JP2002363416A - Resin composition for plating substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition for a plating substrate, having good formability, dimensional stability, mechanical strength and properties for plating, obtained by considering the environmental, and suitable for the use for a galvanized part. SOLUTION: This resin composition for the plating substrate is obtained by compounding (C) 100 pts.wt. resin composition with (D) 2-40 pts.wt. red phosphorus-based flame retardant. The resin composition consists of (A) 10-60 wt.% graft copolymer obtained by graft-polymerizing (A2) monomer components comprising (a) a monomer unit of an aromatic alkenyl compound and (b) a monomer unit of a vinyl cyanide compound, on (A1) a gum polymer, and (B) 40-90 wt.% other polymers [with the proviso that the total of the components (A) and (B) is 100 wt.%].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition for a plating substrate, a resin molded product using the same, and an electroplated part.

[0002]

2. Description of the Related Art Heretofore, non-reinforced type, fiber-reinforced type flame-retardant ABS, flame-retardant PC-ABS, and the like have been mainly used for housings of notebook personal computers and portable devices.
However, in recent years, the demand for lighter and thinner devices has become more stringent, and it has also been required to be able to withstand the impact and load when placed in a bag or the like. It came out. Therefore, high rigidity and impact characteristics are required for the resin used for the housing. In addition, the housings of these devices are required to have an electromagnetic interference shielding property (hereinafter referred to as EMI shielding property). As a method of providing a shielding property, generally, a method using a resin containing about 30% by mass or more of carbon fiber, a method of inserting a metal foil or a metal plate at the time of in-molding or assembling the product, an electroless plating or a conductive method There is a method of painting.

[0003] Among the conventionally used materials, for example, unreinforced type flame-retardant ABS and flame-retardant PC-ABS have insufficient rigidity and cannot cope with recent thinning. Further, in the glass fiber reinforced system, the balance between rigidity and weight is insufficient. Further, in a carbon fiber reinforced system, when a resin containing about 30% by mass or more of carbon fiber is used, EMI shielding properties can be obtained, but the carbon fiber is expensive and the carbon fiber is less than 30% by mass. However, there is a problem in that the above material requires another treatment to have a sufficient EMI shielding property. Also, if the carbon fiber content is large,
There was also a problem that the appearance of a resin molded product made of the material was insufficient.

[0004] Notebook PCs and portable devices have C
Although there are heat sources such as PU, the heat generation amount tends to increase because of high density. In addition, since the thickness of the housing has been reduced, the problem of heat removal has become important. For heat removal, it is desirable that the material used for the housing has a high thermal conductivity, but in general, the thermal conductivity of the resin material is low. To use a resin housing, take another means for heat removal. There is a need. further,
In recent years, in view of the environment, it has been desired to use a flame-retardant material containing no halogen such as chlorine or bromine corresponding to the trend of ecolabels in Germany and Sweden.

[0005] In view of the above situation, housings such as notebook personal computers and portable devices are required to have various characteristics such as light weight, thin thickness, high rigidity, high impact, high thermal conductivity, EMI shielding, and mass productivity. It is also required that materials that are compatible with the environment are used. Japanese Patent Application Laid-Open No. 2000-349486 discloses a method for obtaining a light-weight, high-rigidity, high-thermal-conductivity, and low-cost equipment housing, which is applied to the surface of a resin molded product obtained by molding a thermoplastic resin. A housing plated with metal has been proposed.

[0006]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
With the technique disclosed in Japanese Patent Application Laid-Open No. 000-349486, it is considered difficult to obtain a housing that satisfies all the above-described performances from the following viewpoints. For example, in Examples 1 to 4, 6, and 7 of the publication,
Since a bisphenol A brominated epoxy flame retardant, which is a halogen flame retardant, is used, it is not possible to obtain a product that can obtain an eco-label such as Germany or Sweden. Further, in Example 5 of the publication, a phosphate ester-based flame retardant is used as a flame retardant. However, since the phosphate ester has a low melting point and is easily volatilized, a large amount of gas is generated during molding. Therefore, the generated gas may contaminate the surface of the mold, which may cause formation failure of the plating film or failure in appearance on the electroplating component. Further, in Example 8 of the publication, a polyamide resin blended with a red phosphorus-based flame retardant is used. However, since the polyamide resin is a crystalline polymer, the viscosity at the time of melting is low and burrs are formed during molding. There are problems such as easy occurrence and warpage due to high molding shrinkage. Therefore, when a polyamide resin is used, post-processing such as work for removing burrs and straightening of a molded product is required.

[0007] An object of the present invention is to provide a flame-retardant material for a plating base material which has good formability, dimensional accuracy, mechanical strength, and plating performance, is environmentally friendly, and is suitable for use in electroplating parts. It is to provide a conductive resin composition. Here, "good plating performance" means that there is no plating swelling of the plating layer, the plating adhesion strength is high, and these performances are maintained even when the surrounding environmental temperature changes.

[0008]

Means for Solving the Problems The present inventors have found that a composition in which a red phosphorus-based flame retardant is blended with a specific resin composition has good moldability, dimensional accuracy, mechanical strength and good plating performance. The present inventors have found that it is possible to manufacture an excellent electroplating component that has never been provided before, and have reached the present invention. That is, the resin composition for a plating substrate of the present invention comprises a rubbery polymer (A
1) a graft copolymer (A) obtained by graft-polymerizing a monomer component (A2) containing an aromatic alkenyl compound monomer unit (a) and a vinyl cyanide compound monomer unit (b).
10 to 60% by mass, and the other polymer (B) 40 to 90
2 to 40 parts by mass of a red phosphorus-based flame retardant (D) with respect to 100 parts by mass of the resin composition (C) consisting of 100% by mass (however, (A) + (B) = 100% by mass) It is characterized by.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin composition (C) used in the resin composition for a plating substrate of the present invention comprises a rubbery polymer (A1) and a monomer component (A).
2) graft copolymer (A) obtained by graft polymerization of 10
60% by mass and other polymer (B) 40 to 90% by mass
It consists of: Examples of the rubbery polymer (A1) include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene-non-conjugated diene rubber, acrylic rubber, epichlorohydrin rubber, Diene-acrylic composite rubber, silicone-acrylic composite rubber and the like can be mentioned. Among them, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, diene-acryl composite, because the plating performance of a molded article using the obtained resin composition for a plating substrate is good. Rubber and silicone-acrylic composite rubber are preferred.

Here, the diene component of the diene-acryl composite rubber contains butadiene in an amount of 50% by mass or more, and specific examples thereof include butadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber.
The acrylic rubber component is an alkyl (meth) acrylate rubber. As the composite structure of the diene-acrylic composite rubber, a core-shell form in which a diene rubber is used as a core layer and the periphery thereof is covered with an alkyl (meth) acrylate rubber, and an alkyl (meth) acrylate rubber is used as a core layer. A core-shell configuration in which the periphery is covered with a diene-based rubber, a configuration in which a diene-based rubber and an alkyl (meth) acrylate-based rubber are entangled with each other, and a diene-based monomer unit and an alkyl (meth) acrylate-based monomer unit are random And the like.

The silicone component of the silicone-acrylic composite rubber contains a polyorganosiloxane as a main component, and is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. The acrylic rubber component is an alkyl (meth) acrylate rubber. As the composite structure of the silicone-acryl composite rubber, the core layer is a core-shell type in which the core layer is a polyorganosiloxane rubber and the periphery thereof is an alkyl (meth) acrylate rubber, and the core layer is an alkyl (meth) acrylate rubber and the periphery is a poly. Examples include a core-shell form of an organosiloxane rubber and a form in which a polyorganosiloxane segment and a polyalkyl (meth) acrylate segment are linearly and sterically bonded to each other to form a network-like rubber structure.

Further, these diene-acryl composite rubbers,
The acrylic rubber component in the silicone-acryl composite rubber is composed of an alkyl (meth) acrylate (g) and a polyfunctional monomer (h). Here, the alkyl (meth) acrylate (g) includes, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate. Rate; hexyl methacrylate, 2-ethylhexyl methacrylate, n
-Alkyl methacrylates such as lauryl methacrylate. These can be used alone or in combination of two or more kinds. However, the use of n-butyl acrylate is particularly preferable because the finally obtained resin composition for a plating substrate has excellent impact resistance and molding gloss.

Examples of the polyfunctional monomer (h) include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and 1,3.
-Butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate and the like, and these can be used alone or in combination of two or more.

The rubbery polymer (A1) used in the present invention
There is no particular limitation on the method for producing the rubbery polymer (A).
Since it is easy to control the particle size of 1), it is usually prepared by emulsion polymerization with the action of a radical polymerization initiator. The average particle diameter of the rubbery polymer (A1) is not particularly limited. However, in order to obtain excellent plating performance and impact resistance of the obtained resin composition for a plating substrate, the average particle diameter is 0.1%.
It is preferably about 0.6 μm. When the thickness is less than 0.1 μm, the impact resistance of the resin composition for a plating substrate is reduced, and plating swelling is likely to occur at the same time. On the other hand, 0.6 μm
If it exceeds, the plating adhesion strength will decrease. Further, the content of the rubbery polymer (A1) in the resin composition (C),
When the content is in the range of 5 to 25% by mass, the resin molded product comprising the resin composition for a plating base material has excellent impact resistance and plating adhesion strength.

The monomer component (A2) graft-polymerized to the rubbery polymer (A1) comprises an aromatic alkenyl compound monomer unit (a) and a vinyl cyanide compound monomer unit (b)
And, if necessary, a monomer unit (c) copolymerizable therewith. The composition ratio is not particularly limited, but is preferably 50 to 90% by mass of the aromatic alkenyl compound monomer unit (a) and 10 to 50% by mass of the vinyl cyanide compound monomer unit (b). The monomer unit (c) is 0 to 20% by mass (a + b + c = 100
mass%). If the ratio is out of such a range, at least one of the molding processability and the plating performance of the resin composition for a plating substrate will be inferior.

The aromatic alkenyl compound monomer unit (a) includes, for example, styrene, α-methylstyrene, vinyltoluene and the like, and is preferably styrene. Examples of the vinyl cyanide compound monomer unit (b) include acrylonitrile, methacrylonitrile, and the like, and acrylonitrile is preferable. Examples of the monomer unit (c) copolymerizable therewith include methacrylates such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate and butyl acrylate. And acrylate esters such as N-phenylmaleimide.

The graft copolymer (A) can be obtained by graft-polymerizing the monomer component (A2) to be a graft component to the rubbery polymer (A1), and a known method is applied to the graft polymerization. Yes, there is no particular limitation on the method. At the time of graft polymerization, various chain transfer agents for adjusting the molecular weight and graft ratio of the graft polymer can be used. The graft copolymer (A) was measured at 25 ° C. as a 0.2 g / dl N, N-dimethylformamide solution containing 70 to 99% by mass of an insoluble component in an acetone solvent and containing an acetone-soluble component. Those having a reduced viscosity of 0.30 to 0.70 dl / g are preferred.

Here, the soluble component in the acetone solvent is the monomer component (A2) which often forms simultaneously with the graft polymerization of the rubber component (A1) with the monomer component (A2). It is a non-grafted polymer composed only of A2). Therefore, for example, as the graft copolymer (A), the insoluble content in the acetone solvent is 70%.
When using a material containing 30% by mass, the remaining 30% by mass is used.
Is counted as the other polymer (B).

The amount of the graft copolymer (A) in the resin composition (C) is 10 to 60% by mass ((A) +
(B) = 100% by mass). If the content is less than 10% by mass, the impact resistance and plating adhesion strength of the resin composition for a plating base material will be reduced. When the content exceeds 60% by mass, the flame retardancy of the resin composition for a plating base material is reduced. More preferably 10-4
0% by mass. When the blending amount of the graft copolymer (A) is less than 10% by mass or more than 60% by mass, the thermal cycling property of the electroplated component is reduced. Here, the thermal cycle property is a property that does not cause swelling of a plating film even when, for example, an electroplated component is used alternately in a low-temperature and high-temperature environment.

Other polymers (B) used in the present invention
Is not particularly limited, but an aromatic alkenyl compound monomer unit (a), a vinyl cyanide compound monomer unit (b), and, if necessary, a vinyl monomer copolymerizable therewith. The copolymer (B-
When a resin selected from the group consisting of 1), a polycarbonate resin (B-2), a polyamide resin (B-3), and a polyester resin (B-4) is used, in particular, the moldability and mechanical properties of the resin composition for a plating substrate are increased. It is preferable because of excellent mechanical strength and the like. These can be used alone or in combination of two or more.

Specific examples of the copolymer (B-1) include styrene-acrylonitrile copolymer (SAN resin), α-methylstyrene-acrylonitrile copolymer, and styrene-α-methylstyrene-acrylonitrile copolymer. Styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile-N-
And phenylmaleimide copolymers.

The content of the aromatic alkenyl compound monomer unit (a) in the copolymer (B-1) is preferably in the range of 60% by mass or more and 80% by mass or less.
-1) vinyl cyanide compound monomer unit (b)
Is preferably in the range of 20% by mass to 40% by mass. By setting the content in such a range, the moldability and plating performance of the obtained resin composition for a plating substrate are more excellent. Further, when the vinyl compound monomer unit (c) is used, the ratio is preferably 40% by mass or less. If it exceeds 40% by mass, the moldability and plating performance of the resin composition for a plating substrate may be insufficient. The molecular weight of the copolymer (B-1) is not particularly limited, but the reduced viscosity measured at 25 ° C. as a 0.2 g / dl N, N-dimethylformamide solution is 0.4 to 1.
It is preferably 4 dl / g.

The polycarbonate resin (B-2) is obtained from dihydroxydiarylalkane and may be arbitrarily branched. This polycarbonate resin (B-2) is produced by a known method, and is generally produced by reacting a dihydroxy or polyhydroxy compound with phosgene or a carbonic acid diester. Suitable dihydroxydiarylalkanes are those having an alkyl group ortho to the hydroxy group. Preferred specific examples of the dihydroxydiarylalkane include 4,4-dihydroxy2,2-diphenylpropane (= bisphenol A),
Examples include tetramethylbisphenol A and bis- (4-hydroxyphenyl) -p-diisopropylbenzene.

The branched polycarbonate is, for example, a part of a dihydroxy compound, for example, 0.2 to 2 mol%.
Is substituted by polyhydroxy. Specific examples of the polyhydroxy compound include phloroglicinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptene, 4,6-dimethyl-
2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl)
-Benzene and the like. Also, the molecular weight is not particularly limited, but is preferably a viscosity average molecular weight of M
v15000 to 35000.

As the polyamide resin (B-3), a lactam having three or more ring members, a polymerizable ω-amino acid, or a polyamide obtained by polycondensation of a dibasic acid and a diamine can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminonananoic acid, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, Polymers obtained by polycondensation of diamines such as methylene diamine and meta-xylene diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid and glutaric acid, or polymers thereof. Copolymers, for example, nylon 6, nylon 11, nylon 12, nylon 4.6, nylon 6.6, nylon 6.10, nylon 6.12 and the like.

The polyester resin (B-4) is mainly composed of an aromatic dicarboxylic acid having 8 to 22 carbon atoms and an aromatic dicarboxylic acid having 2 to 22 carbon atoms.
It contains 50% by mass or more of 22 alkylene glycols or cycloalkylene glycols, and may contain a subordinate amount of an aliphatic dicarboxylic acid such as adipic acid or sebacic acid as a constituent unit if desired. Further, a polyalkylene glycol such as polyethylene glycol and polytetramethylene glycol may be included as a constituent unit. Particularly preferred polyester resins include polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polybutylene naphthalate, and the like. These polyester resins are used alone or in combination of two or more.

Other polymers (B) include the above-mentioned copolymer (B-1), polycarbonate resin (B-2), polyamide resin (B-3) and polyester resin (B-4).
May be used alone or in combination of two or more. For example, styrene-acrylonitrile copolymer (SAN resin, B-1) and polycarbonate resin (B-2), SAN resin (B-1) and polyamide resin (B-3), SAN resin (B-1) and polyester Resin (B-4), a combination of two types of polymers such as a polycarbonate resin (B-2) and a polyester resin (B-4),
SAN resin (B-1) and polycarbonate resin (B-
And combinations of 2) and three kinds of polymers such as polyester resin (B-4). Among these, the combination of the SAN resin (B-1) and the polycarbonate resin (B-2), and the SAN resin ( A combination of B-1), a polycarbonate resin (B-2) and a polyester resin (B-4) is preferred.

The amount of the other polymer (B) in the resin composition (C) is from 40 to 90% by mass ((A) +
(B) = 100% by mass), preferably 60 to
90% by mass. When two or more polymers are used in combination as the other polymer (B), a copolymer (B-1), a polycarbonate resin (B-2),
Polyamide resin (B-3), polyester resin (B-
4) is preferably contained in the other polymer (B) at the following composition ratio.

When the styrene-acrylonitrile copolymer (SAN resin, B-1) and the polycarbonate resin (B-2) are used in combination as the other polymer (B), the other polymer (B) is Polymer (B-1)
~ 65 mass%, 35 parts of polycarbonate resin (B-2)
９９99% by mass (the total amount of B-1 and B-2 is 100% by mass). As another polymer (B), SAN resin (B-1) and polyamide resin (B-
When used in combination with 3), the other polymer (B) is 10 to 50% by mass of the copolymer (B-1) and 50 to 90% by mass of the polyamide resin (B-3) (B-1). And the total amount of B-3 is 100% by mass). As another polymer (B), SAN resin (B-
When 1) and the polyester resin (B-4) are used in combination, the other polymer (B) is a copolymer (B-
1) 15 to 55% by mass of a polyester resin (B-4)
From 45 to 85% by mass (the total amount of B-1 and B-4 is 100
% By mass). Further, the polymer (B)
In the case where the polycarbonate resin (B-2) and the polyester resin (B-4) are used in combination, the polymer (B) is obtained by mixing the polycarbonate resin (B-2) with 25 to 85.
It is preferable that the polyester resin (B-4) is contained in an amount of 15 to 75% by mass (the total amount of B-2 and B-4 is 100% by mass). When the SAN resin (B-1), the polycarbonate resin (B-2) and the polyester resin (B-4) are used in combination as the polymer (B), the polymer (B) is a copolymer (B- 1) is 1 to 69% by mass, the polycarbonate resin (B-2) is 30 to 98% by mass, and the polyester resin (B-4) is 1 to 69% by mass (total of B-1, B-2 and B-4). The amount is preferably 100% by mass. By setting each of the polymers (B-1) to (B-4) in the above range, the balance of moldability, mechanical strength, plating performance, and the like of the obtained resin composition for a plating base is more excellent. Things. Even when two or more polymers are used in combination as the other polymer (B), the amount of the other polymer (B) in the resin composition (C) is 4%.
0 to 90% by mass ((A) + (B) = 100% by mass).

The resin composition for a plating substrate of the present invention is obtained by mixing 2 to 40 parts by mass of a red phosphorus-based flame retardant (D) with 100 parts by mass of the above resin composition (C). . As the red phosphorus-based flame retardant (D), for example, known substances such as a red phosphorus-based flame retardant manufactured by Nippon Chemical Co., Ltd. and Rin Kagaku Kogyo Co., Ltd. can be used. Preferably a thermosetting resin, or
Stabilized by coating with a thermosetting resin and a metal hydroxide, for example, “LP Series” and “EP Series” manufactured by Nippon Chemical Co., Ltd., “Nova Red” manufactured by Rin Kagaku Kogyo Co., Ltd. Series "and" Nova Excel Series ".
Since the red phosphorus-based flame retardant (D) is hard to volatilize, it does not generate as a gas at the time of molding, and a resin molded article having an excellent appearance can be obtained. It is also an environmentally friendly flame retardant in that it is not a halogenated compound. When the amount of the red phosphorus-based flame retardant (D) is less than 2 parts by mass, the flame retardancy of the resin composition for a plating base material is reduced, and when it exceeds 40 parts by mass, impact resistance is impaired. Preferably it is in the range of 3 to 30 parts by mass. Further, since the red phosphorus-based flame retardant (D) is ignitable by itself, at least a part of the resin composition (C) is preliminarily prepared.
Preferably, it is preferably mixed in advance with the component (B) to form a master batch.

In addition to the red phosphorus flame retardant (D), a known non-halogen flame retardant may be added to the resin composition (C) and used in combination with the red phosphorus flame retardant (D). . Examples of the non-halogen flame retardant include phosphorus flame retardants, and examples thereof include phosphate esters such as resorcinol (diphenyl) phosphate, triallyl phosphate, and aromatic phosphate. In addition, inorganic flame retardants such as aluminum hydroxide can be used. Further, in order to prevent drip during combustion, polytetrafluoroethylene, a compound containing tetrafluoroethylene, or a silicone polymer can be contained as a flame retardant aid. When polytetrafluoroethylene or a compound containing tetrafluoroethylene is used, the amount of the resin composition (C)
It is preferable that the amount be 0.5 parts by mass or less based on 00 parts by mass.

In the resin composition for a plating substrate of the present invention, the inorganic filler (E) is further added in an amount of 0.1 to 50 parts by mass, preferably 10 parts by mass, per 100 parts by mass of the resin composition (C).
You may mix | blend about 30 mass parts. If the amount is less than 0.1 part by mass, the effect of improving the properties such as rigidity and thermal conductivity by blending the inorganic filler (E) cannot be sufficiently obtained.
If it exceeds 0 parts by mass, the moldability may be insufficient. Examples of the inorganic filler (E) to be blended here include inorganic fibers such as glass fibers and carbon fibers, metal fibers coated with inorganic fibers, wollastonite, talc, mica, glass flakes, glass beads, potassium titanate, and calcium carbonate. Inorganic substances such as magnesium carbonate, carbon black and Ketjen black; metals and alloys such as iron, copper, zinc and aluminum; and fibers and powders of oxides thereof. One or more of these may be used. Although they can be used in combination, it is particularly preferable to use carbon fibers because high rigidity can be obtained with a small amount of blending.

The resin composition for a plating substrate of the present invention may further contain, if necessary, other modifiers, mold release agents, light or heat stabilizers, flame retardant auxiliaries, antistatic agents, dyes and pigments. And various additives can be appropriately compounded.

The resin composition for a plating substrate of the present invention can be kneaded and extruded by a commonly known kneading apparatus, and can be molded into a resin molded article by a commonly known molding method. it can. As a molding method, for example,
Injection molding method, injection compression molding machine method, extrusion method, blow molding method, vacuum molding method, pressure molding method, calender molding method, inflation molding method, etc. are listed, but resin molded products with excellent mass productivity and high dimensional accuracy Thus, injection molding and injection compression molding are preferred.

The average thickness of a resin molded product obtained by molding the resin composition for a plating substrate of the present invention varies depending on the use and shape of the product, but is usually 0.5 to 5.0 mm. You. In the case of a portable device housing that requires thinning and weight reduction, the thickness is usually 0.5 to 1.5 mm.

[0036] Such a resin molded product is subjected to a surface roughening treatment, if necessary, to a known conductivity treatment, and then to an electroplating treatment to form a metal plating layer on the surface. The obtained electroplated component can be obtained. By forming the metal plating layer by the electroplating process, the obtained electroplated component has excellent EMI shielding properties, rigidity, impact resistance, thermal conductivity, and the like. The surface roughening treatment is performed to prevent poor peeling between the metal plating layer and the resin molded product, and a known method can be used.
For example, when the other polymer (B) contained in the resin composition for a plating substrate includes the copolymer (B-1) alone, that is, the copolymer (B-1) alone, or The copolymer (B-1) and the polycarbonate resin (B-
2) In the case of a polymer alloy with one or more resins selected from the three resins of polyamide resin (B-3) and polyester resin (B-4), a mixed solution of chromic acid and sulfuric acid is usually used. If the polyamide resin (B-3) is used alone, hydrochloric acid or stannic chloride solution can be used.

The conductive treatment is carried out to make the resin molded product conductive and enable electroplating. For example, a conductive electroless plating layer is formed on the surface of the resin composition by electroless plating. There is a way to do that. In order to deposit the electroless plating layer, the surface-roughened resin molded product or the surface-roughened resin molded product is immersed in a tin-palladium solution or subjected to a treatment such as sputtering metal palladium. In addition, it is necessary to apply a metal such as palladium having a catalytic action to the surface of the resin molded product. In the method of immersion in the tin-palladium solution, when the other polymer (B) contains only the copolymer (B-1), it contains a vinyl cyanide monomer unit, and thus the tin-palladium is used as it is. Electroless plating can be performed by adsorption of palladium. On the other hand, in other cases, in order to adsorb tin-palladium, it is necessary to perform a treatment such as surfactant treatment or kneading and mixing a resin having another polarity, or coating treatment on the surface. Is not particularly limited. As another method of depositing the electroless plating layer, there is a method of applying a coating containing fine metal particles such as nickel and depositing the electroless plating layer using the nickel particles or the like as a catalyst nucleus.
Examples of the type of electroless plating include copper, nickel, and silver.

As another conductive treatment, carbon black, carbon fiber, metal powder, metal fiber, or carbon fiber or other fiber or cloth is subjected to plating in a resin composition for a plating substrate. , A method of applying a conductive paint, a method of sputtering or vacuum depositing a metal, and the like.

The subsequent electroplating process can be performed by a known method, and examples of the metal plating layer formed include copper, nickel, cobalt, chromium, silver, and gold. The electroplated component of the present invention is obtained by subjecting at least a part of a resin molded product to an electroplating process to form a metal plating layer. The metal plating layer may partially cover the resin molded product as required. However, the characteristics of the electroplated component, that is, excellent EMI shielding properties, flexural modulus, rigidity, impact resistance, thermal conductivity In order to sufficiently exhibit such effects, it is preferable that the metal plating layer covers the entire surface (including the non-effective surface) or 90% or more of the total surface area (including the non-effective surface) of the resin molded product.

The thickness of the metal plating layer formed by the electroplating process is preferably at least 5 μm.
If it is less than 5 μm, the rigidity of the electroplated component becomes insufficient. Further, when the metal plating layer is formed on the front side and the back side of the resin molded product, the difference between the thickness of the metal plating layer on the front side and the thickness of the metal plating layer on the back side is preferably 20% or less. If it exceeds 20%, the tensile stress generated when depositing the metal plating layer on the surface of the resin molded product is greatly different between the front side and the back side of the resin molded product, and as a result, the resin molded product is distorted or stress is accumulated. Troubles are likely to occur. The metal plating layer is not limited to a single-layer structure, and may have a multilayer structure of two or more layers. Further, in the metal plating layer having a multilayer structure, there is no limitation on the type and combination of metals of each layer, and the thickness of each layer is not limited as long as the total thickness of the metal plating layer is 5 μm or more. Further, a coating may be applied on the plating layer before use.

Examples of the electroplated parts of the present invention include audio equipment such as personal computers (including notebook type), projectors (including liquid crystal projectors), TVs, printers, faxes, copiers, MDs, etc., game machines, cameras ( Housing such as video equipment such as video cameras, digital cameras, etc., video equipment such as video, musical instruments, mobile equipment (electronic notebooks, PDAs, etc.), lighting equipment, telephones (including mobile phones), fishing gear, pachinko goods Examples include various parts used for playground equipment such as toys, products for vehicles, products for furniture, sanitary products, products for building materials, etc., and are particularly suitable for notebook PCs and housings of portable devices.

As described above, the resin composition for a plating substrate described above has good moldability, dimensional accuracy, mechanical strength, and plating performance, and is also environmentally friendly.
Therefore, by forming a metal plating layer by electroplating on a resin molded product obtained by molding and processing the resin composition for a plating base material, a high-performance electroplated component having excellent heat conductivity can be obtained. Can be manufactured.

[0043]

EXAMPLES Examples will be specifically described below. The present invention is not limited to these examples. Further, “parts” and “%” in the examples mean “parts by mass” and “% by mass”, respectively. [Production of graft copolymer (A-1)] The solid content is 3
5 parts, 100 parts of polybutadiene latex having an average particle diameter of 0.08 μm (as solid), 85 parts of n-butyl acrylate unit and 15 parts of methacrylic acid unit, 2 parts of a copolymer latex having an average particle diameter of 0.08 μm (solid) ) Was added with stirring, and stirring was continued for 30 minutes to obtain an enlarged butadiene rubber polymer latex having an average particle diameter of 0.28 μm. The resulting enlarged butadiene-based rubbery polymer latex is added to a reaction vessel, and distilled water 10
0 parts, wood rosin emulsifier 4 parts, Demol N (trade name,
0.4 part of naphthalenesulfonic acid formalin condensate manufactured by Kao Corporation), 0.04 part of sodium hydroxide, and 0.7 part of dextrose are added, and the mixture is heated with stirring and heated to an internal temperature of 60 ° C. After adding 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate and 0.06 part of sodium dithionite, the following mixture was continuously dropped over 90 minutes, and then kept for 1 hour. And cooled. 30 parts of acrylonitrile, 70 parts of styrene, 0.4 part of cumene hydroperoxide and tert-dodecyl mercaptan 1
Part After the obtained graft copolymer latex is coagulated with dilute sulfuric acid, washed, filtered and dried, the graft copolymer (A-
A dried powder of 1) was obtained. This graft copolymer (A-
The acetone-soluble matter in 1) was 27%.

[Production of Graft Copolymer (A-2)] Raw materials were charged into a reactor at the following ratios,
The polymerization was completed while stirring at 0 ° C. for 4 hours to obtain a rubber latex. n-butyl acrylate 98 parts 1,3-butylene glycol dimethacrylate 1 part allyl methacrylate 1 part sodium dioctyl sulfosuccinate 2.0 parts deionized water 300 parts potassium persulfate 0.3 part disodium phosphate dodecahydrate 0.5 Part Sodium hydrogen phosphate dodecahydrate 0.3 part 100 parts (solid content) of this rubber latex was placed in a reaction vessel, 280 parts of ion-exchanged water was added for dilution, and the temperature was raised to 70 ° C. On the other hand, acrylonitrile / styrene = 29 /
After dissolving 0.7 parts of benzoyl peroxide in 100 parts of a monomer mixture consisting of 71 (mass ratio) and replacing with nitrogen, the above rubber latex is mixed with the monomer latex at a rate of 30 parts / hour. The metered pump was added to the reaction kettle containing it. After the completion of the injection of all the monomers, the temperature in the system was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The conversion was 99%. The latex produced by the above manner, 3-fold amount of aluminum chloride of the total latex _{(AlCl 3 · 6H 2 O)} 0.15% aqueous solution (90
C.) with stirring. After the addition of all the latex was completed, the temperature in the coagulation bath was raised to 93 ° C., and left as it was for 5 minutes. After cooling, the mixture was drained and washed by a centrifugal separator, dried, and the graft copolymer (A-
2) A dry powder was obtained. This graft copolymer (A-
The acetone-soluble matter in 2) was 21%.

[Production of Graft Copolymer (A-3)] A graft copolymer using a polybutadiene / polybutyl acrylate composite rubber as a rubbery polymer was synthesized as follows. 20 parts (as solid content) of polybutadiene latex having a solid content of 35% and an average particle size of 0.08 μm
-Butyl acrylate unit 82%, methacrylic acid unit 1
0.4% (as solid content) of a copolymer latex of 8% having an average particle diameter of 0.10 μm was added with stirring.
Stirring was continued for 0 minute to obtain an enlarged diene rubber latex having an average particle diameter of 0.36 μm. 20 parts (solid content) of the obtained enlarged diene rubber latex was transferred to a reaction vessel, and 1 part of disproportionated potassium rosinate, 150 parts of ion-exchanged water and the following monomer mixture were added, and the mixture was replaced with nitrogen. ℃ (internal temperature)
The temperature rose. To this was added a solution prepared by dissolving 0.0002 parts of ferrous sulfate, 0.0006 parts of disodium ethylenediaminetetraacetate and 0.25 parts of Rongalite in 10 parts of ion-exchanged water. n-butyl acrylate 80 parts Allyl methacrylate 0.32 parts Ethylene glycol dimethacrylate 0.16 parts The internal temperature at the end of the reaction is 75 ° C, but when the temperature is further raised to 80 ° C and the reaction is continued for 1 hour, the polymerization rate Reached 98.8%, and a composite rubber of an enlarged diene rubber and a polyalkyl acrylate rubber was obtained. 50 parts (solid content) of a composite rubber latex of an enlarged diene rubber and a polyalkyl acrylate rubber were placed in a reaction vessel, 140 parts of ion-exchanged water was added for dilution, and the temperature was raised to 70 ° C. Acrylonitrile /
50 parts of a graft monomer mixture composed of styrene = 29/71 (mass ratio) was adjusted, and 0.35 parts of benzoyl peroxide was dissolved and then replaced with nitrogen. This monomer mixture was added to the above reaction system at a rate of 15 parts / hour using a metering pump. After completion of the injection of all the monomers, the temperature in the system was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The conversion was 99%. The latex produced as described above was poured into a 0.5% aqueous solution of sulfuric acid (90 ° C.) three times as much as the total latex with stirring to coagulate. After the addition of all the latex was completed, the temperature in the coagulation bath was raised to 93 ° C., and left as it was for 5 minutes. After cooling, it was drained and washed by a centrifugal separator and dried to obtain a dry powder of the graft copolymer (A-3). The acetone-soluble matter of the graft copolymer (A-3) is 20.
%Met.

[Production of Graft Copolymer (A-4)] A graft copolymer using a polysiloxane rubber / polybutyl acrylate composite rubber as a rubbery polymer was synthesized as follows. 96 parts of octamethyltetracyclosiloxane,
2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. Distilled water 30 in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added.
After adding 0 parts and stirring with a homomixer at 10,000 revolutions / 2 minutes, the homogenizer was added with 1 MPa at a pressure of 30 MPa.
The mixture was filtered to obtain a stable premixed organosiloxane latex. On the other hand, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours.
The temperature was maintained and cooled for hours. The reaction solution was left at room temperature for 48 hours, and then neutralized with an aqueous solution of sodium hydroxide. A portion of the latex (L-1) thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.3%.

Next, 119.5 parts of polyorganosiloxane latex (L-1) and 0.1% of sodium polyoxyethylene alkylphenyl ether sulfate were placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer. After collecting 8 parts and adding and mixing 203 parts of distilled water,
A mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. Internal temperature is 60
When the temperature reached ℃, an aqueous solution obtained by dissolving 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate and 0.24 part of Rongalite in 10 parts of distilled water was added, and radical polymerization was started. I let it. The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a composite rubber latex of polyorganosiloxane and butyl acrylate rubber. After the temperature of the liquid inside the reactor had dropped to 60 ° C., an aqueous solution obtained by dissolving 0.4 part of Rongalite in 10 parts of distilled water was added, and then acrylonitrile was added.
A mixture of 1 part, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide was dropped and polymerized for about 1 hour. After the dropping was maintained for 1 hour, an aqueous solution in which 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate and 0.25 part of Rongalite were dissolved in 10 parts of distilled water was added, and then acrylonitrile was added. A mixture of 7.4 parts, 22.2 parts of styrene and 0.1 part of tertiary butyl hydroperoxide was dropped and polymerized over about 40 minutes. After dripping 1
After holding for a while, the mixture was cooled to obtain a latex of a graft copolymer in which an acrylonitrile-styrene copolymer was grafted on a composite rubber composed of polyorganosiloxane and butyl acrylate rubber. Subsequently, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. 100 parts of the latex of the graft copolymer was gradually dropped into this, and solidified. Next, the precipitate was separated and washed, and then dried to obtain a dry powder of the graft copolymer (A-4). The acetone-soluble matter of this graft copolymer (A-4) was 26%.

[Production of copolymer (B-1a)] A copolymer having a composition of acrylonitrile unit 30% and styrene unit 70% was produced by a suspension polymerization method. [Polycarbonate resin (B-2a)] "7022A" manufactured by Mitsubishi Engineering-Plastics Corporation was used as the polycarbonate resin (B-2a). [Polyamide resin (B-3a)] Polyamide resin (B-
"1011FB" manufactured by Ube Industries, Ltd. was used as 3a). [Polybutyl terephthalate resin (B-4a)] As a polybutyl terephthalate resin (B-4a), "Toughpet PBT N1000" manufactured by Mitsubishi Rayon Co., Ltd. was used.

[Examples 1 to 20, Comparative Examples 1 to 10] Table 1
And the above graft copolymer (A-
1) to (A-4) and other polymers (B-1a) to
(B-4a), a red phosphorus-based flame retardant (D), and an inorganic filler (E) were respectively blended to prepare a resin composition for a plating substrate. However, each of the graft copolymers (A-1) to
(A-4) contains an acetone-soluble matter, and this acetone-soluble matter is counted as another polymer (B). Accordingly, Table 1 shows the actual amounts of the above graft copolymers (A-1) to (A-4) and the net amount excluding the amount of acetone-soluble components therefrom. The amount of acetone-soluble components in the graft copolymers (A-1) to (A-4) counted as the polymer (B) is also shown. As the red phosphorus-based flame retardant (D), "Nova Excel 140" manufactured by Rin Kagaku Kogyo KK was used. In Comparative Example 2, triphenylene phosphate was used as a flame retardant. As the inorganic filler (E), as glass fiber, NEC Glass Co., Ltd.
"ECS03-T191" (in the table, indicated as GF)
And "TR0" manufactured by Mitsubishi Rayon Co., Ltd.
6U "(indicated as CF in the table). And
The flame retardancy and moldability of each of the obtained resin compositions for a plating substrate were evaluated by the following methods. Further, after molding each resin composition for a plating substrate, a metal plating layer was formed on the resin composition according to the following plating step, and various physical properties were evaluated. The results are shown in Tables 3 and 4.

[Flame retardancy] Test piece (12.7 mm x 127 mm x
1.0 mm [thickness]), and a combustion test was performed in accordance with UL94. Abbreviations in the table indicate the following. ；: V-0 level ×; V-0 level or less [Moldability] (1) Burr A substantially box-shaped product (297 mm x 185 mm x 20 mm [1.25]
mm thickness]), and the occurrence of burrs was confirmed. Abbreviations in the table indicate the following. ○; No ×; Yes (2) Warp Substantially box-shaped product (297 mm x 185 mm x 20 mm [1.25
mm thickness]), and the presence or absence of warpage was confirmed. Abbreviations in the table indicate the following. ○; No ×; Yes (3) Gas Substantially box-shaped product (297 mm x 185 mm x 20 mm [1.25
mm thickness]), and the presence or absence of gas adhesion on the mold surface was confirmed. Abbreviations in the table indicate the following. ○; No ×; Yes

[Flexural Modulus] The flexural modulus was measured as an index indicating the rigidity. In the following [plating step], a test piece (10 mm x 100 mm x 4 mm [thickness]) was plated, and then measured in accordance with ASTM D-790. [Izod impact strength] In the following [plating process], a test piece (12.7 mm x 63.5 mm x 6.4 mm [thickness]) was plated, and then measured in accordance with ASTM D-256. did. [Thermal cycling property] In the following [plating process], a flat plate (100 mm x 100 mm x 3 mm [thickness]) was plated and then tested under the following thermal cycle conditions.
The presence or absence of swelling of the plating film was confirmed. (Thermal cycle condition) -30 ° C x 1 hour → 23
C. × 15 minutes → 80 ° C. × 1 hour → 23 ° C. × 1 hour as one cycle, and three cycles were performed. Abbreviations in the table indicate the following. ○: no change ×: swelling only near the gate xx; swelling other than near the gate xx ×; swelling over the entire surface [Thermal conductivity] In the following [plating process], a flat plate (100 mm
× 100mm × 3mm [thickness]), and then a Shotherm QTM rapid thermal conductivity meter (manufactured by Showa Denko KK)
Was used to measure the thermal conductivity.

[Plating Step] (1) Degreasing (60 ° C. × 3 minutes) → (2) Rinsing → (3) Etching (CrO ₃ 400 g / l, H ₂ SO ₄ 200 cc /
l 60 ° C x 8 minutes) → (4) Washing with water → (5) Acid treatment (normal temperature 1 minute) → (6) Washing with water → (7) Catalytic treatment (25 ° C x 3)
Min) → (8) Rinsing → (9) Activation treatment (40 ° C × 5 min)
→ (10) Rinse with water → (11) Chemical nickel plating → (1
2) Rinse with water → (13) Electro copper plating (Plating thickness 15μm
(20 ° C x 20 minutes) → (14) Rinse with water → (15) Electro-nickel plating (plating film thickness 10μm 55 ° C x 15 minutes) →
(16) Rinse with water → (17) Dry However, in Examples 19 and 20, the steps (13) and (14) of the above steps were omitted, and the process time of (15) was 6 minutes, and the plating film thickness of 4 μm was obtained. Electroplating was performed.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

As is clear from Tables 3 and 4, the resin compositions for plating of this example are all excellent in flame retardancy and moldability, and the resin molded articles obtained by molding the same are subjected to metal plating. Those with a layer, bending elastic modulus, impact strength,
It had excellent thermal conductivity and also excellent thermal cycling (plating performance).

[0058]

As described above, the resin composition for a plating base material of the present invention has good moldability, dimensional accuracy, mechanical strength, plating performance, and is environmentally friendly. . Therefore, by forming a metal plating layer by electroplating on a resin molded product obtained by molding and processing the resin composition for a plating base material, the heat conductivity is good and an excellent electroplated component is obtained. be able to. Therefore, the industrial significance of the present invention is extremely large.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 3/02 C08K 3/02 C08L 51/04 C08L 51/04 C25D 5/56 C25D 5/56 A B 7/00 7 / 00 Y F term (reference) 4F006 AA35 AA36 AA38 AA58 AB73 BA07 CA08 DA01 EA01 4F071 AA12 AA13 AA22 AA22X AA34X AA43 AA50 AA54 AA77 AB03 AB05 AB12 AB18 AB20 AB21 AB26 AB28 AD01 AD02 AE07 AE07 AF23 BN15W BN17W CF06X CF07X CF08X CG01X CL01X CL03X CL05X DA017 DA037 DA056 DC007 DE237 DJ047 DJ057 DL007 FA037 FD017 FD136 GQ00 4K024 AA02 AA03 AA09 AA10 AA11 AB01 BA14 BB09 BB15 BB17 BB18 BB17 BB18 BB17 BC18

Claims (8)

[Claims] 1. A rubber polymer (A1) is graft-polymerized with a monomer component (A2) containing an aromatic alkenyl compound monomer unit (a) and a vinyl cyanide compound monomer unit (b). 10 to 60% by mass of the graft copolymer (A),
Resin composition (C) consisting of 40 to 90% by mass of other polymer (B) (however, (A) + (B) = 100% by mass)
A resin composition for a plating base, wherein 2 to 40 parts by mass of a red phosphorus-based flame retardant (D) is blended with 100 parts by mass. 2. A copolymer in which the other polymer (B) comprises a monomer component containing an aromatic alkenyl compound monomer unit (a) and a vinyl cyanide compound monomer unit (b). (B-1), at least one selected from the group consisting of a polycarbonate resin (B-2), a polyamide resin (B-3), and a polyester resin (B-4). A resin composition for a plating substrate. 3. The content of the rubbery polymer (A1) in the resin composition (C) is 5 to 25% by mass, and the average particle size of the rubbery polymer (A1) is 0.1 to 5%. The resin composition for a plating substrate according to claim 1, wherein the thickness is 0.6 μm. 4. The resin composition according to claim 1, wherein 0.1 to 50 parts by mass of an inorganic filler (E) is further blended with respect to 100 parts by mass of the resin composition (C). 3. The resin composition for a plating base material according to item 1. 5. The resin composition for a plating substrate according to claim 4, wherein the inorganic filler (E) is a carbon fiber. 6. A resin molded product obtained by molding the resin composition for a plating substrate according to any one of claims 1 to 5. 7. An electroplated part, wherein at least a part of the surface of the resin molded article according to claim 6 is subjected to an electroplating treatment to form a metal plating layer. 8. The electroplated part according to claim 7, wherein the thickness of the metal plating layer is 5 μm or more.