectrum measurement using an infrared absorption spectrum calibration curve contains 70.7% by weight of styrene units, 28.1% by weight of acrylonitrile units, and 1.2% by weight of maleic anhydride units. It was something to do. The intrinsic viscosity of the copolymer (d-3) prepared at 0.4 g / 100 ml (methyl ethyl ketone, 30 ° C.) and measured at 30 ° C. using an Ubbelohde viscometer was 0.69 dl / g.

Reference Example 12 Preparation of Comparative Copolymer (d-4) 93 parts by weight of styrene, 4 parts by weight of acrylic acid, and 3 parts by weight of maleic anhydride were dissolved in 130 parts by weight of methyl ethyl ketone, and t-dodecyl mercaptan 0 0.02 part by weight and 0.3 part by weight of 2,2′-azobisisobutyronitrile were added, and solution polymerization was carried out at 80 ° C. for 6 hours. After cooling, it was poured into 5 equivalents of methanol and reprecipitated to obtain a copolymer. This copolymer was dried with hot air at 80 ° C. for 12 hours to obtain a copolymer (d-4) containing 93% by weight of styrene units, 4% by weight of acrylic acid units and 3% by weight of maleic anhydride units. Moreover, the intrinsic viscosity which measured the copolymer (d-4) to 0.4 g / 100 ml (methyl ethyl ketone, 30 degreeC), and measured using the Ubbelohde viscometer was 0.55 dl / g.

(Examples 1-4)
The styrenic resin (A), polyamide resin (B) and copolymer (C) prepared in the reference example were mixed at the blending ratio shown in Table 1, and the screw diameter was 30 mm and the L / D was 44.5 in the same direction. Pellets were produced by charging from a supply port on the upstream side of a rotary twin-screw extruder (TEX-30 manufactured by Nippon Steel Works), and performing melt-kneading and extrusion at a resin temperature of 250 ° C. and a screw rotation speed of 150 rpm. Each pellet was subjected to injection molding under the conditions of a molding temperature of 250 ° C. and a mold temperature of 60 ° C. to prepare each test piece. About these test pieces, the copper plating membrane | film | coat was formed by the method described by the measurement of said (1) plating adhesion strength, and the physical property was evaluated. These results are shown in Table 1.

(Comparative Examples 1-4)
The styrene resin (A), the polyamide resin (B) and the copolymer for the comparative example prepared in the reference example were mixed at the blending ratio shown in Table 1, and the same production method as in Examples 1 to 4 was used. Test specimens were prepared, and about these test specimens, a copper plating film was formed by the method described in (1) Measurement of plating adhesion strength, and physical properties were evaluated. These results are shown in Table 1.

(Examples 5 to 8)
The styrenic resin (A), polyamide resin (B) and copolymer (C) prepared in Reference Example were mixed at the blending ratio shown in Table 2, and a test piece was prepared by the same production method as in Examples 1 to 4. A coating film was formed on these test pieces by the method described in (2) Measurement of coating adhesion strength, and physical properties were evaluated. These results are shown in Table 2.

(Comparative Examples 5-7)
The styrenic resin (A), polyamide resin (B) and copolymer (D) prepared in Reference Example were mixed at the blending ratio shown in Table 2, and the test piece was prepared under the same production conditions as in Examples 1 to 4. About these test pieces, a coating film was formed by the method described in (2) Measurement of coating adhesion strength, and physical properties were evaluated. These results are shown in Table 2.

  From the examples and comparative examples, the following became clear.

  From Table 1, the polyamide resin (B) is added at the center of the molded product, although the specific copolymer (C) is added and the polyamide resin (B) is a smaller component than the styrene resin (A). The resin compositions of Examples 1 to 4 having a phase structure in which a portion that becomes a continuous phase is 10% by volume or more are more effective in surface impact after plating than the resin compositions of Comparative Examples 1 to 4. It was found that the coating film had a high balance between the peel strength of the plated film and the plating adhesion and the surface impact after plating according to the cross-cut test results. From Table 2, the polyamide resin is added at the center of the molded product, although the specific copolymer (C) of the present invention is added and the polyamide resin (B) is a smaller component than the styrene resin (A). In the resin composition of the present invention of Examples 5 to 8 having a phase structure in which (B) forms a continuous phase, the specific copolymer (C) is not used in combination and at the center of the molded body Compared with the resin compositions of Comparative Examples 6 to 8 in which the polyamide resin (B) does not form a continuous phase portion, the surface impact after coating treatment is greatly excellent, and the peel strength and cross-cutness of the coating film after coating are great. From the test results, it was found that there was a high degree of balance between paint adhesion and surface impact after painting.

  The thermoplastic resin composition of the present invention can be usefully used particularly as an automobile part, an automobile interior / exterior material, and a housing / part surrounding material of an electric / electronic device, taking advantage of the above-described excellent characteristics.

It is a model figure which illustrates one of the preferable phase structures formed in the molded object center part of the thermoplastic resin composition of this invention.

Explanation of symbols

1 Part where polyamide resin (B) forms a continuous phase 2 Part where vinyl (co) polymer (A-2) forms a dispersed phase 3 Graft (co) polymer (A-1) forms a dispersed phase Part

Claims (10)

Graft (co) weight obtained by graft polymerization of a monomer unit consisting of 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer on a rubber polymer. Of the vinyl (co) polymer (A-2) comprising the combined (A-1), 100 to 45% by weight of the aromatic vinyl monomer and 0 to 55% by weight of at least one other monomer. Α, β- with respect to 100 parts by weight of a thermoplastic resin composition comprising 55 to 85% by weight of a styrene resin (A) containing at least one of them and 45 to 15% by weight of a polyamide resin (B). 0.05 to 80 parts by weight of a modified vinyl copolymer (C) comprising 0.05 to 20% by weight of an unsaturated carboxylic acid anhydride unit and 0.5 to 60% by weight of a vinyl cyanide monomer unit Of the modified vinyl copolymer (C) A thermoplastic resin composition having an intrinsic viscosity in the range of 0.15 to 0.41 dl / g when dissolved in a tilketone solvent and measured at a temperature of 30 ° C., and further melt-molding the thermoplastic resin composition As a phase structure observed with an electron microscope in a region having a depth of 40 to 60% of the total thickness from the surface, where the thickness is a direction perpendicular to the surface of the molded body, A resin composition for plating, wherein a portion where the resin (B) becomes a continuous phase is formed in an amount of 10% by volume or more. 2. The plating resin according to claim 1, wherein the modified vinyl copolymer (C) is dissolved in a methyl ethyl ketone solvent and has an intrinsic viscosity in the range of 0.15 to 0.30 dl / g when measured at a temperature of 30 ° C. 3. Composition. The modified vinyl copolymer (C) comprises 1.5 to 10% by weight of α, β-unsaturated carboxylic anhydride unit and 0.5 to 60% by weight of vinyl cyanide monomer unit. The resin composition for plating according to claim 1 or 2. A plated test piece obtained by plating a test piece of 80 mm × 80 mm × 3 mm thickness after injection molding with a thickness of 35 ± 5 μm at 23 ° C. with a punch tip diameter of 5/8 inch and a collision speed of 2.5 m / s. The resin composition for plating according to any one of claims 1 to 3, wherein impact energy obtained by performing a high-speed surface impact test under conditions is 20 J or more. A plated test piece obtained by plating an 80 mm × 80 mm × 3 mm thick test piece after injection molding is provided with a 1 mm square grid (10 × 10), and a grid defined in JIS K5400-1990. The plating resin composition according to any one of claims 1 to 4, wherein the remaining number of plating films is 70 or more when the tape method is performed and the cellophane tape peeling test is performed. Graft (co) weight obtained by graft polymerization of a monomer unit consisting of 100 to 40% by weight of an aromatic vinyl monomer and 0 to 60% by weight of at least one other monomer on a rubber polymer. Of the vinyl (co) polymer (A-2) comprising the combined (A-1), 100 to 45% by weight of the aromatic vinyl monomer and 0 to 55% by weight of at least one other monomer. Α, β- with respect to 100 parts by weight of a thermoplastic resin composition comprising 55 to 85% by weight of a styrene resin (A) containing at least one of them and 45 to 15% by weight of a polyamide resin (B). 0.05 to 80 parts by weight of modified vinyl copolymer (C) comprising 0.05 to 10% by weight of unsaturated carboxylic acid anhydride unit and 0.5 to 60% by weight of vinyl cyanide monomer unit Of the modified vinyl copolymer (C) A thermoplastic resin composition having an intrinsic viscosity in the range of 0.15 to 0.41 dl / g when dissolved in a tilketone solvent and measured at a temperature of 30 ° C., and further melt-molding the thermoplastic resin composition As a phase structure observed with an electron microscope in a region having a depth of 40 to 60% of the total thickness from the surface when the thickness is a direction perpendicular to the surface of the molded body, A resin composition for coating, wherein a portion where the resin (B) becomes a continuous phase is formed in an amount of 10% by volume or more. A test piece having a pencil hardness of H on the surface of the coating film obtained by coating a test piece of 80 mm × 80 mm × 3 mm thickness after injection molding, punch tip diameter 5/8 inch, collision speed 2 at 23 ° C. The resin composition for coating according to claim 6, wherein the impact energy obtained by conducting a high-speed surface impact test under a condition of 0.5 m / s is 20 J or more. For the test piece obtained by coating the test piece of 80 mm × 80 mm × 3 mm thickness after injection molding, a 1 mm square grid (10 × 10) is attached, and the grid defined in JIS K5400-1990 The coating resin composition according to claim 6 or 7, wherein the remaining number of coating films when a cellophane tape peeling test is performed by a tape method is 70 or more. A plated molded body obtained by plating a resin molded body obtained by melt-molding the thermoplastic resin composition according to any one of claims 1 to 5. The coating molded object formed by coating the resin molded object formed by melt-molding the thermoplastic resin composition of any one of Claims 6-8.

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