Plating resin composition

Abstract

The plating resin composition of the present application contains a graft copolymer (A) in which a monomer component (a) containing a specific amount of an aromatic vinyl compound (al), a cyano-containing vinyl compound (a2), and another vinyl compound (a3) is graft-polymerized on a rubbery polymer, and a polycarbonate resin (P), the content of the polycarbonate resin (P) being 40 to 70 mass% relative to the total mass of the plating resin composition, the rubber content (X) in the graft copolymer (A) being more than 40 mass% relative to the total mass of the graft copolymer (A), the grafting rate (Y) of the graft copolymer (A) satisfying the following formula (1), and the rubber content (Z) in the plating resin composition being 10 to 18 mass% relative to the total mass of the plating resin composition.793e ‑0.041X ≥ Y ≥ 515e ‑0.041X (1).

Description

Technical Field

[0001] This invention relates to a resin composition for plating.

[0002] This application claims priority based on Japanese Patent Application No. 2020-214083, filed on December 23, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] Molded products made from acrylonitrile-butadiene-styrene copolymer (ABS resin) are widely used in a wide range of fields, including OA (office automation) equipment, information and communication equipment, electronic and electrical equipment, home appliances, automobiles, and construction, due to their excellent impact resistance, mechanical strength, and chemical resistance. Furthermore, ABS resin molded products are also used in various plastic coating applications due to their plating properties, namely, high adhesion strength of the plating film and excellent thermal cycling characteristics when coated. For example, in the automotive industry, applications are being explored for plating radiator grille components, emblem components, etc.

[0004] In addition, in recent years, especially with the increasing demands for impact resistance, heat resistance, and moldability, polycarbonate resin (PC resin) and PC / ABS resin have also been used.

[0005] The properties of plating are easily affected by the characteristics of the resin composition used to form the molded article and by factors such as molding conditions. Therefore, even when using a resin composition containing ABS resin, there is a possibility of poor plating appearance. Under poor molding conditions, appearance defects such as peeling and lifting of the plating film can occur, significantly impairing the commercial value of the final product.

[0006] Under such circumstances, a thermoplastic resin composition for plating, which has high adhesion strength and does not cause expansion or cracking of the plating film during thermal cycling, has been proposed (Patent Document 1). The composition contains a specified copolymer, a graft copolymer and an organosilicon compound in a specified proportion.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 8-193162 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, in the case of the coating resin composition of Patent Document 1, the coating adhesion strength of the coated article may not be sufficient, and sometimes the coating film peels off or lifts due to thermal cycling tests.

[0012] The purpose of this invention is to provide a resin composition for plating, which can yield plating products with excellent plating properties.

[0013] Methods for solving problems

[0014] The present invention has the following solutions.

[0015] [1] A resin composition for plating, comprising a graft copolymer (A) in which monomer component (a) is grafted and polymerized in a rubbery polymer and a polycarbonate resin (P),

[0016] The content of the above-mentioned polycarbonate resin (P) is 40-70% by mass relative to the total mass of the above-mentioned coating resin composition.

[0017] The monomer component (a) comprises, by mass, 60-80% of an aromatic vinyl compound (a1), 20-40% of a cyanide vinyl compound (a2), and 0-20% of other vinyl compounds (a3) ​​capable of copolymerizing with the aromatic vinyl compound (a1) and the cyanide vinyl compound (a2) relative to the total mass of the monomer component (a).

[0018] The rubber content (X) in the above-mentioned graft copolymer (A) is more than 40% by mass relative to the total mass of the above-mentioned graft copolymer (A).

[0019] The grafting rate (Y) of the above-mentioned graft copolymer (A) satisfies the following equation (1).

[0020] The rubber content (Z) in the above-mentioned coating resin composition is 10 to 18% by mass relative to the total mass of the above-mentioned coating resin composition.

[0021] 793e -0.041X ≥Y≥515e -0.041X ···(1)

[0022] [2] According to the above [1] coating resin composition, the content of the above graft copolymer (A) is 10 to 50% by mass relative to the total mass of the above coating resin composition, more preferably 15 to 50% by mass, even more preferably 17 to 50% by mass, even more preferably 20 to 50% by mass, even more preferably 21 to 50% by mass, even more preferably 21 to 45% by mass, even more preferably 21 to 40% by mass, particularly preferably 21 to 35% by mass, and most preferably 21 to 33% by mass.

[0023] [3] According to the above [1] or [2] plating resin composition, wherein the rubber content (Z) in the above plating resin composition is 10 to 15% by mass relative to the total mass of the above plating resin composition.

[0024] [4] According to any one of [1] to [3] above, the rubber content (X) in the graft copolymer (A) is more than 40% by mass and less than 80% by mass relative to the total mass of the graft copolymer (A), more preferably 45% to 75% by mass, and even more preferably 50% to 70% by mass.

[0025] [5] According to any one of [1] to [4] above, the grafting rate (Y) of the above-mentioned graft copolymer (A) is 20 to 100% by mass, more preferably 25 to 95% by mass, and even more preferably 30 to 90% by mass.

[0026] [6] The plating resin composition according to any one of [1] to [5] above further comprises a copolymer (B) formed by copolymerizing an aromatic vinyl compound (b1), a cyanide vinyl compound (b2) and other monovinyl compounds (b3) as needed.

[0027] [7] According to the above [6] plating resin composition, the content of the above copolymer (B) is 0 to 50% by mass relative to the total mass of the above plating resin composition, more preferably 1 to 45% by mass.

[0028] Invention Effects

[0029] According to the present invention, a resin composition for plating can be provided, which can yield plating products with excellent plating properties. Detailed Implementation

[0030] The following definitions of terms apply to this specification and the claims.

[0031] "Molded article" refers to an article formed by molding the coating resin composition of the present invention.

[0032] "Platinum-coated products" are products made by plating on molded products, with at least a portion of the surface of the molded product having a plating film.

[0033] "Excellent plating characteristics" refers to high plating adhesion strength and good thermal cycling characteristics.

[0034] "(Meth)acrylic acid" is a general term for acrylic acid and methacrylic acid.

[0035] "(Meth)acrylate" is a general term for acrylates and methacrylates.

[0036] The "~" sign indicating a range of values ​​refers to the values ​​recorded before and after it as the lower and upper limits.

[0037] [Resin Composition for Plating]

[0038] The coating resin composition of the present invention contains a graft copolymer (A) and a polycarbonate resin (P).

[0039] The resin composition for plating may further contain copolymer (B) as needed, without impairing the effects of the present invention.

[0040] In addition, the resin composition for plating may, as needed, contain other components besides the graft copolymer (A), polycarbonate resin (P), and copolymer (B) without impairing the effects of the present invention.

[0041] <Graft copolymer (A)>

[0042] Graft copolymer (A) is a copolymer in which monomer component (a) is grafted onto a rubbery polymer.

[0043] It should be noted that in graft copolymers (A), it is not easy to specify how the monomer component (a) in the rubber polymer polymerizes. That is, regarding graft copolymers (A), there are cases where it is impossible or largely impractical to directly specify them by their structure or properties (impossible / impractical). Therefore, graft copolymers (A) are more suitable to be defined as "in which monomer component (a) is grafted and polymerized in a rubber polymer".

[0044] (Rubber polymer)

[0045] Examples of rubbery polymers constituting the graft copolymer (A) include: butadiene-based rubbers such as polybutadiene, styrene-butadiene copolymer, and acrylate-butadiene copolymer; conjugated diene-based rubbers such as styrene-isoprene copolymer; acrylic-based rubbers such as polybutyl acrylate; olefin-based rubbers such as ethylene-propylene copolymer; and silicone-based rubbers such as polyorganosiloxane. It should be noted that these rubbery polymers can be used depending on the monomers. Rubbery polymers can also adopt composite rubber structures or core / shell structures.

[0046] As a rubber polymer, butadiene-based rubber, acrylic rubber, or their composite rubber polymers are preferred from the perspective of a good balance between color tone and impact resistance.

[0047] These rubber polymers can be used alone or in combination of two or more.

[0048] The average particle size of the rubber polymer is preferably 0.20 to 0.50 μm, more preferably 0.25 to 0.40 μm. If the average particle size of the rubber polymer is above the lower limit, the plating exudation property during plating treatment of the molded article is improved. Furthermore, the thermal cycling characteristics of the plated article are further improved. If the average particle size of the rubber polymer is below the upper limit, the plating adhesion strength of the plated article is further improved. Additionally, the flowability of the resin composition for plating is improved.

[0049] The average particle size of rubber polymers can be determined using a particle size distribution analyzer to measure the particle size distribution of a mass reference, and calculations can be performed based on the obtained particle size distribution.

[0050] The average particle size of rubber polymers can be controlled by adjusting the polymerization conditions (temperature, time, etc.) during the manufacturing of rubber polymers, as well as the types and proportions of monomers.

[0051] There are no particular limitations on the manufacturing method of rubber-like polymers, but emulsion polymerization is preferred from the perspective of easy particle size control. Emulsion polymerization can be carried out using known methods, and there are no particular limitations on the catalysts, emulsifiers, etc. that can be used.

[0052] Rubber polymers can be enlarged rubber. Furthermore, the average particle size and distribution can be adjusted through enlargement. Examples of enlargement methods include mechanical coagulation, chemical coagulation, and coagulation methods based on acid-containing copolymers.

[0053] As a chemical coagulation method, the following approach can be used: An acidic substance is added to the latex of a rubber polymer to destabilize the emulsion and induce coagulation, achieving the target particle size. Then, an alkaline substance is added to restabilize the latex. Examples of acidic substances include acetic acid, acetic anhydride, sulfuric acid, and phosphoric acid. Examples of alkaline substances include potassium hydroxide and sodium hydroxide.

[0054] As a coagulation method based on acid-containing copolymers, one example is a method in which latex of a rubbery polymer is mixed with latex of an acid-containing copolymer to obtain a latex of a hypertrophic rubber. Examples of acid-containing copolymer latex include, for instance, latex of an acid-containing copolymer obtained by polymerizing monomer components (including: acid-containing monomers (e.g., carboxyl-containing monomers such as (meth)acrylic acid), alkyl methacrylate monomers, and other monomers that can copolymerize with these monomers as needed) in water.

[0055] (Monomer component (a))

[0056] The monomer component (a) constituting the graft copolymer (A) includes an aromatic vinyl compound (a1), a cyanide vinyl compound (a2), and other vinyl compounds (a3) ​​as needed.

[0057] Examples of aromatic vinyl compounds (a1) include styrene, α-methylstyrene, vinyltoluenes (such as p-methylstyrene), halostyrene compounds (such as p-bromostyrene and p-chlorostyrene), p-tert-butylstyrene, dimethylstyrene, and vinylnaphthalene. Among these, styrene and α-methylstyrene are preferred.

[0058] These aromatic vinyl compounds (a1) can be used alone or in combination of two or more.

[0059] Examples of vinyl cyanide compounds (a2) include acrylonitrile and methacrylonitrile. Acrylonitrile is preferred.

[0060] These vinyl cyanide compounds (a2) can be used alone or in combination with two or more.

[0061] Other vinyl compounds (a3) ​​are vinyl compounds capable of copolymerizing with aromatic vinyl compounds (a1) and cyanide vinyl compounds (a2). Examples of such vinyl compounds include: alkyl methacrylates such as methyl methacrylate and ethyl methacrylate; alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide; and unsaturated carboxylic acid compounds such as (meth)acrylic acid, itaconic acid, and fumaric acid.

[0062] These other vinyl compounds (a3) ​​can be used alone or in combination of two or more.

[0063] Regarding the proportions of each vinyl compound in monomer component (a), relative to the total mass of monomer component (a), aromatic vinyl compounds (a1) are 60–80% by mass, cyanide vinyl compounds (a2) are 20–40% by mass, and other vinyl compounds (a3) ​​are 0–20% by mass. If the proportions of each compound are within the above range, the performance balance of the resin composition for plating, the plating adhesion strength of the plated product, and the thermal cycling characteristics is improved.

[0064] (Rubber content (X))

[0065] In this invention, the ratio of the rubber polymer to the total mass of the graft copolymer (A) is referred to as "the rubber content (X) in the graft copolymer (A)".

[0066] Regarding the ratio of the rubber polymer to the monomer component (a), relative to the total mass of the graft copolymer (A), the rubber polymer is more than 40% by mass, and the monomer component (a) is less than 60% by mass. If the ratio of the rubber polymer to the monomer component (a) is within the above range, the coating adhesion strength and thermal cycling characteristics of the plated product are improved. In addition, the impact resistance of the molded product is improved.

[0067] The proportion of the rubbery polymer (rubber content (X)) relative to the total mass of the graft copolymer (A) is preferably 45% by mass or more, more preferably 50% by mass or more. Furthermore, the proportion of the rubbery polymer relative to the total mass of the graft copolymer (A) is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. That is, the proportion of the rubbery polymer relative to the total mass of the graft copolymer (A) is more than 40% by mass, preferably 80% by mass or less, more preferably 45-75% by mass, and even more preferably 50-70% by mass.

[0068] The proportion of monomer component (a) relative to the total mass of graft copolymer (A) is 20% by mass or more, preferably less than 60% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

[0069] (Grafting rate (Y))

[0070] As detailed below, plated products are obtained by plating molded parts. However, to improve the adhesion of the plating film, the molded parts are usually etched before plating. When the molded parts are etched, the rubbery polymer dissolves into the etching solution, forming micropores on the surface of the molded body. It is believed that the plating adhesion strength is improved because metal can enter through these micropores. Generally, there is a tendency that the closer the shape of the micropores is to a circle, and the more uniformly the micropores are distributed, the better the plating adhesion strength and thermal cycling characteristics.

[0071] Rubber polymers can sometimes deform or agglomerate due to shear forces during the molding of coating resin compositions. If the rubber polymer deforms, the shape of the fine pores formed by the etching process also changes. Furthermore, if the rubber polymer agglomerates, the dispersion of the fine pores deteriorates.

[0072] There is a tendency that the higher the grafting rate (Y) of the graft copolymer (A), the less likely the rubber polymer will deform and agglomerate during molding, and the higher the coating adhesion strength and thermal cycling characteristics of the plated product.

[0073] To improve the grafting rate (Y), it is best to reduce the rubber content (X) in the graft copolymer (A) during polymerization.

[0074] However, there is a tendency that the lower the rubber content (X), the lower the impact resistance of the molded product or the lower the bonding strength of the plated product.

[0075] The inventors of this invention have conducted repeated and in-depth studies and found that in graft copolymers (A) with a rubber content (X) exceeding 40% by mass, if the grafting rate (Y) satisfies the following formula (1), both the rubber content (X) and the grafting rate (Y) can be improved in a balanced manner, resulting in extremely good plating characteristics.

[0076] From the viewpoint of further improving the adhesion strength and thermal cycling characteristics of plated products, the grafting rate (Y) is more preferably satisfied by the following formula (2).

[0077] 793e -0.041X ≥Y≥515e -0.041X ···(1)

[0078] 793e -0.041X ≥Y≥594e -0.041X ···(2)

[0079] The grafting rate (Y) of the graft copolymer (A) is not particularly limited as long as it satisfies the above formula (1), but it is preferably 20 to 100% by mass, more preferably 25 to 95% by mass, and even more preferably 30 to 90% by mass.

[0080] It should be noted that the grafting rate (Y) is a value expressed as the percentage of the mass (Wa) of the monomer component (a) grafted onto the rubber polymer relative to the mass (Wd) of the rubber polymer ((Wa / Wd)×100). However, in general, it can be calculated from the acetone-insoluble component of the graft copolymer (A) obtained after graft polymerization in the following manner.

[0081] Acetone was added to the graft copolymer (A), and the mixture was heated at 55°C for 3 hours to extract the acetone-soluble components. Then, the acetone-insoluble components were filtered, dried, and their mass was measured. The grafting rate was calculated according to the following formula (3). It should be noted that in the following formula (3), "m" represents the mass (g) of the graft copolymer (A) before extraction, "n" represents the mass (g) of the acetone-insoluble components, and "L" represents the rubber content (mass%) of the graft copolymer (A).

[0082] Grafting rate (%) = {(nm×L) / (m×L)}×100···(3)

[0083] Alternatively, the substance after filtering and drying the acetone-insoluble components can be determined by measuring the monomer components (a) of the grafted polymer with the rubbery polymer using an infrared spectrophotometer.

[0084] As a method for obtaining the acetone-insoluble component, besides dissolving the graft polymer (A) in acetone as described above, it can also be obtained by dissolving the plating resin composition in acetone. In the case of a polycarbonate resin, methods such as dissolving in chloroform or the like can be used to remove it. Subsequently, the monomer component (a) of the graft polymerized with the rubber polymer can also be determined by measuring it using an infrared spectrophotometer.

[0085] (Manufacturing method)

[0086] The graft copolymer (A) is obtained by polymerizing the monomer component (a) in the presence of a rubbery polymer (graft polymerization). The graft copolymer (A) thus obtained has the morphology of grafting a vinyl copolymer (which is obtained by polymerizing the monomer component (a)) into the rubbery polymer.

[0087] There are no particular limitations on the method for graft polymerization; however, emulsion polymerization is preferred from the perspective of controlling the reaction to ensure its stability. Specifically, examples include: methods where monomer component (a) is added to the latex of a rubber-based polymer in one step before polymerization; methods where a portion of monomer component (a) is added to the latex of a rubber-based polymer first, allowing it to polymerize while the remaining portion is added dropwise to the polymerization system; and methods where all the monomer component (a) is added dropwise to the latex of a rubber-based polymer while polymerization is underway. The polymerization of monomer component (a) can be carried out in one stage or in two or more stages. When carried out in two or more stages, the types and proportions of vinyl compounds constituting monomer component (a) in each stage can be varied.

[0088] Graft copolymers (A) obtained by emulsion polymerization are usually in the form of latex.

[0089] The polymerization conditions can be, for example, 1 to 10 hours at 30 to 95°C.

[0090] In emulsion polymerization, polymerization initiators, chain transfer agents (molecular weight regulators), and emulsifiers are typically used.

[0091] The rubber content (X) of the graft copolymer (A) can be adjusted by the amount of rubber polymer added (compounding amount).

[0092] The grafting ratio (Y) can be adjusted by the amount of rubber polymer and monomer component (a) added, as well as the amount of polymerization initiator and emulsifier used. Specifically, if the amount of polymerization initiator and emulsifier used is reduced, it is easy to obtain a graft copolymer (A) with a grafting ratio (Y) that satisfies the above formula (1).

[0093] Examples of polymerization initiators include: redox initiators (composed of organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide combined with reducing agents such as sugar pyrophosphate and hyposulfate); persulfates such as potassium persulfate; and peroxides such as benzoyl peroxide (BPO), azobisisobutyronitrile, lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl percarbonate. Polymerization initiators can be oil-soluble or water-soluble, and they can also be used in combination.

[0094] These polymerization initiators can be used alone or in combination of two or more.

[0095] Polymerization initiators can be added to the latex of rubbery polymers either once or continuously.

[0096] The amount of polymerization initiator used is preferably 0.05 to 0.25 parts by mass relative to 100 parts by mass of the total rubber polymer and monomer component (a), more preferably 0.08 to 0.2 parts by mass.

[0097] Examples of chain transfer agents include: thiols such as octyl thiol, n-dodecyl thiol, tert-dodecyl thiol, n-hexamethyl thiol, n-tetradecyl thiol, and tert-tetradecyl thiol; terpinolenes; and dimers of α-methylstyrene.

[0098] These chain transfer agents can be used alone or in combination of two or more.

[0099] Chain transfer agents can be added to the latex of rubber polymers either once or continuously.

[0100] The amount of chain transfer agent used is preferably 0.1 to 0.3 parts by mass relative to 100 parts by mass of the total rubber polymer and monomer component (a), more preferably 0.1 to 0.2 parts by mass.

[0101] Examples of emulsifiers include sodium sarcosinate, potassium fatty acid, sodium fatty acid, dipotassium alkenyl succinate, calcium rosinate, carboxylates such as heterogeneous calcium rosinate, and alkylbenzene sulfonates.

[0102] These emulsifiers can be used alone or in combination of two or more.

[0103] The amount of emulsifier used is preferably 0.1 to 0.4 parts by mass relative to 100 parts by mass of the total rubber polymer and monomer component (a), more preferably 0.1 to 0.3 parts by mass.

[0104] Graft copolymer (A) is usually obtained in the form of latex. Examples of methods for recovering graft copolymer (A) from the latex of graft copolymer (A) include: a wet method in which the latex of graft copolymer (A) is coagulated in a slurry by immersing it in hot water containing a coagulant; and a spray drying method in which the latex of graft copolymer (A) is recovered semi-directly by spraying it into a heated atmosphere.

[0105] Examples of coagulants used in wet processes include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. The selection depends on the emulsifier used in the polymerization. For example, if only a carboxylate is used as the emulsifier, one or more of the coagulants mentioned above can be used. When an emulsifier that exhibits stable emulsifying power even in acidic regions such as sodium alkylbenzene sulfonate is used as the emulsifier, a metal salt is suitable as the coagulant.

[0106] If a wet process is used, a slurry-like graft copolymer (A) can be obtained. Methods for obtaining a dried graft copolymer (A) from this slurry-like graft copolymer (A) include: first, dissolving residual emulsifier residue in water for washing; then, dehydrating the slurry using a centrifuge or pressure dewatering machine, followed by drying using an airflow dryer; or simultaneously performing dehydration and drying using a press dewatering machine, extruder, etc. By these methods, a powder or particulate dried graft copolymer (A) can be obtained.

[0107] There are no particular restrictions on the cleaning conditions, but it is preferable to clean the graft copolymer (A) under conditions that reduce the amount of emulsifier residue contained in 100% by mass of the dried graft copolymer (A) to less than 2% by mass.

[0108] It should be noted that the graft copolymer (A) discharged from the press dehydrator and extruder can also be sent directly to the extruder and molding machine for manufacturing resin compositions without being recycled, in order to produce molded products.

[0109] <Polycarbonate resin (P)>

[0110] Polycarbonate resin (P) is a resin with carbonate bonds in its main chain.

[0111] There are no particular limitations on polycarbonate resins (P), and examples include aromatic polycarbonate resins, aliphatic polycarbonate resins, aliphatic-aromatic polycarbonate resins, and aromatic polyester polycarbonate resins. These polycarbonate resins (P) can have their ends modified to R-CO- or R'-O-CO- groups (R- and R'- both represent monovalent organic groups).

[0112] From the viewpoint of improving the impact resistance and heat resistance of the molded article, the polycarbonate resin (P) is preferably selected from at least one of the group consisting of aromatic polycarbonate resin and aromatic polyester polycarbonate resin, and from the viewpoint of further improving the impact resistance, aromatic polycarbonate resin is more preferred.

[0113] Aromatic polycarbonate resins are those with the general formula -(-OX) 1 The polymer whose constituent units are shown as -OC(=O)-). X in the above general formula 1 It is a hydrocarbon group having one or more aromatic rings, or a group in which heteroatoms or heterobonds are introduced. In X 1 In the middle, in relation to X 1 The atoms directly bonded to the adjacent oxygen atom are carbon atoms that form the aromatic ring.

[0114] Examples of aromatic polycarbonate resins include: reaction products obtained by transesterification of aromatic dihydroxy compounds with carbonate diesters; condensation polymers obtained by interfacial condensation of aromatic dihydroxy compounds with carbonyl chloride; and condensation polymers obtained by the pyridine method of aromatic dihydroxy compounds with carbonyl chloride.

[0115] As an aromatic dihydroxy compound, any compound containing two hydroxyl groups bonded to an aromatic ring within its molecule is acceptable. Examples include hydroquinone, resorcinol (a dihydroxybenzene), 4,4'-biphenol, 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as "bisphenol A"), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)pentane, 1,1-bis(p-hydroxyphenyl)ethane, 2,2-bis(p-hydroxyphenyl)butane, 2,2-bis(p-hydroxyphenyl)pentane, and 1,1-bis(p-hydroxyphenyl)ethane. Phenylated cyclohexane, 1,1-bis(p-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(p-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(p-hydroxyphenyl)-1-phenylethane, 9,9-bis(p-hydroxyphenyl)fluorene, 9,9-bis(p-hydroxy-3-methylphenyl)fluorene, 4,4'-(p-phenylene diisopropylidene)bisphenol, 4,4'-(m-phenylene diisopropylidene)bisphenol, bis(p-hydroxyphenyl)oxide, bis(p-hydroxyphenyl) ketone, bis(p-hydroxyphenyl) ether, bis(p-hydroxyphenyl) ester, bis(p-hydroxyphenyl) sulfide, bis(p-hydroxy-3-methylphenyl) sulfide, bis(p-hydroxyphenyl) sulfone, bis(3,5-dibromo-4-hydroxyphenyl) sulfone, bis(p-hydroxyphenyl) sulfoxide, etc.

[0116] These aromatic dihydroxy compounds can be used alone or in combination of two or more.

[0117] As an aromatic dihydroxy compound, it is preferred to have a hydrocarbon group between two benzene rings. In this compound, examples of hydrocarbon groups include alkylene groups. The hydrocarbon group can be a halogen-substituted hydrocarbon group. The benzene ring can be a benzene ring in which the hydrogen atoms contained in the benzene ring are replaced by halogen atoms.

[0118] Examples of compounds having a hydrocarbon group between two benzene rings include bisphenol A, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl-3-methylphenyl)propane, 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(p-hydroxyphenyl)ethane, and 2,2-bis(p-hydroxyphenyl)butane.

[0119] Bisphenol A is preferred.

[0120] These compounds, which have a hydrocarbon group between two benzene rings, can be used alone or in combination with two or more.

[0121] Examples of carbonate diesters used to obtain aromatic polycarbonates via transesterification include dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and dimethyl carbonate.

[0122] These diesters can be used alone or in combination of two or more.

[0123] Polycarbonate resin (P) can be used alone or in combination with two or more. For example, two or more polycarbonate resins with different viscosity-average molecular weights can be used together.

[0124] The molecular weight of the polycarbonate resin (P) is arbitrary and not particularly limited; however, the viscosity-average molecular weight (Mv) calculated from the solution viscosity is generally preferably 15,000 to 40,000, more preferably 17,000 to 30,000, and particularly preferably 18,000 to 28,000. If the viscosity-average molecular weight is above the lower limit mentioned above, the impact resistance of the molded article is improved. If the viscosity-average molecular weight is below the upper limit mentioned above, the flowability of the resin composition for plating is improved.

[0125] The viscosity-average molecular weight (Mv) of polycarbonate resin (P) is determined by the solution viscosity method. Specifically, using a solution (sample) prepared by dissolving 0.7 g of polycarbonate resin (P) in 100 mL of dichloromethane and an Ubbelohde viscometer, the intrinsic viscosity [η] (in dl / g) at 25 °C is determined, and the viscosity-average molecular weight (Mv) is obtained according to the following formula (4).

[0126] [η] = 1.23 × 10 -4 ×Mv 0.83 ···(4)

[0127] <Copolymer (B)>

[0128] The copolymer (B) is a copolymer formed by copolymerizing an aromatic vinyl compound (b1), a cyanide vinyl compound (b2), and other monovinyl compounds (b3) as needed. That is, the copolymer (B) is a copolymer having monomer units from the aromatic vinyl compound (b1), monomer units from the cyanide vinyl compound (b2), and monomer units from other monovinyl compounds (b3) as needed.

[0129] The aromatic vinyl compound (b1), cyanide vinyl compound (b2), and other vinyl compounds (b3) used as needed in the copolymer (B) can be the same compounds as those previously illustrated in the description of the graft copolymer (A), namely the aromatic vinyl compound (a1), cyanide vinyl compound (a2), and other vinyl compound (a3), and preferably in the same manner.

[0130] The content of monomer units from aromatic vinyl compounds (b1) in copolymer (B) is not particularly limited, but is preferably 50 to 80% by mass relative to the total mass of copolymer (B).

[0131] The content of monomer units from the cyanide vinyl compound (b2) in the copolymer (B) is not particularly limited, but is preferably 20 to 50% by mass relative to the total mass of the copolymer (B).

[0132] The content of monomer units from other vinyl compounds (b3) in copolymer (B) is not particularly limited, but is preferably 0 to 20% by mass relative to the total mass of copolymer (B).

[0133] The mass-average molecular weight of copolymer (B) is preferably, for example, 50,000 to 150,000.

[0134] The mass-average molecular weight of copolymer (B) is a value converted from standard polystyrene, determined using gel permeation chromatography (GPC).

[0135] The copolymer (B) can be manufactured by copolymerizing an aromatic vinyl compound (b1), a cyanide vinyl compound (b2), and other vinyl compounds (b3) as needed.

[0136] As polymerization methods, well-known polymerization methods such as emulsion polymerization, suspension polymerization, bulk polymerization, or methods combining them can be applied.

[0137] <Other Ingredients>

[0138] Other components include various additives, other resins, etc.

[0139] Examples of additives include well-known antioxidants, light stabilizers, ultraviolet absorbers, lubricants, plasticizers, stabilizers, transesterification inhibitors, hydrolysis inhibitors, release agents, antistatic agents, colorants (pigments, dyes, etc.), fillers (carbon fiber, glass fiber, wollastonite, calcium carbonate, silica, talc, etc.), flame retardants (bromine-based flame retardants, phosphorus-based flame retardants, etc.), flame-retardant additives (antimony trioxide, etc.), anti-drip agents (fluoropolymers, etc.), antibacterial agents, mildew inhibitors, silicone oils, coupling agents, etc.

[0140] These additives can be used alone or in combination of two or more.

[0141] Other examples of resins include HIPS resin, ABS resin (excluding graft copolymer (A)), ASA resin, AES resin, SAS resin, and other rubber-reinforced styrene resins, polystyrene resins, nylon resins, methacrylic resins, polyvinyl chloride resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyphenylene ether resins, and substances modified from these resins by means of compatibilizers or functional groups.

[0142] These other resins can be used alone or in combination of two or more.

[0143] It should be noted that, for the necessary or arbitrary components used in this invention, as long as there are no quality issues, recycled products from the polymerization process, processing process, molding process, etc., or recycled products from the market can be used.

[0144] <Content of each component>

[0145] The content of the graft copolymer (A) relative to the total mass of the coating resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 17% by mass or more, particularly preferably 20% by mass or more, and most preferably 21% by mass or more. Furthermore, the content of the graft copolymer (A) relative to the total mass of the coating resin composition is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 35% by mass or more, and most preferably 33% by mass or more. The upper and lower limits of the above-mentioned graft copolymer (A) content can be arbitrarily combined. For example, the content of the above-mentioned graft copolymer (A) relative to the total mass of the coating resin composition is preferably 10 to 50% by mass, more preferably 15 to 50% by mass, further preferably 17 to 50% by mass, even more preferably 20 to 50% by mass, even more preferably 21 to 50% by mass, even more preferably 21 to 45% by mass, even more preferably 21 to 40% by mass, particularly preferably 21 to 35% by mass, and most preferably 21 to 33% by mass.

[0146] If the content of graft copolymer (A) is above the lower limit mentioned above, the fluidity of the resin composition for plating is improved. Additionally, the impact resistance of the molded article is improved. If the content of graft copolymer (A) is below the upper limit mentioned above, the plating precipitation is improved.

[0147] The content of polycarbonate resin (P) is 40-70% by mass relative to the total mass of the coating resin composition. If the content of polycarbonate resin (P) is above the lower limit mentioned above, the impact resistance of the molded article is improved. Furthermore, the thermal cycling characteristics of the coated article are improved. If the content of polycarbonate resin (P) is below the upper limit mentioned above, the fluidity of the coating resin composition is improved. Furthermore, the coating adhesion strength and thermal cycling characteristics are improved.

[0148] The content of copolymer (B) relative to the total mass of the coating resin composition is preferably 0 to 50% by mass, more preferably 1 to 45% by mass. If the content of copolymer (B) is above the lower limit mentioned above, the fluidity of the coating resin composition is improved. If the content of copolymer (B) is below the upper limit mentioned above, the impact resistance of the molded article is improved.

[0149] The content of other components is preferably 0 to 60 parts by mass relative to the total of 100 parts by mass of the graft copolymer (A), polycarbonate resin (P) and copolymer (B).

[0150] <Rubber content (Z)>

[0151] The rubber content (Z) in the coating resin composition is 10-18% by mass relative to the total mass of the coating resin composition, preferably 10-15% by mass. If the rubber content (Z) is above the lower limit mentioned above, the impact resistance of the molded article is improved. In addition, the coating adhesion strength of the coated article is improved. If the rubber content (Z) is below the upper limit mentioned above, the thermal cycling characteristics of the coated article are improved.

[0152] The rubber content (Z) in the resin composition for plating can be determined by measurement using an infrared spectrophotometer, the amount of rubber polymer used, and the amount of graft copolymer (A).

[0153] <Method for manufacturing thermoplastic resin composition for plating>

[0154] The thermoplastic resin composition for plating is manufactured by mixing and kneading one or more of a graft copolymer (A), polycarbonate resin (P), and a desired copolymer (B) and other components. There are no particular limitations on the method of mixing and kneading the components; any general mixing and kneading method can be used. Examples include methods such as mixing with an extruder, a Banbury mixer, or a kneading roller, followed by granulation using a granulator or similar means.

[0155] The thermoplastic resin composition for plating of the present invention is molded into a molded article.

[0156] <Effects>

[0157] The plating resin composition of the present invention described above contains a graft copolymer (A) with a rubber content (X) exceeding 40% by mass and a grafting rate (Y) satisfying the above formula (1), and 40-70% by mass of polycarbonate resin (P). The rubber content (Z) in the plating resin composition is 10-18% by mass, thus plating processed articles with excellent plating characteristics can be obtained. In addition, the plating resin composition of the present invention can yield molded articles with excellent impact resistance and excellent flowability.

[0158] [Molded product]

[0159] The molded article is made from the above-described coating resin composition of the present invention.

[0160] The molded article is obtained by molding the coating resin composition of the present invention. Examples of molding methods include injection molding, extrusion molding, compression molding, insert molding, vacuum molding, blow molding, etc.

[0161] The molded articles exhibit excellent impact resistance due to the use of the coating resin composition of the present invention. Furthermore, during the coating process, they demonstrate excellent coating adhesion strength, the coating appearance is not easily altered during thermal cycling, and they also exhibit excellent impact resistance.

[0162] [Plated products]

[0163] The plated article has the above-described molded article and a plated film formed on at least a portion of the surface of the molded article.

[0164] Plated products are obtained by applying a plating process to molded parts. There are no particular limitations on the plating process, and examples include non-electrolytic plating, direct plating, and non-chromium plating.

[0165] In addition, it is preferable to perform etching treatment using etching solutions such as permanganate solution or chromic acid solution before plating.

[0166] The plated product is obtained by plating a molded article formed by the plating resin composition of the present invention. Therefore, the molded article and the plating film have excellent adhesion strength, the plating appearance is not easily changed during hot and cold cycles, and the impact resistance is also excellent.

[0167] Plated products are suitable for a wide variety of applications, including OA (office automation) equipment, information and communication equipment, electronic and electrical equipment, home appliances, automobiles, and construction.

[0168] Example

[0169] The present invention will be specifically described below through embodiments, but the present invention is not limited to these embodiments.

[0170] The various measurement and evaluation methods in the following examples and comparative examples are as follows.

[0171] It should be noted that, unless otherwise specified, "parts" refers to parts by mass and "%" refers to percentage by mass in the following description.

[0172] [Measurement and Evaluation Methods]

[0173] <Particle size distribution of rubber-based polymers>

[0174] For an aqueous dilution solution of rubber polymer latex, a nanoparticle size distribution measuring machine (manufactured by Nikkiso Co., Ltd., "Nanotrac UPA-EX150") based on the dynamic scattering theory was used to measure the particle size distribution of a mass reference. Based on the obtained particle size distribution, the mass-average particle size (μm) was calculated.

[0175] <Determination of grafting rate of graft copolymer (A)>

[0176] Weigh approximately 2.5 g of the dried, powdered graft copolymer (A), add 60 mL of acetone, and heat at 55°C for 3 hours to extract the acetone-soluble components. Then, centrifuge the acetone solution at 8000 rpm (10,000 G) for 30 minutes, and filter the acetone-insoluble components. Dry the acetone-insoluble components under reduced pressure at 70°C for 5 hours, determine the dried mass, and calculate according to the following formula (3). It should be noted that in the following formula (3), "m" is the mass (g) of the graft copolymer (A) before extraction (i.e., weighed), "n" is the dried mass (g) of the acetone-insoluble components, and "L" is the rubber content (mass %) of the graft copolymer.

[0177] Grafting rate (%) = {(nm×L) / (m×L)}×100···(3)

[0178] <Determination of mass-average molecular weight (Mw) of copolymer (B)>

[0179] The solution obtained by dissolving copolymer (B) in tetrahydrofuran was used as the test sample, and the test was performed using a GPC apparatus (manufactured by Tosoh Corporation). The calculation was performed using the standard polystyrene conversion method.

[0180] <Determination of Charpy Impact Strength>

[0181] The granules of the coating resin composition were injection molded using an 80-ton injection molding machine (J80ADS-110U, manufactured by Nippon Steel Corporation) to obtain test pieces (80 mm in length × 10 mm in width × 4 mm in thickness). The injection molding was performed at a molding temperature of 250°C, a mold temperature of 60°C, and an injection speed of 42 mm / sec.

[0182] For the obtained test pieces, the Charpy impact strength (with notch) was determined at a test temperature of 23°C according to ISO 179, and the impact resistance was determined according to the following criteria.

[0183] 3: Charpy impact strength is 45 kJ / m 2 The above is excellent.

[0184] 2: Charpy impact strength is 40 kJ / m 2 Above but less than 45 kJ / m 2 It works perfectly in practical terms.

[0185] 1: Charpy impact strength is less than 40 kJ / m 2 It has not reached a practical level.

[0186] <Determination of deflection temperature under load>

[0187] The granules of the coating resin composition were injection molded using an 80-ton injection molding machine (J80ADS-110U, manufactured by Nippon Steel Corporation) to obtain test pieces (80 mm in length × 10 mm in width × 4 mm in thickness). The injection molding was performed at a molding temperature of 250°C, a mold temperature of 60°C, and an injection speed of 42 mm / sec.

[0188] For the obtained test pieces, the load flexural temperature was measured according to ISO 75 under a load of 1.80 MPa and a FLAT Width (4 mm thickness), and the heat resistance was determined according to the following criteria.

[0189] 3: The load flexural temperature is above 100℃, which is excellent.

[0190] 2: The load flexural temperature is above 90℃ but below 100℃, which is not a problem in practical applications.

[0191] 1. The load flexural temperature is less than 90℃, which does not meet the practical requirements.

[0192] <Evaluation of Liquidity (Spiral Flow)>

[0193] Using a spiral flow mold (15mm width × 2mm thickness), granules of the coating resin composition were injection molded using an 85-ton injection molding machine (J85AD-110H, manufactured by Nippon Steel Corporation) under conditions of cylinder temperature 280°C, mold temperature 60°C, and injection pressure 100MPa. The spiral flow length (mm) of the resulting molded product was measured, and the flowability (spiral flow) was determined according to the following criteria.

[0194] 3: The spiral flow length is over 300mm, and the material properties are excellent.

[0195] 2: A spiral flow length of 250mm or more but less than 300mm is not a problem in practical applications.

[0196] 1. The spiral flow length is less than 250mm, which does not meet the practical requirements.

[0197] <Evaluation of Plating Adhesion Strength>

[0198] The granules of the coating resin composition were injection molded using an 80-ton injection molding machine (J80ADS-110U, manufactured by Nippon Steel Corporation) to obtain test pieces (90 mm in length × 50 mm in width × 3 mm in thickness). The injection molding was performed at a molding temperature of 250°C, a mold temperature of 60°C, and an injection speed of 5 mm / sec.

[0199] The obtained test pieces were coated in the following manner: the coating film was peeled off vertically on a load tester, its strength was measured, and the coating adhesion strength was determined according to the following criteria.

[0200] 3: The coating adhesion strength is above 15 N / cm, which is excellent.

[0201] 2: The coating adhesion strength is above 10N / cm but less than 15N / cm, which is not a problem in practical use.

[0202] 1: If the coating adhesion strength is less than 10 N / cm or the coating film is not fully deposited on the test piece (cannot be evaluated), it does not meet the practical level.

[0203] (Platinum coating)

[0204] In evaluating the adhesion strength of the plating, the plating process is carried out according to the following steps (1) to (15).

[0205] (1) Degreasing → (2) Water washing → (3) Etching → (4) Water washing → (5) Acid treatment → (6) Water washing → (7) Catalytic treatment → (8) Water washing → (9) Activation treatment → (10) Water washing → (11) Chemical Ni plating → (12) Water washing → (13) Electrolytic copper plating → (14) Water washing → (15) Drying

[0206] Conditions in each process

[0207] (1) Degreasing: The product was treated with a 50 mL / L solution of CRP Cleaner (manufactured by Okuno Pharmaceutical Co., Ltd.) at 50°C for 5 minutes.

[0208] (2) Washing: Wash at 20°C. It should be noted that the washing after (4) is also carried out under the same conditions as (2).

[0209] (3) Etching: A mixture of 400 g / L anhydrous chromic acid and 200 mL / L sulfuric acid was used as the etching solution for etching treatment. The immersion conditions were set at 68℃ for 15 minutes.

[0210] (5) Acid treatment: Immerse in 100 mL of 35% hydrochloric acid at 23°C for 1 minute.

[0211] (7) Catalytic treatment: Immerse in a mixture of 40 mL / L CRP catalyst and 250 mL / L 35% hydrochloric acid (Pd-Sn colloidal catalyst) at 30 °C for 3 minutes.

[0212] (9) Activation treatment: Immerse in 100 mL of sulfuric acid at 40 °C for 3 minutes.

[0213] (11) Chemical Ni plating: Immerse the sample in a mixture of 160 mL / L of chemical nickel A (manufactured by Okuno Pharmaceutical Co., Ltd.) and 160 mL / L of chemical nickel B (manufactured by Okuno Pharmaceutical Co., Ltd.) at 35°C for 5 minutes to form a chemical plating film with a thickness of 0.5 μm.

[0214] (13) Electrolytic copper plating: at 20℃ and a current density of 3A / dm 2 Under the specified conditions, the copper plating film with a thickness of 35 μm was formed by immersing the sample in a mixture of 200 g / L copper sulfate, 30 mL / L sulfuric acid and a brightener for 60 minutes.

[0215] (15) Drying: Dry at 80℃ for 2 hours.

[0216] <Evaluation of thermal cycling characteristics>

[0217] Particles of the coating resin composition were injection molded using an 80-ton injection molding machine (J80ADS-110U, manufactured by Nippon Steel Corporation) to obtain test pieces (100mm in length × 100mm in width × 3mm in thickness). Injection molding was performed at a cylinder temperature of 250°C, a mold temperature of 60°C, and an injection speed of 50mm / sec.

[0218] The obtained test pieces were subjected to plating processing as follows: 10 cycles were performed, with one cycle consisting of cooling at -35°C for 1 hour and heating at 90°C for 1 hour. Afterward, the state of the plating film on the plated products was visually observed, and the thermal cycling characteristics were determined according to the following criteria.

[0219] ◎(3): There are no morphological changes such as plating expansion or peeling on the effective side and back of the plated product, which is excellent.

[0220] 〇(2): Several expansion and peeling morphological changes appear on the back side of the plated product, but there are no expansion and peeling morphological changes on the effective side of the plated product, which is not a problem in practical use.

[0221] △(1): If the effective surface of the plated product shows morphological changes such as plating expansion or peeling, or if the plating film does not precipitate out completely onto the test piece (cannot be evaluated), it does not reach the practical level.

[0222] (Platinum coating)

[0223] In the evaluation of thermal cycling characteristics, the plating process is carried out according to the following steps (1) to (17).

[0224] (1) Degreasing → (2) Water washing → (3) Etching → (4) Water washing → (5) Acid treatment → (6) Water washing → (7) Catalytic treatment → (8) Water washing → (9) Activation treatment → (10) Water washing → (11) Chemical Ni plating → (12) Water washing → (13) Electrolytic copper plating → (14) Water washing → (15) Electroplating Ni → (16) Water washing → (17) Electroplating Cr

[0225] Conditions in each process

[0226] (1) Degreasing: The product is processed at 50°C for 5 minutes using a CRP Cleaner (manufactured by Okuno Pharmaceutical Co., Ltd.).

[0227] (2) Washing: Wash at 20°C. It should be noted that the washing after (4) is also carried out under the same conditions as (2).

[0228] (3) Etching: A mixture of 400 g / L anhydrous chromic acid and 200 mL / L sulfuric acid was used as the etching solution for etching treatment. The immersion conditions were set at 68℃ for 20 minutes.

[0229] (5) Acid treatment: Immerse in 100 mL of 35% hydrochloric acid at 23°C for 1 minute.

[0230] (7) Catalytic treatment: Immerse in a mixture of 40 mL / L CRP catalyst and 250 mL / L 35% hydrochloric acid (Pd-Sn colloidal catalyst) at 30 °C for 3 minutes.

[0231] (9) Activation treatment: Immerse in 100 mL of sulfuric acid at 40 °C for 3 minutes.

[0232] (11) Electroless Ni plating: Immerse the sample in a mixture of 160 mL / L of electroless nickel A (manufactured by Okuno Pharmaceutical Co., Ltd.) and 160 mL / L of electroless nickel B (manufactured by Okuno Pharmaceutical Co., Ltd.) at 35°C for 5 minutes to form an electroless plating film with a thickness of 0.5 μm.

[0233] (13) Electrolytic copper plating: at 20℃ and a current density of 3A / dm 2 Under the conditions of immersion in a mixture of 200 g / L copper sulfate, 30 mL / L sulfuric acid and a brightener for 20 minutes, a copper plating film with a thickness of 20 μm is formed.

[0234] (15) Ni electroplating: at 55℃ and a current density of 3A / dm 2 Under the specified conditions, the nickel plating film was immersed in a mixture of 200 g / L nickel sulfate, 45 g / L nickel chloride, 45 g / L boric acid and a brightener for 15 minutes to form a nickel plating film with a thickness of 10 μm.

[0235] (17) Electroplating of Cr: at 45℃ and a current density of 15A / dm2 Under certain conditions, the sample was immersed in a mixture of 200 g / L anhydrous chromic acid and 1.5 g / L sulfuric acid for 2 minutes to form a chromium plating film with a thickness of 0.3 μm.

[0236] <Comprehensive Judgment>

[0237] In the above evaluation results, cases with a total score of 13 to 15 points are judged as "◎" in the comprehensive judgment, cases with a total score of 11 to 12 points are judged as "〇" in the comprehensive judgment, and cases with a total score of less than 10 points or any evaluation result containing 1 point are judged as "△" in the comprehensive judgment.

[0238] [Preparation of graft copolymer (A)]

[0239] <Synthetic Example 1: Preparation of Rubber Polymer (g)>

[0240] 150 parts water, 3.3 parts potassium salt of tallow fatty acid, 0.14 parts potassium hydroxide, 0.3 parts sodium pyrophosphate, and 0.20 parts tert-dodecyl mercaptan were added to the reactor. Then, 100 parts 1,3-butadiene were added, and the temperature was raised to 62°C. Next, 0.12 parts potassium persulfate were injected to initiate polymerization. The reaction proceeded for 10 hours, reaching 75°C. After further reacting at 75°C for 1 hour, 0.08 parts sodium formaldehyde sulfoxylate were injected. After removing the residual 1,3-butadiene, the polymer was extracted, resulting in a rubbery polymer latex (solid content 35%). The mass-average particle size of the obtained rubbery polymer was 0.08 μm.

[0241] Two parts (converted to solids content) of copolymer latex with an average particle size of 0.11 μm, consisting of 85% n-butyl acrylate units and 15% methacrylic acid units, were added to 100 parts (converted to solids content) of the latex of the resulting rubber polymer while stirring. The stirring was continued for 30 minutes to obtain a latex of fattened butadiene-based rubber polymer (g) with an average particle size of 0.28 μm.

[0242] <Synthetic Example 2: Graft Copolymer (A-1-1)>

[0243] In a closed reactor equipped with a reagent injection container, cooling pipe, nitrogen purging device, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 70 parts of latex of the rubber polymer (g) based on solid content, and 0.13 parts of heterogeneous potassium rosinate were added. While purging with nitrogen, the liquid temperature inside the reactor was raised to 55°C and maintained for 30 minutes. Then, a solution obtained by dissolving 0.15 parts of sodium pyrophosphate, 0.008 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 7.5 parts of acrylonitrile, 22.5 parts of styrene, 0.07 parts of cumene hydroperoxide, and 0.09 parts of tert-dodecyl mercaptan was added dropwise over 5 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 55°C, and then cooled to obtain the latex of the graft copolymer.

[0244] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-1-1).

[0245] The resulting graft copolymer (A-1-1) has a rubber content (X) of 70% by mass and a grafting rate (Y) of 38.6%.

[0246] It should be noted that, in this embodiment, the amount of rubber polymer (g) added is set as the rubber content (X).

[0247] <Synthetic Example 3: Graft Copolymer (A-1-2)>

[0248] In a closed reactor equipped with a reagent injection container, cooling pipe, nitrogen purging device, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 55 parts of latex of the rubber polymer (g) based on solid content, and 0.15 parts of heterogeneous potassium rosinate were added. While purging with nitrogen, the liquid temperature inside the reactor was raised to 55°C and maintained for 30 minutes. Then, a solution obtained by dissolving 0.15 parts of sodium pyrophosphate, 0.008 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 11.25 parts of acrylonitrile, 33.75 parts of styrene, 0.07 parts of cumene hydroperoxide, and 0.09 parts of tert-dodecyl mercaptan was added dropwise over 5 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 55°C, and then cooled to obtain the latex of the graft copolymer.

[0249] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-1-2).

[0250] The resulting graft copolymer (A-1-2) has a rubber content (X) of 55% by mass and a grafting rate (Y) of 73.6%.

[0251] <Synthetic Example 4: Graft Copolymer (A-1-3)>

[0252] In a reactor equipped with a reagent injection container, cooling pipes, a jacketed heater, and a stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 70 parts of latex of the rubber polymer (g) based on solid content, and 0.2 parts of heterogeneous potassium rosinate were added to raise the internal liquid temperature of the reactor to 60°C. Then, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 7.5 parts of acrylonitrile, 22.5 parts of styrene, 0.08 parts of cumene hydroperoxide, and 0.09 parts of tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the dropwise addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 60°C, and then cooled to obtain the latex of the graft copolymer.

[0253] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-1-3).

[0254] The resulting graft copolymer (A-1-3) has a rubber content (X) of 70% by mass and a grafting rate (Y) of 34.3%.

[0255] <Synthetic Example 5: Graft Copolymer (A-1-4)>

[0256] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 55 parts of latex of the rubber polymer (g) converted to solids, and 0.2 parts of heterogeneous potassium rosinate were added to raise the internal liquid temperature of the reactor to 60°C. After maintaining this temperature for 30 minutes, a solution obtained by dissolving 0.15 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 11.25 parts of acrylonitrile, 33.75 parts of styrene, 0.1 parts of cumene hydroperoxide, and 0.12 parts of tert-dodecyl mercaptan was added dropwise over 3.5 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 60°C, and then cooled to obtain the latex of the graft copolymer.

[0257] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-1-4).

[0258] The resulting graft copolymer (A-1-4) has a rubber content (X) of 55% by mass and a grafting rate (Y) of 65.5%.

[0259] <Synthetic Example 6: Graft Copolymer (A-1-5)>

[0260] In a closed reactor equipped with a reagent injection container, cooling pipe, nitrogen purging device, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 60 parts of the latex of the rubber polymer (g) based on solid content, and 0.18 parts of heterogeneous potassium rosinate were added. While purging with nitrogen, the liquid temperature inside the reactor was raised to 55°C and maintained for 30 minutes. Then, a solution obtained by dissolving 0.15 parts of sodium pyrophosphate, 0.008 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 10 parts of acrylonitrile, 30 parts of styrene, 0.1 parts of cumene hydroperoxide, and 0.12 parts of tert-dodecyl mercaptan was added dropwise over 4.5 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 55°C, and then cooled to obtain the latex of the graft copolymer.

[0261] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-1-5).

[0262] The resulting graft copolymer (A-1-5) has a rubber content (X) of 60% by mass and a grafting rate (Y) of 56.7%.

[0263] <Synthetic Example 7: Graft Copolymer (A-2-1)>

[0264] In a closed reactor equipped with a reagent injection container, cooling pipe, nitrogen purging device, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 50 parts of latex of the rubber polymer (g) based on solid content, and 0.18 parts of heterogeneous potassium rosinate were added. While purging with nitrogen, the liquid temperature inside the reactor was raised to 55°C and maintained for 30 minutes. Then, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 12.5 parts of acrylonitrile, 37.5 parts of styrene, 0.1 parts of cumene hydroperoxide, and 0.13 parts of tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 55°C, and then cooled to obtain the latex of the graft copolymer.

[0265] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-2-1).

[0266] The resulting graft copolymer (A-2-1) has a rubber content (X) of 50% by mass and a grafting rate (Y) of 90.0%.

[0267] <Synthetic Example 8: Graft Copolymer (A-2-2)>

[0268] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 70 parts of latex of the rubber polymer (g) on ​​a solids basis and 0.25 parts of heterogeneous potassium rosinate were added. After the liquid temperature inside the reactor was raised to 65°C, a solution was added which was obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water.

[0269] Next, a mixture of 7.5 parts acrylonitrile, 22.5 parts styrene, 0.13 parts cumene hydroperoxide, and 0.09 parts tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0270] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-2-2).

[0271] The resulting graft copolymer (A-2-2) has a rubber content (X) of 70% by mass and a grafting rate (Y) of 30.0%.

[0272] <Synthetic Example 9: Graft Copolymer (A-2-3)>

[0273] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 50 parts of latex of the rubber polymer (g) converted to solid components and 0.25 parts of heterogeneous potassium rosinate were added. After the liquid temperature inside the reactor was raised to 65°C, a solution was added which was obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate 7-hydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water.

[0274] Next, a mixture of 12.5 parts acrylonitrile, 37.5 parts styrene, 0.23 parts cumene hydroperoxide, and 0.15 parts tert-dodecyl mercaptan was added dropwise over 2.5 hours to carry out polymerization. After the addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0275] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-2-3).

[0276] The resulting graft copolymer (A-2-3) has a rubber content (X) of 50% by mass and a grafting rate (Y) of 70.0%.

[0277] <Synthetic Example 10: Graft Copolymer (A-2-4)>

[0278] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 45 parts of latex of the rubber polymer (g) converted to solid components and 0.25 parts of heterogeneous potassium rosinate were added. After the liquid temperature inside the reactor was raised to 65°C, a solution was added which was obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate and 0.3 parts of glucose in 8 parts of ion-exchanged water.

[0279] Next, a mixture of 13.75 parts acrylonitrile, 41.25 parts styrene, 0.23 parts cumene hydroperoxide, and 0.16 parts tert-dodecyl mercaptan was added dropwise over 2.5 hours to carry out polymerization. After the addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0280] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-2-4).

[0281] The resulting graft copolymer (A-2-4) has a rubber content (X) of 45% by mass and a grafting rate (Y) of 85.6%.

[0282] <Synthetic Example 11: Graft copolymer (A-3-1)>

[0283] In a closed reactor equipped with a reagent injection container, cooling pipe, nitrogen purging device, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 40 parts of latex of the rubber polymer (g) based on solid content, and 0.18 parts of heterogeneous potassium rosinate were added. While purging with nitrogen, the liquid temperature inside the reactor was raised to 55°C and maintained for 30 minutes. Then, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.008 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Next, a mixture of 15 parts of acrylonitrile, 45 parts of styrene, 0.07 parts of cumene hydroperoxide, and 0.09 parts of tert-dodecyl mercaptan was added dropwise over 5 hours to carry out polymerization. After the dropwise addition was completed, the reactor was stirred for 30 minutes while maintaining the internal temperature at 55°C, and then cooled to obtain the latex of the graft copolymer.

[0284] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-3-1).

[0285] The resulting graft copolymer (A-3-1) has a rubber content (X) of 40% by mass and a grafting rate (Y) of 135.0%.

[0286] <Synthetic Example 12: Graft copolymer (A-3-2)>

[0287] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 70 parts of latex of the rubber polymer (g) based on solid content, and 0.3 parts of heterogeneous potassium rosinate were added. After the liquid temperature inside the reactor was raised to 65°C, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Then, a mixture of 7.5 parts of acrylonitrile, 22.5 parts of styrene, 0.13 parts of cumene hydroperoxide, and 0.09 parts of tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0288] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-3-2).

[0289] The resulting graft copolymer (A-3-2) has a rubber content (X) of 70% by mass and a grafting rate (Y) of 25.7%.

[0290] <Synthetic Example 13: Graft copolymer (A-3-3)>

[0291] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 55 parts of latex of the rubber polymer (g) based on solid content, and 0.3 parts of heterogeneous potassium rosinate were added. After the internal liquid temperature of the reactor was raised to 65°C, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Then, a mixture of 11.25 parts of acrylonitrile, 33.75 parts of styrene, 0.2 parts of cumene hydroperoxide, and 0.13 parts of tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the dropwise addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0292] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-3-3).

[0293] The resulting graft copolymer (A-3-3) has a rubber content (X) of 55% by mass and a grafting rate (Y) of 49.1%.

[0294] <Synthetic Example 14: Graft Copolymer (A-3-4)>

[0295] In a reactor equipped with a reagent injection container, cooling pipe, jacketed heater, and stirring device, 180 parts of water (including water in the latex of the rubber polymer (g)), 40 parts of latex of the rubber polymer (g) based on solid content, and 0.3 parts of heterogeneous potassium rosinate were added. After the liquid temperature inside the reactor was raised to 65°C, a solution obtained by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate hexahydrate, and 0.3 parts of glucose in 8 parts of deionized water was added. Then, a mixture of 15 parts of acrylonitrile, 45 parts of styrene, 0.27 parts of cumene hydroperoxide, and 0.17 parts of tert-dodecyl mercaptan was added dropwise over 2 hours to carry out polymerization. After the addition was completed, the mixture was stirred for 30 minutes while maintaining the internal temperature at 65°C, and then cooled to obtain the latex of the graft copolymer.

[0296] The latex of the obtained graft copolymer was diluted with distilled water to a ratio of 1.25 and slowly added dropwise to a 3% sulfuric acid aqueous solution at 50°C. After the entire amount was added, the temperature was raised to 90°C and maintained for 5 minutes to allow it to solidify. Then, the solidified material was centrifuged using a filter cloth, and the wet powder graft copolymer was dried to obtain graft copolymer (A-3-4).

[0297] The resulting graft copolymer (A-3-4) has a rubber content (X) of 40% by mass and a grafting rate (Y) of 90.0%.

[0298] [Preparation of copolymer (B)]

[0299] <Synthetic Example 15: Copolymer (B-1)>

[0300] A monomer mixture consisting of 125 parts water, 0.4 parts calcium phosphate, 0.003 parts potassium alkenyl succinate, 0.05 parts 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, 0.04 parts 1,1-di(tert-hexylperoxy)cyclohexane, 0.04 parts tert-butyl peroxide-2-ethylhexyl carbonate, 0.85 parts tert-dodecyl mercaptan, 23 parts acrylonitrile, and 77 parts styrene was added to a reactor and allowed to react. The reaction was carried out as follows: while adding water, a portion of acrylonitrile, and a portion of styrene sequentially, the temperature was increased from an initial temperature of 65°C to 125°C for 6.5 hours. The reaction was then carried out at 125°C for 1 hour to obtain a slurry of copolymer (B-1). After cooling, the slurry was centrifuged and dehydrated to obtain copolymer (B-1). The mass-average molecular weight of the obtained copolymer (B-1) was 60,000.

[0301] <Synthetic Example 16: Copolymer (B-2)>

[0302] Except for changing the amount of acrylonitrile to 26 parts, the amount of styrene to 74 parts, and the amount of tert-dodecyl mercaptan to 0.45 parts, copolymer (B-2) was obtained in the same manner as in Synthesis Example 15. The resulting copolymer (B-2) had a mass-average molecular weight of 115,000.

[0303] <Synthetic Example 17: Copolymer (B-3)>

[0304] Except for changing the amount of acrylonitrile to 32 parts, the amount of styrene to 68 parts, and the amount of tert-dodecyl mercaptan to 0.65 parts, copolymer (B-3) was obtained in the same manner as in Synthesis Example 15. The resulting copolymer (B-3) had a mass-average molecular weight of 89,000.

[0305] [Polycarbonate resin (P)]

[0306] The following substances are used as polycarbonate resin (P).

[0307] • P-1: Iupilon H3000F manufactured by Mitsubishi Process Plastics Co., Ltd. (viscosity-average molecular weight (Mv): 18,000).

[0308] • P-2: Iupilon S2000F manufactured by Mitsubishi Process Plastics Co., Ltd. (viscosity-average molecular weight (Mv): 22,000).

[0309] [Examples 1-21, Comparative Examples 1-11]

[0310] A resin composition for plating was prepared by mixing graft copolymer (A), copolymer (B) and polycarbonate resin (P) in the proportions (parts by mass) shown in Tables 1 to 6.

[0311] Using a 30mm twin-screw extruder ("TEX30α" manufactured by Nippon Steel Corporation), the obtained coating resin composition was melt-blended at a temperature of 200°C, and then granulated to obtain granules of the coating resin composition.

[0312] The rubber content (Z) in the coating resin compositions of each example was calculated from the rubber content (X) in the graft copolymer (A) and the amount of graft copolymer (A). The results are shown in Tables 1 to 6.

[0313] In addition, Charpy impact strength and load flexural temperature were measured using the various plating resin compositions, and the spiral flow, plating adhesion strength, and thermal cycling characteristics were evaluated. The results are shown in Tables 1 to 6.

[0314] It should be noted that the empty columns in Tables 1 to 6 indicate that the component was not incorporated (the amount incorporated is 0 parts by mass).

[0315] Table 1

[0316]

[0317] Table 2

[0318]

[0319] Table 3

[0320]

[0321] Table 4

[0322]

[0323] Table 5

[0324]

[0325] Table 6

[0326]

[0327] The coating resin compositions of each embodiment exhibit excellent flowability. These coating resin compositions can yield molded articles (test pieces) with excellent impact resistance and heat resistance. Furthermore, the coated finished products obtained by coating these molded articles (test pieces) exhibit high coating adhesion strength, excellent thermal cycling characteristics, and good coating properties.

[0328] In contrast, in Comparative Example 1, which used a graft copolymer (A-3-1) with a rubber content (X) of 40% by mass, the plated finished product exhibited low plating adhesion strength and poor thermal cycling characteristics.

[0329] In Comparative Examples 2 to 6, which use any of the graft copolymers (A-3-2) to (A-3-4) whose grafting ratio (Y) does not satisfy the above formula (1), the plating adhesion strength of the plated product is low and the thermal cycling characteristics are also poor.

[0330] In the case of the coating resin compositions of Comparative Examples 7 and 8, where the rubber content (Z) is 9.0% by mass, the molded articles (test pieces) exhibit poor impact resistance. Furthermore, the coating adhesion strength of the coated articles is low.

[0331] In the case of the coating resin composition of Comparative Example 9, where the rubber content (Z) is 20.4% by mass, the coated product exhibits poor thermal cycling characteristics.

[0332] The coating resin composition of Comparative Example 10, with a polycarbonate resin (P) content of 75% by mass, exhibited poor flowability. It should be noted that in the case of Comparative Example 10, no coating was deposited on the molded article (test piece), making it impossible to evaluate the coating adhesion strength and thermal cycling characteristics.

[0333] In the case of the plating resin composition of Comparative Example 11, where the polycarbonate resin (P) content is 35% by mass, the molded article (test piece) exhibits poor impact resistance. Furthermore, the plated product exhibits poor thermal cycling characteristics.

[0334] Industrial availability

[0335] According to the present invention, a coating resin composition is provided that yields coated finished products with excellent coating properties, and the present invention is of great industrial importance.

Claims

1. A plated product, characterized in that, The plated article has a molded article and a plating film formed on at least a portion of the surface of the molded article. The molded article comprises a resin composition containing a graft copolymer (A) in which monomer component (a) is grafted and polymerized in a rubbery polymer and a polycarbonate resin (P). The content of the polycarbonate resin (P) is 40-70% by mass relative to the total mass of the resin composition. The monomer component (a) comprises 60-80% by mass of an aromatic vinyl compound (a1), 20-40% by mass of a cyanide vinyl compound (a2), and 0-20% by mass of other vinyl compounds (a3) ​​capable of copolymerizing with the aromatic vinyl compound (a1) and the cyanide vinyl compound (a2). The rubber content (X) in the graft copolymer (A) is more than 40% by mass relative to the total mass of the graft copolymer (A). The grafting ratio (Y) of the graft copolymer (A) satisfies the following formula (2), and the grafting ratio (Y) is in the range of 30% to 73.6%. The rubber content (Z) in the resin composition is 10-18% by mass relative to the total mass of the resin composition. 793e -0.041X ≥Y≥594e -0.041X (2) 2. The plated article according to claim 1, wherein, The rubber content (X) is 50-70% by mass relative to the total mass of the graft copolymer (A).

3. The plated article according to claim 1, wherein, The plating adhesion strength of the plated product, as measured by the following method, is 15 N / cm or higher: Uses "J80ADS" manufactured by Nippon Steel Co., Ltd. An 80-ton 110U injection molding machine was used to injection mold the resin composition particles to obtain test pieces with a length of 90mm × width of 50mm × thickness of 3mm. The injection molding was carried out under the conditions of a molding temperature of 250℃, a mold temperature of 60℃, and an injection speed of 5mm / sec. The obtained test pieces were subjected to plating processing according to the following steps (1) to (15). The plating film was peeled off in the vertical direction on a load measuring device, and its strength was measured as the plating adhesion strength. (1) Degreasing, (2) Water washing, (3) Etching, (4) Water washing, (5) Acid treatment, (6) Water washing, (7) Catalytic treatment, (8) Water washing, (9) Activation treatment, (10) Water washing, (11) Chemical Ni plating, (12) Water washing, (13) Electrolytic copper plating, (14) Water washing, (15) Drying Conditions in each process (1) Degreasing: The product was treated with 50 mL / L CRP Cleaner solution manufactured by Okuno Pharmaceutical Co., Ltd. at 50°C for 5 minutes; (2) Washing: Wash at 20°C. It should be noted that the washing after (4) is also carried out under the same conditions as (2). (3) Etching: A mixture of 400 g / L anhydrous chromic acid and 200 mL / L sulfuric acid was used as the etching solution for etching treatment. The immersion conditions were set at 68°C for 15 minutes. (5) Acid treatment: Immerse in 100 mL of 35% hydrochloric acid at 23°C for 1 minute; (7) Catalytic treatment: At 30°C, a mixture of 40 mL / L CRP catalyst and 250 mL / L 35% hydrochloric acid, i.e., Pd Immerse in Sn colloidal catalyst for 3 minutes; (9) Activation treatment: Immerse in 100 mL of sulfuric acid at 40 °C for 3 minutes; (11) Chemical Ni plating: Immerse in a mixture of 160 mL / L chemical nickel A and 160 mL / L chemical nickel B manufactured by Okuno Pharmaceutical Co., Ltd. at 35°C for 5 minutes to form a chemical plating film with a thickness of 0.5 μm. (13) Electrolytic copper plating: at 20℃ and a current density of 3A / dm 2 Under the conditions of immersion in a mixture of 200 g / L copper sulfate, 30 mL / L sulfuric acid and brightener for 60 minutes, a copper plating film with a thickness of 35 μm is formed. (15) Drying: Dry at 80℃ for 2 hours.

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