JPH0770446A - Resin composition for plating, plating method of molded product, and plated molded product - Google Patents

Abstract

PURPOSE:To obtain the composition capable of forming molded products having an excellent shielding effect for electromagnetic waves, and having high adhesion to the plating. CONSTITUTION:A resin composition for plating characterized by containing 100wt.pt. of a thermoplastic resin and 0.1-15wt.pt. of a cationic surfactant. A method of plating a molded product by plating a molded product of a thermoplastic resin composition obtained by combining 0.1-15wt.pt. of a cationic surfactant to 100wt.pt. of a thermoplastic resin in a resin composition containing a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for plating, a plating method and a plated product, and more specifically, it is possible to carry out a plating treatment using the step of plating the surface of an ABS resin as it is. A resin composition for plating, which can easily produce a molded product capable of
A resin molding other than S, which is said to be difficult to plate, can be plated easily regardless of the type of resin used as a plating method and material. The present invention relates to a plated molded body.

[0002]

2. Description of the Related Art Conventionally, a technique for plating the surface of an ABS resin molded body is well known. However, even if a surface of a molded body such as polyolefin or polystyrene is plated with an ABS resin plating line, the plating does not adhere to the surface of the molded body.

If a plating layer can be formed on the surface of a molded product such as polyolefin or polystyrene with good adhesiveness, an electromagnetic wave shield molded product or an electromagnetic wave shield molded product can be produced at a low material cost.
It is possible to manufacture decorative molded products and other industrial materials.

At present, it is possible to use a special plating line to plate the surface of a resin molding such as polypropylene or polystyrene. However, it is not possible to use a general-purpose plating line for ABS resin molding. Unable to use the equipment. The special plating line has a number of steps as compared with the plating line for the ABS resin molded body, and there are problems that the treating agent is different for each kind of resin. Moreover, in this special plating line, the insulating portion of the jig or the like is also plated. Therefore, when the electroplating process is required, there is a problem that a jig replacement or a peeling process is further required. .

As an old technique for plating a molded body of a polyolefin composition, there is a method described in Japanese Patent Publication No. 46-4674.

In this publication, a polyolefin composition containing a polyolefin and a nonionic surfactant is
It is disclosed that a metal plating having good adhesion can be formed on the surface of the molded body. According to this publication,
It has been suggested that a composition containing a polyolefin and an ionic surfactant cannot be plated with good adhesion. In this publication, it is unclear whether a resin composition suitable for metal plating can be obtained by adding a nonionic surfactant to a thermoplastic resin other than polyolefin.

After all, according to the description in the above publication, the polyolefin composition containing the polyolefin and the nonionic surfactant can be plated, but the resin containing another resin and the nonionic surfactant is used. It is unclear whether the composition can be plated well, and it has been clarified that good plating cannot be carried out even if an ionic surfactant is combined.

The present invention has been completed based on the above circumstances.

That is, an object of the present invention is to provide a plating resin composition capable of performing good plating with good adhesion even on the surface of a molded body of any thermoplastic resin including polyolefin. To provide.

Another object of the present invention is to provide a plating method capable of applying excellent plating to the surface of a molded body of any thermoplastic resin.

Another object of the present invention is to provide a molded product in which the surface of a resin which has not been plated in the past can be plated well.

[0012]

The invention according to claim 1 for solving the above-mentioned problems contains 100 parts by weight of a thermoplastic resin and 0.1 to 15 parts by weight of a cationic surfactant. The resin composition for plating, characterized in that the invention according to claim 2 further comprises 0.01 to 5 parts by weight of a lubricant and / or 1 to 500 parts by weight of a high melting point compound with respect to 100 parts by weight of the thermoplastic resin. The resin composition for plating according to claim 1, wherein the cationic surfactant is a quaternary ammonium salt, and the invention according to claim 3 further comprises: The resin composition for plating according to claim 4, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin, polystyrene and polycarbonate. A resin composition for kicks, wherein the invention according to claim 5 is characterized in that a molded body obtained by molding the resin composition for plating according to claim 1 or 2 is plated. It is a method for plating a molded body, and the invention according to claim 6 is a plated molded body plated by the plating method according to claim 5.

The present invention will be described in detail below.

(A) Resin Composition for Plating--Thermoplastic Resin-- Examples of the thermoplastic resin in the present invention include polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polypropylene, 4- Methylpentene-1, polystyrene, polystyrene having syndiotactic structure, ABS resin, AS resin, A
CS resin, methyl methacrylate resin, vinyl chloride resin,
Vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-acrylic acid ester copolymer resin, vinyl chloride-methacrylic acid copolymer resin,
Vinyl chloride-acrylonitrile copolymer, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer,
Vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, polyvinyl ether,
Polyamide 6,6 (nylon 6,6), polyamide 6
(Nylon 6), polyamide 4,6 (nylon 4,
6), polyamide MXD6, polycarbonate, polyacetal, polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, unsaturated polyester resin, polyarylate, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyetherimide, polyamideimide, polyimide And so on.

Among these, polyolefins such as polyethylene and polypropylene and polystyrene are convenient resins for producing various molded products at low cost. Polyolefin is suitable for applications making use of its excellent chemical resistance, for example, automobile materials and packaging materials. Polystyrene is suitable as a material for the outer shell by taking advantage of its excellent dimensional characteristics, and is suitable for applications such as housings and covers in home electric appliances and office automation.

Polycarbonate is suitable for applications that make use of its excellent heat resistance, rigidity and impact resistance, for example, as a material for chassis of housing.

In the present invention, various thermoplastic resins including the above-mentioned various thermoplastic resins can be appropriately selected and used alone, or two or more thereof can be used in combination. You can also

-Cationic Surfactant- Examples of the cationic surfactant in the present invention include amine salts and quaternary ammonium salts.

Examples of the amine salt include aliphatic amine salts which can be obtained by neutralizing primary, secondary and tertiary higher alkylamines with an acid.

Examples of the quaternary ammonium salt include aromatic quaternary ammonium salt, aliphatic quaternary ammonium salt, and heterocyclic quaternary ammonium salt. As the aromatic quaternary ammonium salt, benzalkonium salt,
Examples thereof include benzethonium chloride salt. Examples of the aliphatic quaternary ammonium salt include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, and alkyl dimethyl benzyl ammonium salt. Examples of the heterocyclic quaternary ammonium salt include an alkylpyridinium salt, an imidazolinium salt, an alkylisoquinolinium salt, and a dialkylmorpholinium salt. In addition to these, examples of the quaternary ammonium salt include quaternary ammonium chloride, quaternary ammonium sulfate, and quaternary ammonium nitrate.

Of these, the use of an aliphatic quaternary ammonium salt is particularly preferable because it has an excellent effect of improving the plating adhesion. However, not limited to this aliphatic quaternary ammonium salt, in the present invention, one of the various cationic surfactants can be appropriately selected and used alone, or two or more thereof can be used in combination. You can also

In the present invention, the content of the cationic surfactant in the plating resin composition is 0.1 to 15 parts by weight, preferably 0.2 parts by weight, based on 100 parts by weight of the thermoplastic resin. 10 to 10 parts by weight, more preferably 0.3 to 7 parts by weight. When the content of the cationic surfactant is less than 0.1 part by weight, the plating does not adhere sufficiently to the surface of the molded product, and when it exceeds 15 parts by weight, the plating can adhere to the surface of the molded product. However, the plating is easily peeled off. Moreover, if it exceeds 15 parts by weight, physical properties such as heat resistance of the molded product are deteriorated and it becomes difficult to knead the resin composition.

When the cationic surfactant is liquid at room temperature, it may cause a problem of bite failure during kneading. In such a case, the cationic surfactant may be adsorbed on an inorganic compound such as silica or calcium carbonate in advance, or a high-concentration master batch may be formed. The kneading workability is further improved by making such a device.

-Lubricant- In order to improve the dispersion of the cationic surfactant in the plating resin composition of the present invention, it is preferable to add a lubricant.

Examples of the lubricant include hydrocarbon-based lubricants such as liquid paraffin, paraffin wax, microwax, low-polymerization polyethylene, polystyrene and ethylene-vinyl acetate copolymer, stearic acid, myristic acid, palmitic acid, stearic acid, arachidine. Fatty acid-based lubricants such as acids and behenic acid, fatty acid amide-based lubricants such as stearylamide, palmitylamide, oleylamide, methylenebisstearamide and ethylenebisstearamide,
Butyl stearate, ester lubricants such as ethylene glycol monostearate, alcohol lubricants such as cetyl alcohol, stearyl alcohol, lead stearate, calcium stearate, zinc stearate, metallic soaps such as magnesium stearate, carnauba wax, candelilla wax, Mention may be made of natural or synthetic waxes such as montan wax.

Among the various lubricants, metallic soaps are preferable, and zinc stearate, calcium stearate, magnesium stearate and the like are particularly preferable.

The content of the lubricant in the plating resin composition is usually 0.01 to 5 parts by weight, preferably 0.02 to 3 parts by weight, based on 100 parts by weight of the thermoplastic resin. . When the content of the lubricant is within the above range, the adhesion of the plating is further improved, the plating does not easily peel off, and the resin can be kneaded smoothly and without any trouble. In other words, if the amount is less than 0.01 parts by weight, the adhesion of the plating may be reduced, and if it is more than 5 parts by weight, the plating may be easily peeled off, and the kneading of the plating resin composition may be difficult. It can be difficult.

From another point of view, in some cases, the content of the lubricant in 100 parts by weight of the thermoplastic resin is
It is also possible to employ any range of 0.01 parts by weight and 0.02 parts by weight as a lower limit value and 1 part by weight as an upper limit value as a preferable content range.

—High Melting Point Compound— In order to improve the dispersion of the cationic surfactant in the plating resin composition of the present invention, a high melting point compound that does not melt at the kneading temperature of the resin composition is added. Preferably.

Therefore, the high melting point compound is selected depending on the kneading temperature of the plating resin composition of the present invention. As a general description, 250 ° C. or higher,
Preferably, the compound has a melting point of 300 ° C. or higher, or does not have a definite melting point and has a softening point or a decomposition point of 250.
A compound having a temperature of not less than 0 ° C, preferably not less than 300 ° C is adopted. Therefore, the "high melting point compound" in the present invention
Certainly the concept is not limited to substances with a "melting point".

In any case, talc, calcium carbonate, magnesium hydroxide, decabromodiphenyl ether, decabromodiphenylethane, decabromodiphenylpropane, decabromodiphenyl, tetradecabromodiphenoxybenzene are used as the high melting point compound in the present invention. , Ethylenebistetrabromophthalimide, titanium oxide, antimony oxide, barium sulfate, glass powder,
Examples thereof include glass fiber, carbon black, zinc oxide, magnesium oxysulfate and titanium whiskers.

The high melting point compound has a particle size of 15 μm.
It is preferably the following or less, and particularly preferably 10 μm or less. When the particle size of the high melting point compound is not more than the above value, the adhesion of plating on the surface of the molded product is improved.

The content of this high melting point compound in the plating resin composition is usually 1 per 100 parts by weight of the thermoplastic resin.
To 500 parts by weight, preferably 2 to 300 parts by weight, and more preferably 3 to 200 parts by weight. When the content is within the above range, the adhesion of plating is good and the peeling of plating is unlikely to occur. Although it is not always the case, if the content of the high melting point compound is less than 1 part by weight, the adhesion of the plating may decrease, and if it is more than 500 parts by weight, the plating is likely to peel off. May be.

In the plating resin composition of the present invention, the high melting point compound may be used in combination with the lubricant.

High melting compounds suitable for use in the present invention, whether used in combination or not, are disclosed in the examples of this specification.

-Other Optional Components- The plating resin composition of the present invention may contain various other components as long as the object of the present invention is not impaired.

Examples of such other components include flame retardants, antioxidants, release agents, colorants, inorganic fillers, reinforcing materials, light stabilizers, compatibilizers, plasticizers, heat stabilizers, copper. Examples include harm inhibitors and the like.

Examples of the antioxidant include 2,6
-Di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 2,2-
Methylenebis (4-methyl-6-t-butylphenol), 2,2-methylene-bis- (4-ethyl-6-t
-Butylphenol), 4,4-thiobis (3-methyl-6-t-butylphenol), 4,4-butylidenebis- (3-methyl-6-t-butylphenol), tetrakis {methylene-3- (3,5- Di-t-butyl-4
-Hydroxyphenyl) propionate} methane, 1,
1,3-tris- (2-methyl-4-hydroxy-5-
phenol-based compounds such as t-butylphenyl) butane, amine-based compounds such as phenyl-β-naphthylamine, N, N-diphenyl-p-phenylenediamine,
Phosphorus compounds such as tris (nonylphenyl) phosphite, triphenylphosphite, trioctadecylphosphite, diphenylisodecylphosphite, dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate Examples thereof include sulfur compounds.

Examples of the releasing agent include carnauba wax, paraffin wax, silicone oil and the like.

As the colorant, colorants such as usual pigments and dyes used for coloring plastics can be used.

Examples of the inorganic fillers include calcium sulfate, magnesium sulfate, mica, silica, asbestos, glass beads, glass flakes, zinc oxide, magnesium oxide, molybdenum oxide, tin oxide, zirconium oxide, iron oxide, alumina, Examples thereof include quartz powder and metal powder.

Examples of the reinforcing agent include carbon fiber, synthetic fiber, metal fiber and the like.

Examples of the light resistance stabilizer include salicylic acid type ultraviolet absorbers such as phenyl salicylate and pt-butylphenyl salicylate, and benzophenone type ultraviolet rays such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone. Absorbent, 2- (2
-Hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl)
Examples thereof include benzotriazole-based UV absorbers, cyanoacrylate-based UV absorbers, hindered amine-based light stabilizers, and nickel-based compounds.

The method for preparing the plating resin composition of the present invention is not particularly limited. For example, the thermoplastic resin, the cationic surfactant and various optional components used as desired may be added to a ribbon blender or a tumble mixer. , Henschel mixer, open roll, Banbury mixer, single screw extruder, twin screw extruder, single screw reciprocating screw extruder and the like.

The resin composition for plating of the present invention can be produced by a known molding method such as rotational molding method, inflation molding method,
By a cast molding method, an extrusion molding method, an injection molding method, an extrusion molding method, etc., various molded products including a sheet, a film, a pipe, various casings and the like can be molded.

The plating resin composition of the present invention can be plated on the surface of various molded products of the plating resin composition by the plating method described below.

(B) Plating Method In the plating method of the present invention, a resin composition containing a thermoplastic resin is mixed with 0.1 to 15 parts by weight of a cationic surfactant per 100 parts by weight of the thermoplastic resin. Then, the basic content is to plate the molded product obtained by molding the obtained thermoplastic resin composition.

The plating resin composition of the present invention can be preferably used as the thermoplastic resin composition.

A molded product obtained by molding the thermoplastic resin composition, particularly the plating resin composition of the present invention, is made into ABS.
For example, the surface of the resin molding can be plated by the following steps for plating the resin molding.

(1) Degreasing step This step is intended to improve the wetting of the molded body by the etching solution in the next step.

In this step, the molded body is dipped in an alkaline solution at 40 to 60 ° C. for 1 to 2 minutes, for example. Note that this step is not an essential step. The temperature and immersion time of the alkaline solution in this step may be appropriately selected according to the type of thermoplastic resin in the plating resin composition. This is because, depending on the type of thermoplastic resin, the molded body may be deformed.
The time for immersing the molded body in the alkaline solution is not limited to the above time, and can be appropriately changed depending on the type of the thermoplastic resin forming the resin composition for plating.

(2) Etching Step This step is intended to chemically etch the surface of the molded body to ensure adhesion with the metal plating film.

In this step, the molded body is dipped in the etching solution.

Examples of the etching solution include a mixed solution of chromic acid and sulfuric acid, a mixed solution of chromic acid, sulfuric acid and phosphoric acid.

The composition of the etching solution, the temperature, and the etching conditions for immersing the molded body in the etching solution can be appropriately changed depending on the kind of the thermoplastic resin forming the plating resin composition.

(3) Catalytic Step The molded body that has undergone the etching step is subjected to the catalytic step. This catalyzation step aims at precipitating precious metal nuclei, which is a catalyst necessary for starting the chemical plating reaction, on the surface of the molded body. In order to sufficiently achieve this purpose, it is necessary to avoid as much as possible the chromic acid of the etching solution in the etching step from being brought into this step, so the molded body to be subjected to the catalyzing step should be thoroughly washed with water and, in some cases, It is desirable to sufficiently neutralize with a weak acid or alkali after or after washing with water.

In this catalysis step, for example, the molded body is dipped in the sensitizing solution, and then the molded body is dipped in the activating solution.

Examples of the sensitizing solution include a solution of stannous chloride in hydrochloric acid. Examples of the activating solution include a hydrochloric acid solution of palladium chloride, an aqueous ammonia solution of silver nitrate, a solution in which stannous chloride, palladium chloride and hydrochloric acid are mixed in an appropriate ratio.

(4) Chemical Plating Step The molded body that has undergone an appropriate catalyzing step is washed with water, for example, and then subjected to a chemical plating step. This chemical plating step involves immersing the molded body in a chemical plating bath.

Examples of the chemical plating bath include chemical copper bath and chemical nickel bath.

In this chemical plating step, when the molded body is immersed in the chemical plating bath, a chemical plating reaction immediately occurs on the surface of the molded body, and a metal is deposited on the surface of the molded body by chemical reduction.

The film thickness of the deposited metal is proportional to the time for immersing the molded body in the chemical plating bath. Therefore, it is preferable to appropriately select the immersion time so as to obtain a desired metal film thickness.

By this chemical plating step, metal plating having a desired film thickness is formed on the surface of the molded body. A molded product having plating (hereinafter, also referred to as a plated molded product) is used for electromagnetic wave shielding, such as a communication device product, a home electric appliance, a home information device, an office automation device, an automobile interior / exterior product, etc. Can be used as a product. However, the plated molded body that has been subjected to this chemical plating step may be subjected to the next electroplating step and further plated.

(5) Electroplating Step In this electroplating step, metal plating is formed on the plating surface of the above-mentioned plated molded body by the same treatment as the plating formation on the metal surface.

Before the plated molded body is subjected to this electroplating step, it is desirable that the surface of the plated molded body be sufficiently cleaned, for example, by acid immersion or degreasing.

Examples of the plating bath include a simple salt bath and a complex ion bath. Examples of the plating bath include a copper plating bath, a nickel plating bath, a chrome plating bath, a zinc plating bath, a tin plating bath, a gold plating bath, a silver plating bath, and a rhodium plating bath.

The composition of each of the various plating baths is appropriately determined according to the kind of metal to be further formed on the surface of the plated molded body.

The electrolysis conditions may include current density, temperature, current efficiency and the like.

For example, when the current density is low, the frequency of generation of crystal nuclei is generally low, so that the crystal grains of the precipitate are large and the plating tends to be large in internal stress. When the current density is high, a large number of crystal nuclei are generated. The crystal grains are small and hard plating. When the current density further increases, the plating is performed under the control of diffusion of metal ions, so that protrusions, dendritic or spongy precipitates may appear, and dense plating may not be obtained. Therefore, in consideration of these general tendencies, it is preferable to appropriately select the current density so as to obtain a desired product. Regarding the temperature during electrolysis, if the temperature is low, the mobility of metal ions is low, so diffusion control may occur even at low current densities, and dense plating may not be obtained. Since there is a general tendency that adhesion becomes poor, it is preferable to appropriately select the temperature during electrolysis in consideration of such a tendency.

As described above, a molded product having a plated surface is obtained. In some cases, the final plated molded body suitable for industrial materials or decorative articles can be obtained by further subjecting the plated molded body to electroplating.

In the resin composition for plating of the present invention, when polyolefin or polystyrene is used as the thermoplastic resin, the surface of the molded product can be obtained by using the plating line of the ABS resin molded product or a simple plating line equivalent thereto. Can be plated with good adhesion. Therefore, when the plating resin composition or the plating method of the present invention is adopted, a special treatment such as when plating a molded product such as a polyolefin becomes unnecessary, and a process for obtaining a plated molded product or a final plated molded product is achieved. The number can be significantly reduced.

[0072]

【Example】

(Examples 1 to 17, Comparative Examples 1 to 15) Each component shown in Table 1 and Table 2 was dry blended with 0.1 part by weight of an antioxidant (Irganox 1010 manufactured by Ciba Geigy),
Heating temperature 220-250 ° C and rotor speed 800r
The mixture was kneaded with a twin-screw kneader under the condition of pm to obtain pellets.

The components in Tables 1 and 2 are shown below.

Thermoplastic resin A1; ethylene-propylene block copolymer (manufactured by Idemitsu Petrochemical Co., Ltd., J-785H), MI = 10 g / 10
Minute A2: HI polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd., HT
53) A3; ethylene-octene-1 copolymer (manufactured by Idemitsu Petrochemical Co., Ltd., Moretec 0138N), MI = 1 g / 10
Minute A4: Polycarbonate (Teflon IN-1900A, manufactured by Idemitsu Petrochemical Co., Ltd.), MI = 19 g / 10 minutes A5: Polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd., E-2)
50G), MI = 1 g / 10 minutes Surfactant B1; Cationic surfactant, NOF Corporation, Elegan 264WAX (aliphatic quaternary ammonium sulfate) B2; Cationic surfactant, NOF Corporation ), Cation M2-100 (aromatic quaternary ammonium salt) B3; cationic surfactant, manufactured by NOF CORPORATION, cation AR-4 (heterocyclic quaternary ammonium salt) B4; cationic interface Activator, manufactured by NOF CORPORATION, cationic SA (aliphatic amine salt) B5; nonionic surfactant, manufactured by NOF CORPORATION, nonion NS-210 (polyoxyethylene nonylphenyl ether) B6; nonionic interface Activator, manufactured by NOF Corporation, Stahome DL (lauric acid diethanolamide) B7; amphoteric surfactant, manufactured by NOF Corporation, Nissa Anone BF (Dimethylalkylbetaine) B8; Anionic surfactant, NOF CORPORATION, Elegan A-2000S (alkyl sulgate) B9; Cationic surfactant [NOF Corporation, ELEGAN 264WAX (fat) Group quaternary ammonium sulfate)] silica-impregnated powder (silica 20% by weight / elegan 264WAX 80% by weight) The above silica; decomposition temperature 950 ° C., manufactured by Fuji Silysia Chemical Ltd., synthetic silica SYLYSIA-350 B10; cationic surfactant Agent [Nippon Oil and Fats Co., Ltd., Elegan 264WAX (aliphatic quaternary ammonium sulfate)] impregnated with calcium carbonate (D1) powder (20% by weight calcium carbonate / 80% by weight Elegan 264WAX) Lubricants C1; metal soap, Nippon Oil & Fats Manufactured by Magnesium Steale Preparative high melting compounds D1; calcium carbonate, grain size 0.8 [mu] m, no melting point. Decomposition temperature 898 ° C., Casen Industry Co., Ltd., Ryton 32
XD2; magnesium hydroxide, particle size 1 μm, no melting point. Decomposition temperature 340 ° C., Kyowa Chemical Industry Co., Ltd., Kisuma 5B D3; antimony oxide, particle size 0.5 μm, melting point 656 ° C.
As described above, manufactured by Nippon Seiko Co., Ltd., Atox SD4; decabromodiphenyl ether, particle size 3 to 5 µ
m, melting point 305 ° C or higher, Manac Co., Ltd., EB-10
WS D5; talc, particle size 2 μm, melting point 1,200 ° C., Asada Flour Milling Co., Ltd., FFR D6; glass fiber, particle size 10 μm, length 3 mm, softening temperature 840 ° C., Asahi Fiber Glass Co., Ltd., JA -42
9A D7: Decabromodiphenylethane, particle size 5 μm, melting point 350 ° C., manufactured by Ethyl Co., Saytex 8010 <Evaluation test> (1) Physical properties of resin Various pellets obtained by the above method were molded by an injection molding method, and obtained. The test pieces were evaluated. The results are shown in Tables 1 to 3.

(A) Bending strength: According to JIS K7203.

(B) Izod impact strength; JIS K-
7110 (notched).

(C) Heat distortion temperature (HDT); JIS K
It conformed to -7207 (low load).

(2) Plating Adhesion Various pellets obtained by the above method were molded by an injection molding method to obtain a rectangular plate having a length and width of 150 × 150 mm and a thickness of 3 mm. ABS this square plate in the following process
The plate was subjected to electroless nickel plating on a plating line to obtain a plated square plate. The ratio of the area where plating was attached on this square plate was measured.

The measurement results are shown in Tables 1 to 3 when the plating did not adhere, 0 when the plating adhered to about 80%, and 100 when the plating adhered to 100%.

<Plating line><1> Degreasing (degreasing temperature: 50 ° C., degreasing time: 5 minutes, degreasing solution: alkaline), <2> water washing (water washing time 30 seconds), <3> etching (etching solution composition: CrO) ₃ 40
0 g / liter, H ₂ SO ₄ 400 g / liter, etching solution temperature 70 ° C., immersion time 10 minutes), <4> Washing with water (washing time 1 minute), <5> Neutralization (sulfuric acid 10 ml / liter, hydrogen peroxide 10)
Washing with a solution of ml / liter for 2 minutes), <6> Washing with water (washing time 30 seconds), <7> Catalysis (sensitizing solution; stannous chloride 10 g / liter hydrochloric acid solution, palladium chloride 0.3 g / Immersion in liter hydrochloric acid solution, sensitizing solution; 3 minutes, temperature; 3
5 ° C), <8> Immerse in activation solution (sulfuric acid) at 35 ° C for 2 minutes <9> Wash with water (washing time 30 seconds), <10> Soak in nickel sulfate bath at 42 ° C for 5 minutes, <11> Wash with water (Washing time 30 seconds), <12> Drying at 80 ° C for 30 minutes (3) Plating adhesion ASTM D3359 using the plated square plate
The tape test based on That is, a 1.5 mm cross hatch was attached to the plated surface of the square plate, and the judgment was made according to the following criteria. The results are shown in Tables 1 to 3.

◯: Peeling within 5% Δ: Peeling within 5 to 50% X: Peeling over 50% (4) Shielding effect Advantest Co., Ltd. using the plated square plate
By using a spectrum analyzer TR4172 and a plastic shield material evaluator TR17301A manufactured by
The probe antenna was set to 1A and the shield effect of the electric field wave at 300 MHz was measured. This measuring method is a measuring method developed by Advantest Corporation based on MIL-STD-285. The results are shown in Table 1
Shown in 3.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

(Examples 18 to 20, Comparative Example 16) (1) Electroplating Adhesiveness In Example 18, the same resin composition as that described in Example 13 was used, and in Example 19 Using the same resin composition as the resin composition described in Example 14 above, for Example 20 using the same resin composition as the resin composition described above in Example 15, and Comparative Example 16 For the above, using the same resin composition as the resin composition described in Comparative Example 14, pellets were respectively prepared, and these pellets were molded by an injection molding method to have a length and width of 150 × 150 mm and a thickness of 3 mm. I got a square plate. This square plate was electroless plated through the same <plating line> as in Example 1, and then electroplated according to the following <electroplating line>. The ratio of the area where the electroplating was adhered on this square plate was measured. The results are shown in Table 4.

<12> Immersion in copper sulfate bath at room temperature for 50 minutes (current density; 3 A / dm ² ) <13> Washing with water for 30 minutes <14> Immersion in semi-bright nickel bath at 50 ° C. for 9 minutes (current density; 4 A) / Dm ² ) <15> Immersed in bright nickel bath at 50 ° C for 9 minutes (current density; 4 A / dm ² ) <16> Washed for 30 minutes <17> Immersed in chromium bath at 45 ° C for 1.5 minutes (current density 15A / dm ² ) <18> Washing with water for 30 minutes <19> Drying at 80 ° C. for 60 minutes (2) Electroplating adhesion A tape test was conducted using the above electroplated square plate. A 90 mm peel test was performed after the 10 mm width adhesive tape was adhered to the plated surface of the square plate. Peeling speed is 50 mm
/ Min. The peel strength of 0.8 kg / cm or more was evaluated as a practical level. This peel strength corresponds to the level of peel strength of the plating on commercial ABS.

[0087]

[Table 4]

[0088]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain a molded product having a plating, which is excellent in electromagnetic wave shielding effect and plating adhesion, by a simple plating line such as a plating line for ABS resin molded products. A resin composition for use can be provided.

According to the present invention, plating can be applied to a molded product with good adhesion by using a simple plating line such as a plating line of an ABS resin molded product, regardless of the type of the thermoplastic resin. A method can be provided.

According to the present invention, it is possible to provide a molded product obtained by plating the surface of a molded product obtained from various resins.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 25/04 KFZ 69/00 KKK C23C 18/16 A

Claims (6)

[Claims] 1. A resin composition for plating comprising 100 parts by weight of a thermoplastic resin and 0.1 to 15 parts by weight of a cationic surfactant. 2. The resin composition for plating according to claim 1, further comprising 0.01 to 5 parts by weight of a lubricant and / or 1 to 500 parts by weight of a high melting point compound with respect to 100 parts by weight of the thermoplastic resin. object. 3. The plating resin composition according to claim 1, wherein the cationic surfactant is a quaternary ammonium salt. 4. The plating resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin, polystyrene and polycarbonate. 5. A method for plating a molded body, which comprises subjecting a molded body obtained by molding the resin composition for plating according to claim 1 or 2 to a plating treatment. 6. A plated molded body plated by the plating method according to claim 5.