JP2006219757A - Method for producing plated resin formed article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a plated resin formed article having a great strength of the adhesion of a plating layer to the resin and exhibiting fine appearance. <P>SOLUTION: The method comprises a step of subjecting a thermoplastic resin formed article to a contacting treatment with an acid or a base not containing a heavy metal, a step of treating the resultant resin formed article with a catalyst imparting fluid, a step of forming a conductive layer on the surface of the thermoplastic resin formed article by a direct plating method, and a step of conducting the electroplating. The above method does not involve an etching step which uses an acid containing a heavy metal. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a plated resin molded article having high adhesion strength of plating and a plated resin molded article obtained by the production method.

  For the purpose of reducing the weight of automobiles, resin molded products such as ABS resin and polyamide resin are used as automotive parts, and copper, nickel, etc. are plated to give this resin molded product a high-class feeling and beauty. ing.

  Conventionally, when plating is performed on a molded body such as an ABS resin, an etching process for roughening the resin molded body after the degreasing process is essential in order to increase the adhesion strength between the resin molded body and the plating layer. For example, when plating an ABS resin molded body or a polypropylene molded body, it is necessary to perform an etching treatment at 65 to 70 ° C. for 10 to 15 minutes using a chromic acid bath (mixed solution of chromium trioxide and sulfuric acid) after the degreasing treatment. Yes, wastewater contains toxic hexavalent chromate ions. For this reason, the process of neutralizing and precipitating the hexavalent chromate ions after reducing them to trivalent ions is essential, and there is a problem during wastewater treatment.

In this way, in consideration of safety during work at the site and the environmental impact of wastewater, it is desirable not to perform etching using a chromium bath, but in that case, to a molded body obtained from ABS resin, etc. There is a problem that the adhesion strength of the plating layer cannot be increased.
JP 2003-82138 A Japanese Patent Laid-Open No. 2003-166067 JP-A-5-239660 WO98 / 45505 (Japanese Patent No. 3208410)

  The inventions of Patent Documents 1 and 2 are excellent in that a plated resin molded body having high plating strength can be obtained without using chromic acid etching, but in that the number of steps in the manufacturing process (plating process) is large. There is room for improvement.

  Patent Documents 3 and 4 describe that the direct plating method is used in the process of plating the surface of the resin molded body. However, in Experimental Example 1 of Patent Document 3, since the surface is roughened with pumice as a pretreatment, it is difficult to produce a plated resin molded body having a beautiful appearance. Since etching is performed, the problems of the prior art cannot be solved.

  The present invention eliminates the need for an etching treatment with chromic acid or the like, and provides a plating resin molded body having a high adhesion strength between the resin molded body and the plating layer and having a beautiful appearance, and the method described above. It is an object of the present invention to provide a plated resin molded body obtained by a manufacturing method.

As a means for solving the problems, the present invention
A step of contact-treating the thermoplastic resin molded body with an acid or base not containing heavy metal,
A step of treating with a catalyst applying liquid,
A method for producing a plated resin molded body comprising a step of forming a conductive layer on the surface of a thermoplastic resin molded body by a direct plating method and a step of electroplating, and does not include an etching step using an acid containing heavy metal I will provide a.

  In another aspect of the present invention, the direct plating method uses a selector liquid containing a metal compound, a reducing compound, and a metal hydroxide to form a conductive layer on the surface of the thermoplastic resin molded body. The manufacturing method of the plating resin molding of Claim 1 which is a process made to provide is provided.

  The present invention provides, as another means for solving the problems, a method for producing a plated resin molded article according to claim 1 or 2, wherein the thermoplastic resin molded article contains polyamide.

  According to the present invention, as another means for solving the problem, the thermoplastic resin molded body further contains a substance having a solubility in water (23 ° C.) of 10 g / 100 g or less. A method for producing a plated resin molded body is provided.

The present invention provides a solution to other problems.
It is the plating resin molding obtained by the manufacturing method of the plating resin molding in any one of Claims 1-4,
It has at least one of the following (1) phase structure of the resin molded body and (2) the bonding state between the resin molded body and the metal plating layer. The present invention provides a plated resin molded product in which no is observed.

(1) Phase structure of molded resin (1-1) Sea-island structure where component (A) is sea and component (B) is an island, or (1-2) Component (A) is sea, (B) Island (B-1) in the sea-island structure when the component is an island-island structure, including the components (A) to (C) and not including the component (D), B-2) must be a sea-island structure.

(2) Joined state of resin molded body and metal plating layer In the vicinity of the surface of the resin molded body, the component (A) which is the sea forms a swelling layer, and the plating metal penetrates into the swelling layer, The plating metal is not substantially permeated into the component (B).
(Heat cycle test 1)
Using a plated resin molded body having a length of 100 mm, a width of 50 mm, and a thickness of 3 mm as a test piece, held at −30 ° C. for 60 minutes, held at room temperature (20 ° C.) for 30 minutes, held at 75 ° C. for 60 minutes, and at room temperature (20 ° C.) A heat cycle test of a total of 3 cycles is performed with 30 minutes holding as one cycle.
(Heat cycle test 2)
Using a plated resin molded body having a length of 100 mm, a width of 50 mm, and a thickness of 3 mm as a test piece, held at −30 ° C. for 60 minutes, held at room temperature (20 ° C.) for 30 minutes, held at 85 ° C. for 60 minutes, and at room temperature (20 ° C.) A heat cycle test of a total of 3 cycles is performed with 30 minutes holding as one cycle.

  In the production method of the present invention, by applying the direct plating method, man-hours can be reduced as compared with the inventions of Patent Documents 1 and 2, and no harmful substances such as formalin are required as a reducing agent.

<Manufacturing method of plating resin molding>
Hereinafter, it demonstrates for every process. In each of the following processes, one process may be separated into two or more processes, or two or more processes may be combined into one process. Moreover, the well-known process in a plating method can be added as needed as follows.

  First, a degreasing treatment is performed on a thermoplastic resin molded body formed into a desired shape suitable for the application by a known method such as injection molding.

  The degreasing treatment is performed with an aqueous surfactant solution containing an alkali such as sodium hydroxide or sodium carbonate or an acid such as sulfuric acid or carbonic acid. In the present invention, it is possible to proceed to the next step after this degreasing treatment, and there is no need for an etching step with chromic acid or the like, which is a roughening treatment for increasing the adhesion strength of the plating layer, and a physical rough surface. There is also no need for a chemical treatment (for example, a process of rubbing the surface with pumice as in Patent Document 3).

  In the next step, the thermoplastic resin molded product is contact-treated with an acid or base that does not contain heavy metals (metals such as chromium and manganese). In addition, the degreasing process of a previous process is abbreviate | omitted and this process is good also as a first process process.

  As the acid not containing a heavy metal, in addition to hydrochloric acid, phosphoric acid and sulfuric acid, those selected from organic acids such as acetic acid, citric acid and formic acid can be used. As the base not containing a heavy metal, a base selected from alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide can be used.

The concentration of the acid or base containing no heavy metal varies depending on the type, but in the case of hydrochloric acid, 1.5 to 3.5 N hydrochloric acid is preferred. The hydrochloric acid is preferably 1.8 to 3.5 N, more preferably 2 to 3 N. When other acids or bases are used, the concentration at which the treated thermoplastic resin surface (for example, confirmed by a scanning electron microscope (SEM)) is comparable to that of hydrochloric acid treatment may be selected.

  For the treatment of this step, for example, a method of immersing the thermoplastic resin molded body in an acid or base that does not contain heavy metals can be applied, and 0.5 to 0.5 wt. A method of immersion for ˜20 minutes can be applied. When 1.5 to 3.5 N hydrochloric acid is used, a method of immersing in an aqueous hydrochloric acid solution in the above concentration range at 20 to 60 ° C. for 1 to 10 minutes can be applied.

  Next, the process of processing with a catalyst provision liquid is performed with respect to the thermoplastic resin molded object in which the process of the previous process was made. This process itself is known, and it is preferable to provide a water washing process before and after this process.

  A well-known thing can be used as a catalyst provision liquid, For example, what contains a catalyst metal, a tin compound, and an acid, and contains another component as needed can be used.

  Known catalysts can be used, such as platinum compounds (such as platinum chloride salts), gold compounds (such as gold sulfites), palladium compounds (such as palladium chloride and palladium sulfate), silver compounds (such as silver nitrate and silver sulfate). ). The amount of catalyst is preferably 100 to 500 mg / L in terms of metal.

  Examples of the tin compound include stannous chloride and stannous sulfate. The usage-amount of a tin compound is 10-50 g / L in conversion of a tin, and 50-120 times amount (mass basis) of a catalyst metal amount is preferable.

  The acid may be hydrochloric acid, sulfuric acid, or a mixed acid of hydrochloric acid and sulfuric acid, and may be one in which sodium chloride is added to the acid, and the pH of the catalyst imparting solution is adjusted to about 1.

  As a catalyst provision liquid, what contains a palladium compound as a catalyst, stannous chloride as a tin compound, and hydrochloric acid as an acid is preferable. For the treatment in this step, a method of immersing the thermoplastic resin molded article in the catalyst applying liquid at room temperature for about 1 to 10 minutes can be applied.

  In the next step, a conductive layer is formed on the surface of the thermoplastic resin molding by a direct plating method. The direct plating method is known and disclosed in Japanese Patent Application Laid-Open No. 2002-338636 (paragraph number 5) in addition to Patent Documents 3 and 4. In this step, a plating solution called a selector solution is used, and a very thin conductive layer is formed as compared with a plating layer (conductive layer) formed by chemical plating that has been widely used conventionally.

Applying the direct plating method is advantageous in the following points as compared with the manufacturing methods of the inventions of Patent Documents 1 and 2 including an electroless plating method (chemical plating method).
(1) It is highly safe because it has a strong reducing power such as formalin and does not use harmful substances like the electroless plating method (chemical plating method).
(2) The activation step after the catalyst addition step is not necessary, and the number of steps can be reduced, so that the manufacturing time can be shortened and the manufacturing cost can be reduced.
(3) When the electroless plating method (chemical plating method) is applied, more steps are required between the electroplating and when the direct plating method is applied, it is possible to immediately move to the electroplating step. Man-hours can be reduced, manufacturing time can be shortened, and manufacturing costs can be reduced.
(4) In the electroless plating method (chemical plating method), plating is also deposited on the jig used during plating, so it is necessary to replace the jig. Almost no plating is deposited.

  As the selector liquid, a liquid containing a metal compound, a reducing compound and a metal hydroxide can be used.

  As the metal compound, a copper compound is preferable, and examples thereof include copper sulfate, copper chloride, copper carbonate, copper oxide, and copper hydroxide. The content of the copper compound is preferably 0.1 to 5 g / L, more preferably 0.8 to 1.2 g / L in terms of copper.

  Reducing compounds do not include those with strong reducing power such as formalin and hypophosphorous acid, which are widely used in known electroless plating (chemical plating), and those with low reducing power compared to these, For example, the following can be mentioned.

  Examples thereof include stannous chloride, sodium borohydride, dimethylamine borane, trimethylamine borane, formic acid or salts thereof, alcohols such as methanol, ethanol, propanol, ethylene glycol, and glycerin and salts thereof.

  Examples of reducing sugars include butter sugar, glucose, sorbit, cellulose, sucrose, mannitol, and gluconolactone. The saccharide content is preferably 3 to 50 g / L, more preferably 10 to 20 g / L.

  Examples of the metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. As for content of a metal hydroxide, 10-80 g / L is preferable, More preferably, it is 30-50 g / L.

  The selector liquid can contain a complexing agent as required. Examples of complexing agents include hydantoins and organic carboxylic acids. Examples of hydantoins include hydantoin, 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin, and allantoin. Examples of organic carboxylic acids include citric acid, tartaric acid, succinic acid, and these. Examples thereof include salts. The content of the complexing agent in the selector is preferably 2 to 50 g / L, more preferably 10 to 40 g / L.

  The pH of the selector liquid is preferably in the range of 10.0 to 14.0, more preferably in the range of 11.55 to 13.5.

  As a specific example of the selector liquid, the plating bath described in (c) of Experimental Example 1 of Patent Document 3 and the present invention baths 1 to 8 described in Patent Document 4 can be used. In addition, other known components can also be added.

  In the treatment of this step, the temperature of the selector liquid is preferably adjusted to 20 to 70 ° C., more preferably 35 to 50 ° C., and then the thermoplastic resin molded product is subjected to about 30 seconds to 20 minutes, preferably 3 to 5 minutes. A method of soaking to the extent can be applied.

  By the treatment in this step, a very thin conductive layer is formed on the surface of the thermoplastic resin molded body, and therefore, electroplating can be performed directly in the next step.

  Next, the thermoplastic resin molded body having a conductive layer formed on the surface in the previous step is electroplated with copper, nickel, chromium or the like by a known method.

  As a thermoplastic resin molding to which the production method of the present invention is applied, a thermoplastic resin composition containing one or a combination of two or more selected from the following thermoplastic resins and other components as required is molded. Can be obtained.

  The thermoplastic resin can be appropriately selected from known ones according to the application. In the present invention, a polyamide resin, a styrene resin, an olefin resin, a polyphenylene ether resin (PPE), a polyphenylene sulfone resin (PPS). ), A polysulfone resin is preferable, and a thermoplastic resin composition containing a polyamide-based resin is more preferable.

  The thermoplastic resin preferably has a water absorption rate (water absorption rate after 24 hours under water at 23 ° C., ISO 62) of 0.6% or more, more preferably 0.6 to 5%, and more preferably 0.6 to 2 % Is more preferable. As the resin having a good water absorption rate, a polyamide resin, an acrylate resin, a cellulose resin, a vinyl alcohol resin, a polyether resin and the like are preferable, a polyamide resin and a polyether resin are more preferable, and a polyamide resin Is most preferred.

  The thermoplastic resin may be a combination of the above-described resin having a good water absorption rate and a resin having a poor water absorption rate (having a water absorption rate of less than 0.6%, preferably a water absorption rate of 0.4% or less). . As the resin having poor water absorption, a styrene resin is preferable.

  When using a thermoplastic resin with poor water absorption and applying a manufacturing method including the direct plating method, to obtain a plated resin molded product with a beautiful appearance and high plating adhesion strength, the optimum conditions are set. However, an increase in man-hours is inevitable. However, when the above-described thermoplastic resin with good water absorption (good metal adsorption) or a resin composition containing a thermoplastic resin with good water absorption is used, it is easily conductive by applying the direct plating method. It is preferable because a conductive layer can be formed and the total man-hour can be reduced.

  In addition, when using the thermoplastic resin composition containing 2 or more types of resin, it is preferable to contain 30 mass% or more of thermoplastic resins which satisfy | fill the above-mentioned water absorption.

  The polyamide-based resin is a polyamide resin formed from diamine and dicarboxylic acid and a copolymer thereof, and may be crystalline, amorphous, or a mixture thereof. When both crystalline and amorphous are mixed, the crystallinity is preferably 60% or less, more preferably 40% or less.

  Polyamide resins include nylon 66, polyhexamethylene sebacamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon 6 · 12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene azide Pamide (nylon MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66, nylon 66 / 6T in which 6T component is 50 mol% or less (6T: polyhexamethylene) Terephthalamide), copolymers of nylon 66 / 6I (6I: polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 610, etc. whose 6I component is 50 mol% or less; polyhexa Methylene terephthalamide (nylon 6T), polyhexamethylene isophthal Copolymers such as imide (nylon 6I), poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.

  Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.

  Among the polyamide-based resins, PA (nylon) 6, PA (nylon) 66, and PA (nylon) 6/66 are preferable among the above.

  The polyamide resin preferably has a heat of crystal melting of 10 J / g or more, more preferably 10 to 150 J / g, still more preferably 15 to 120 J / g, particularly preferably 20 to 100 J / g, and most preferably 25 to 25 J / g. 90 J / g. The crystal melting heat quantity within the above range includes the remaining amorphous part together with the crystal part specified by the crystal melting heat quantity.

  By setting the heat of crystal fusion of the polyamide resin within the above range, the amorphous part of the polyamide resin is removed from the surface of the thermoplastic resin molded body, and strong plating is achieved by the action of the micropores generated after the removal. This is preferable because a layer is formed.

  The amount of crystal melting heat is measured by DSC measurement. Take a 5-10 mg sample from the polyamide resin pellet to be measured, and use a DSC 600E manufactured by Shimadzu Corporation to perform a temperature scan twice under the conditions of a temperature increase rate of 20 ° C / min and a temperature decrease rate of 20 ° C / min. The amount of heat of fusion is defined as the amount of heat of crystal fusion.

  Examples of the styrenic resin include polymers of styrene and styrene derivatives such as α-substituted and nucleus-substituted styrene. Also included are copolymers composed mainly of these monomers and monomers of vinyl compounds such as acrylonitrile, acrylic acid and methacrylic acid and / or conjugated diene compounds such as butadiene and isoprene. For example, polystyrene, high impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), styrene-butadiene A copolymer (SBS resin) etc. can be mentioned.

Further, the polystyrene resin may include a styrene copolymer in which a carboxyl group-containing unsaturated compound for increasing compatibility with the polyamide resin is copolymerized. The styrene-based copolymer in which the carboxyl group-containing unsaturated compound is copolymerized in the presence of the rubber-like polymer, the carboxyl group-containing unsaturated compound and, if necessary, other monomers copolymerizable therewith Is a copolymer obtained by polymerizing Specific examples of ingredients include
1) In the presence of a rubbery polymer copolymerized with a carboxyl group-containing unsaturated compound, a monomer containing an aromatic vinyl monomer as an essential component or an aromatic vinyl and a carboxyl group-containing unsaturated compound as an essential component A graft polymer obtained by polymerizing monomers;
2) A graft copolymer obtained by copolymerizing a monomer having an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer,
3) a mixture of a rubber-reinforced styrenic resin that is not copolymerized with a carboxyl group-containing unsaturated compound, and a copolymer of monomers that have a carboxyl group-containing unsaturated compound and an aromatic vinyl as essential components;
4) A mixture of the above 1), 2), a copolymer containing an unsaturated compound containing a carboxyl group and an aromatic vinyl,
5) There is a mixture of the above 1), 2), 3), 4) and a copolymer containing aromatic vinyl as an essential component.

  In the above 1) to 5), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl. The carboxyl group-containing unsaturated compound is preferably 0.1 to 8% by mass, more preferably 0.2 to 7% by mass in the styrene resin.

  The olefin-based resin is a polymer having a C 2-8 monoolefin as a main monomer component, such as low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene random copolymer, One or more kinds selected from ethylene-propylene block copolymer, polymethylpentene, polybutene-1, modified products thereof and the like can be exemplified, and among these, polypropylene and acid-modified polypropylene are preferable.

Examples of polyphenylene ethers that can be used in the present invention include poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-chloromethyl-1). , 4-phenylene ether), poly (2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly (2-methyl-6-n-butyl-1,4-phenylene ether), poly (2- Ethyl-6-isopropyl-1,4-phenylene ether), poly (2-ethyl-6-n-propyl 1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether) , Poly (2- (4'-methylphenyl) -1,4-phenylene ether), poly (2-bromo-6-phenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1) , 4-phenylene ether), poly (2-phenyl-1,4-phenylene ether), poly (2-chloro-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether) Ter), poly (2-chloro-6-ethyl-1,4-phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-di-n-propyl) 1,4-phenylene ether), poly (2-methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-phenylene ether), poly (2-methyl -6-ethyl-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), poly (2,6 -Diethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) and the like. Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used.

  As other components blended together with the thermoplastic resin as necessary, from the viewpoint of increasing the adhesion strength between the thermoplastic resin molded body and the plating layer, a chelating agent, a water-soluble substance, a surfactant and / or a coagulant, A phosphorus compound can be mentioned.

  A chelating agent is a component which acts so that the metal contained in a plating bath becomes easy to adhere to the resin molding surface, and what is chosen from the following group can be used.

Aliphatic diamines such as methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine and hexamethylene diamine, aromatic diamines such as o-, m- and p-phenylene diamine, benzidine and diaminostilbene;
Ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane- Phosphonic acids such as 1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, or alkali metal salts or alkanolamine salts thereof;
Phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, or alkali metal salts or alkanolamine salts thereof;
Amino acids such as aspartic acid, glutamic acid, glycine, or alkali metal salts or alkanolamine salts thereof;
Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, aminopolyacetic acid such as diencoric acid or alkali metal salts or alkanolamine salts thereof ;
Glycolic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, malonic acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, α-hydroxy Organic acids such as propionic acid and α-hydroxyisobutyric acid or alkali metal salts or alkanolamine salts thereof;
Alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A;
Aminopoly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof, or polyethylenepolyamine poly (methylenephosphonic acid) or an alkali metal salt or alkanolamine salt thereof.

  The content of the chelating agent in the thermoplastic resin molded body is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 0.1-10 mass parts is still more preferable.

  A water-soluble substance means a substance that is soluble in water regardless of solubility, and is a polysaccharide such as starch, dextrin, pullulan, hyaluronic acid, carboxymethylcellulose, methylcellulose, ethylcellulose, or a salt thereof; propylene glycol, ethylene Polyhydric alcohols such as glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, polyoxyethylene glycol, polyoxypropylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin; polyvinyl alcohol, polyacrylic acid, polymalein Acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, acrylic acid-maleic anhydride copolymer, maleic anhydride-diisobutylene Copolymers, maleic anhydride - vinyl acetate copolymer, naphthalene sulfonate formalin condensates and their salts.

  Among these, those that are soluble in water but low in solubility are preferred, and specifically, those having a solubility in water (23 ° C.) of 300 g / 100 g or less are preferred, and those having a solubility of 100 g / 100 g or less are more preferred. The thing of 10 g / 100g or less is still more preferable. Examples of such include pentaerythritol (7.2 g / 100 g), dipentaerythritol (0.1 g / 100 g or less), and the like.

  The content ratio of the water-soluble substance in the thermoplastic resin molded body is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 0.01-15 mass parts is still more preferable.

  As the surfactant and / or coagulant, the surfactant (emulsifier) used when emulsion polymerization is applied during the production of the thermoplastic resin may remain in the resin, or an emulsifier such as bulk polymerization may be used. When a manufacturing method that is not used is applied, it may be added separately in a thermoplastic resin.

  The surfactant and / or the coagulant may be other than those used in emulsion polymerization in addition to those used in the emulsion polymerization of resins. The surfactant may be an anionic surfactant, a cationic surfactant, or a nonion. An ionic surfactant and an amphoteric surfactant are preferred.

  These surfactants include fatty acid salts, rosinates, alkyl sulfates, alkyl benzene sulfonates, alkyl diphenyl ether sulfonates, polyoxyethylene alkyl ether sulfates, sulfosuccinic acid diester salts, α-olefin sulfate salts, Anionic surfactants such as α-olefin sulfonates; Cationic surfactants such as mono- or dialkylamines or polyoxyethylene adducts thereof, mono- or di-long alkyl quaternary ammonium salts; alkyl glucosides, polyoxyethylene alkyls Ether, polyoxyethylene alkyl phenyl ether, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene propylene butyl ether Nonionic surfactants such as lock copolymers, fatty acid monoglycerides, amine oxides; amphoteric surfactants such as carbobetaine, sulfobetaine, and hydroxysulfobetaine.

  The surfactant and / or coagulant content in the thermoplastic resin molding is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin. 0.01 to 5 parts by mass is more preferable, and 0.01 to 2 parts by mass is even more preferable.

  The phosphorus compound is a component that acts to increase the adhesion strength of the plating, and can be used alone or in combination of two or more selected from the following.

Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o- or p-phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl ( 2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresyl phosphate, tris (2,6-dimethylphenyl) phosphate, tetraphenyl-m-phenylene diphosphate, tetraphenyl-p-phenylene diphosphate , Phenyl resorcinol polyphosphate, bisphenol A-bis (diphenyl phosphate), bisphenol A polyphenyl phosphate Feto, condensation type phosphoric acid ester such as di-pyrocatechol Hi-Posi phosphate;
Fatty acids such as normal phosphates such as diphenyl (2-ethylhexyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, ethyl pyrocatechol phosphate・ Aromatic phosphate esters;
Melamine polyphosphate, tripolyphosphoric acid, pyrophosphoric acid, orthophosphoric acid, hexametaphosphoric acid and other alkali metal salts, phytic acid and other phosphoric acid compounds or alkali metal salts or alkanolamine salts thereof;
Furthermore, as phosphorus compounds other than the above, phosphorus compounds that are used as known flame retardants and antioxidants for resins can be used.

  The content ratio of the phosphorus compound in the thermoplastic resin molded body is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin, 10 parts by mass is more preferable.

  The plating resin molded body obtained by applying the production method of the present invention has an adhesion strength (JIS H8630) between the thermoplastic resin molded body and the metal plating layer, preferably a maximum value of 10 kPa or more, more preferably a maximum value. A product having a maximum value of 50 kPa or more, more preferably a maximum value of 100 kPa or more, and particularly preferably a maximum value of 150 kPa or more can be obtained.

  The shape of the plated resin molded product obtained by applying the production method of the present invention, the type and thickness of the plated layer can be appropriately selected according to the application, and can be applied to various applications. Suitable for automotive parts such as emblems, wheel caps, interior parts and exterior parts.

<Plating resin molding>
The plated resin molded product of the present invention is obtained by the above-described production method, and in particular, a product obtained by plating a resin molded product obtained from a resin composition having the following composition is preferable.
(A) 10 to 90% by mass of a matrix resin having a water absorption rate (ISO 62) after 24 hours in water of 23 ° C. of 0.6% or more,
(B) 10-90% by mass of a styrene resin having a water absorption rate (ISO 62) of less than 0.6% after 24 hours in water at 23 ° C.
(C) Compatibilizer 0 to 40 parts by mass,
(D) Water-soluble substance having a solubility in water (25 ° C.) of 0.01 / 100 g to 10 g / 100 g (A) to (C) 0.01 to 20 parts by mass with respect to a total of 100 parts by mass and (E) As needed, 0.01-10 mass parts with respect to the total of 100 mass parts of surfactant (A)-(C) component The plating resin molding of this invention does not perform the etching process by chromic acid, Although a beautiful and strong plating layer is formed, the present invention includes a direct plating process and does not include a conventional electroless plating (chemical plating) process. ) A beautiful and strong plating layer is formed by a mechanism different from that including the step.

  Hereinafter, for comparison, the plating mechanism in the case of applying a plating method (without etching treatment with chromic acid) including a conventional electroless plating (chemical plating) step will be described first, and then the direct play of the present invention will be described. A plating mechanism when a plating method including a plating process is applied will be described.

(Plating method including electroless plating (chemical plating) process)
The plating of this method is formed by the following mechanisms (I) to (V).

(I) By using the components (A) to (D) and, if necessary, the component (E), the polyamide-based resin (sea) and the styrene-based resin (island) form a sea-island structure. The water-soluble substance of component (D) is greatly involved in the formation (or the combination of component (D) and component (E) is synergistically involved);
(II) A part of the polyamide-based resin phase (sea) forms a swollen layer in the sea-island structure by contact treatment with an acid (excluding harmful acids such as chromic acid) in the plating process;
(III) The well-known catalyst solution used in the plating step penetrates into the swelling layer and the catalyst is precipitated (the penetration depth of the catalyst solution in this case is deeper than that without the swelling layer);
(IV) When the plating metal penetrates into the swelling layer, it grows in the shape of a tree using the deposited catalyst as a nucleus to firmly bond the resin and the plating layer;
(V) Styrenic resin (island) acts to disperse in the swelling layer and suppress swelling, suppresses shrinkage of the swelling layer after plating, and suppresses interface breakdown between the resin molded body and the plating layer To act.

  Next, the manufacturing method of the plating resin molding of this invention is demonstrated for every process, clarifying the relationship with above-described mechanism (I)-(V) using FIG. FIG. 1 is a diagram conceptually showing the relationship between the manufacturing process and mechanisms (I) to (V).

  The plated resin molded body of the present invention is a known plating method, that is, a degreasing treatment step with an acid or a base (however, it is not a treatment with a known method such as chromic acid or potassium permanganate), and a step of treating with a catalyst application liquid By applying the electroless plating process, the surface of the resin molded body can be metal-plated.

[Molding resin moldings; Mechanism (I)]
A resin molded body containing the components (A) to (D) is molded into a desired shape suitable for the application by a known method such as injection molding. A 1st sea island structure is maintained or a 2nd sea island structure is formed because a resin molding contains (D) component and the (D) component and (E) component as needed. These sea-island structures are also present in the final product.

  By forming such a sea-island structure, in the next step, a swelling layer is easily formed in the sea [component (A)] near the surface of the resin molded body [expression of mechanism (II)], and island [(B ) Component] facilitates the swelling-inhibiting action of the swelling layer [expression of mechanism (V)].

When the second sea-island structure is formed, the area of the island (B-2) compared by observation with TEM is at least twice the area of the island (B-1).

[Degreasing treatment and contact treatment step with acid, etc .; Mechanism (II)]
The degreasing treatment is performed with a surfactant aqueous solution containing a base or an acid. In this invention, the etching etching process by the acid containing heavy metals, such as chromic acid used as the roughening process for improving the adhesive strength of a plating layer is unnecessary.

By this degreasing treatment and contact treatment with acid or the like, mechanism (II) is expressed, and as shown in FIG. 1 (a), in the resin molded body 11 forming the sea-island structure, the phase of component (A) (sea) Among them, the swelling layer 13 is formed in the phase of the component (A) near the surface, so that the mechanism (III) is easily developed in the next step. The phase (island) 14 of the component (B) is dispersed in both the phase 12 and the swelling layer 13. Swelling means a state where the volume is increased from the original volume, and the degree of increase is not limited. Note that the interface between the phase 12 and the swelling layer 13 is not a smooth boundary as shown in the figure.

  The acid or base used in the degreasing treatment is preferably in a low concentration, preferably less than 4N, more preferably 3.5N or less, and still more preferably 3.0N or less.

  For the degreasing treatment, a method of immersing the resin molded body in an acid or a base can be applied, and a method of immersing at a liquid temperature of 10 to 80 ° C. for 0.5 to 20 minutes can be applied.

  The acid may be selected from hydrochloric acid, phosphoric acid, sulfuric acid, and organic acids such as acetic acid, citric acid, and formic acid. The base may be selected from alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, carbonates such as sodium carbonate and potassium carbonate, and the like. it can.

  In this process, since chromic acid or the like is not used, the surface of the resin molded body 11 does not become rough as when chromic acid etching is performed, and maintains the same surface state as when it is molded.

[Processing with catalyst application liquid; Mechanism (III)]
After the degreasing treatment, for example, a water washing step, a step of treating with a catalyst application liquid, a water washing step, a step of treating with an activation liquid (activation step) and a water washing step can be performed. In addition, the process with a catalyst provision liquid and the process with an activation liquid can be performed simultaneously.

By this treatment step, as shown in FIG. 1B, mechanism (III) is expressed, the catalyst solution penetrates into the swelling layer 13 and the catalyst (Sn, Pd) 15 is deposited. (IV) and (V) are easily expressed. At this time, the penetration depth of the catalyst solution is deeper than that when the swelling layer 13 is not present, and penetrates the swelling layer from the surface of the resin molded body 11 to at least 10 nm.

  The treatment with the catalyst applying liquid is, for example, immersed in a 35% hydrochloric acid solution (10 to 20 mg / L) of tin chloride (20 to 40 g / L) at room temperature for about 1 to 5 minutes. In the treatment with the activation liquid, immersion is performed in a 35% hydrochloric acid solution (3 to 5 mg / L) of palladium chloride (0.1 to 0.3 g / L) at room temperature for 1 to 2 minutes.

[Electroless plating process; Mechanism (IV), (V)]
Next, electroless plating is performed. By this electroless plating, mechanisms (IV) and (V) are expressed as shown in FIG.

  That is, when the plating metal 16 penetrates into the swelling layer 13, it grows in the shape of a tree with the deposited catalyst 15 as a nucleus, and the resin molded body 11 and the plating layer 17 are firmly bonded.

  At this time, the phase (island) 14 of the component (B) is dispersed in the phase (sea) 12 and the swelling layer 13 of the component (A) and acts to suppress the swelling, and the swelling layer 13 after plating. It acts to suppress the shrinkage of the resin and to suppress the interface destruction between the resin molded body 11 and the metal plating layer 17. When the phase (island) 14 of the component (B) does not exist, an interface breakage occurs, and a phenomenon that the plating layer floats from the surface of the resin molded body 11 occurs.

  As a result, a plated resin molded body 10 having a beautiful and strong metal plating layer 17 on the surface of the resin molded body 11 is obtained. In addition, the plating metal does not substantially permeate into the phase (island) 14 of the component (B).

In the electroless plating step, a plating bath containing nickel, copper, cobalt, a nickel-cobalt alloy, gold or the like and a reducing agent such as formalin or hypophosphite can be used.
The pH and temperature of the plating bath are selected according to the type of plating bath used.

  When further plating is performed after electroless plating, after the activation treatment with acid or alkali, a multilayer electroplating process with one or more known plating metals such as copper is added depending on the application and function You can also

(Plating method including direct plating process)
When the plating method including the direct plating step of the present invention is applied, the mechanisms (I) to (III) are the same as the plating method including the electroless plating step, but the direct plating step and the electroless plating step. Mechanisms (IV) and (V) are different due to the difference.

When a plating method including an electroless plating process is applied, a thick electroless plating layer is formed due to the manifestation of mechanisms (IV) and (V) (thickness is about 200 nm or more).
However, when a plating method including a direct plating process is applied, the thickness of the conductive layer (corresponding to the above electroless plating layer) can be made less than about 10 to 200 nm (of course, processing conditions are set) In addition, the conductive metal can be dispersed without forming a layer in the thickness direction of the thermoplastic resin molded body continuously with the conductive layer. Can be.
In other words, as in the mechanism (IV) above, when the plating metal penetrates into the swelling layer, the conductive metal is dispersed without forming a layer, instead of growing as a tree root with the deposited catalyst as the core. Due to the presence, a strong conductive layer is considered to be formed despite the thinner layer.
Further, the conductive layer is not a uniform layer such as an electroless plating layer, but is present as a non-uniform layer as a whole (the thickness of the layer and the state of dispersion of the conductive metal are not constant). It is particularly preferable that a part of the conductive metal is present so as to be dispersed so as to surround the island made of the component (B).

(Plating layer adhesion test)
Using the plating resin moldings obtained in Examples and Comparative Examples, the adhesion strength (maximum value) between the resin molding and the metal plating layer was measured by the adhesion test method described in JIS H8630 Appendix 6.

(Components contained in thermoplastic resin moldings)
A-1 Polyamide (Polyamide 6, Ube Industries, UBE nylon 6 1013B, water absorption 1.8%)
B-1 ABS resin (styrene content 45% by mass, acrylonitrile 15% by mass, polybutadiene rubber 40% by mass, water absorption 0.2%)
B-2 AS resin (styrene content 75% by mass, acrylonitrile 25% by mass, water absorption 0.2%)
B-3 Acid-modified ABS resin (styrene content 42% by mass, acrylonitrile 16% by mass, rubber content 40% by mass, methacrylic acid 2% by mass, water absorption 0.2%)
C-1 Dipentaerythritol

Examples 1-4
Each component shown in Table 1 was mixed with a V-type tumbler and then melt-kneaded with a twin-screw extruder (manufactured by Nippon Steel, TEX30, cylinder temperature 230 ° C.) to obtain pellets.

  Next, a molded body of 100 × 50 × 3 mm was obtained by an injection molding machine (cylinder temperature 240 ° C., mold temperature 60 ° C.), and electroless plating was performed in the following process sequence using this molded body as a test piece. A resin molded body was obtained. Table 1 shows the adhesion strength of the plating layers in these plated resin moldings.

(1) Degreasing process The resin molding was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50g / L aqueous solution (liquid temperature of 40 degreeC) for 5 minutes.

(2) Etching Step The resin molded body was immersed for 5 minutes in an aqueous solution (liquid temperature 40 ° C.) of 35% by mass hydrochloric acid 200 ml / L (2.3 N).

(3) Catalyst application process It immersed for 3 minutes in the mixed aqueous solution (liquid temperature of 25 degreeC) of 35 mass% hydrochloric acid 150ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd. product) 40ml / L aqueous solution.

(4) Direct plating process The resin molding was immersed in the selector liquid (45 degreeC, pH12) of the following composition for 3 minutes, and the electroconductive layer was formed in the resin molding surface.
In FIG. 2, the transmission electron microscope (TEM) photograph after the direct plating of Example 1 is shown. The TEM photograph was taken as follows. After embedding the sample in an epoxy resin, an ultrathin section was prepared with a diamond microtom, and then observed using a JSM1200EX transmission electron microscope at an acceleration voltage of 120 KV.

Copper sulfate 3g / L
Sodium hydroxide 30g / L
Glucose 10g / L
Hydantoin 10g / L

(5) Copper electroplating step The resin molded body was immersed in a plating bath (liquid temperature 25 ° C.) having the following composition, and electroplated for 120 minutes.

(Composition of plating bath)
Copper sulfate _{(CuSO 4 · 5H 2 O)} 200g / L
Sulfuric acid (98%) 50g / L
Chloride ion (Cl ⁻ ) 5 ml / L,
Top Lucina 2000MU (Okuno Pharmaceutical Co., Ltd.) 5ml / L

  The appearances of the molded bodies of Examples 1 to 4 were smooth and beautiful.

Comparative Example 1
Using the same thermoplastic resin molded body as in Example 2, a plated resin molded body was produced by the following steps not including the direct plating method. Although the maximum value of the adhesion strength of the plated resin molded body was 100 kPa and the appearance was smooth and beautiful, more man-hours were required as compared with Example 2.

(1) Degreasing process The test piece was immersed in an aceclin A-220 (Okuno Pharmaceutical Co., Ltd.) 50 g / L aqueous solution (liquid temperature 40 degreeC) for 20 minutes.

(2) Step of contact treatment with acid The substrate was immersed in 100 ml of 1.0 N hydrochloric acid (liquid temperature 40 ° C.) for 5 minutes.

(3) Catalyst application process It immersed for 3 minutes in the mixed aqueous solution (liquid temperature of 25 degreeC) of 35 mass% hydrochloric acid 150ml / L and catalyst C (Okuno Pharmaceutical Co., Ltd. product) 40ml / L aqueous solution.

(4) 1st activation process The test piece was immersed for 3 minutes in 98 mass% sulfuric acid 100ml / L aqueous solution (liquid temperature of 40 degreeC).

(5) 2nd activation process The test piece was immersed for 2 minutes in 15 g / L sodium hydroxide aqueous solution (liquid temperature of 40 degreeC).

(6) Electroless plating step of nickel The test pieces were made of 150 ml / L of chemical nickel HR-TA (Okuno Pharmaceutical Co., Ltd.) and 150 ml / L of chemical nickel HR-TB (Okuno Pharmaceutical Co., Ltd.). It was immersed in a mixed aqueous solution (liquid temperature 40 ° C.) for 5 minutes. FIG. 3 shows a transmission electron microscope (TEM) photograph after electroless plating.

(7) Acid activation process The test piece was immersed for 1 minute in 100 g / L aqueous solution (liquid temperature 25 degreeC) of top sun (Okuno Pharmaceutical Co., Ltd. product).

(8) Copper electroplating process The test piece was immersed in the same plating bath (liquid temperature 25 degreeC) as Example 1, and electroplated for 120 minutes.

  In the TEM photograph after the direct plating process of Example 1, the lower left half is a thermoplastic resin molded body, the upper right half is an epoxy resin, and the black line at the boundary portion indicates a conductive layer, Black dots present along the black lines indicate conductive metals dispersed without forming a layer. As can be seen from the 200 nm scale shown in the figure, the conductive layer was very thin and not uniform, and part of the conductive metal was dispersed so as to surround the island made of component (B). .

In the TEM photograph after the electroless plating treatment of Comparative Example 1, the upper black layer is the electroless plating layer. As can be seen from the 200 nm scale shown in the figure, the thickness was about 200 nm.
In both Example 1 and Comparative Example 1, no changes in appearance such as wrinkles, cracks, and swelling of the plating layer were observed at all by visual observation after the heat cycle tests 1 and 2.

It is a figure for demonstrating the plating formation mechanism (plating formation mechanism by the method including an electroless-plating process) of a plating resin molding. 2 is a TEM photograph showing a phase structure of a molded body after direct plating in Example 1. FIG. 4 is a TEM photograph showing a phase structure of a molded body after electroless plating in Comparative Example 1.

Claims (10)

A step of contact-treating the thermoplastic resin molded body with an acid or base not containing heavy metal,
A step of treating with a catalyst applying liquid,
A method for producing a plated resin molded body comprising a step of forming a conductive layer on the surface of a thermoplastic resin molded body by a direct plating method and a step of electroplating, and does not include an etching step using an acid containing heavy metal .   The plating resin molding according to claim 1, wherein the direct plating method is a step of forming a conductive layer on the surface of the thermoplastic resin molding using a selector liquid containing a metal compound, a reducing compound and a metal hydroxide. Body manufacturing method.   The manufacturing method of the plating resin molding of Claim 1 or 2 with which the thermoplastic resin molding contains polyamide.   The method for producing a plated resin molded article according to any one of claims 1 to 3, wherein the thermoplastic resin molded article further contains a substance having a solubility in water (23 ° C) of 300 g / 100 g or less. It is the plating resin molding obtained by the manufacturing method of the plating resin molding in any one of Claims 1-4,
It has at least one of the following (1) phase structure of the resin molded body and (2) the bonding state between the resin molded body and the metal plating layer. Plated resin molded product that cannot be recognized.
(1) Phase structure of molded resin (1-1) Sea-island structure where component (A) is sea and component (B) is an island, or (1-2) Component (A) is sea, (B) Island (B-1) in the sea-island structure when the component is an island-island structure, including the components (A) to (C) and not including the component (D), B-2) must be a sea-island structure.
(2) Joined state of resin molded body and metal plating layer In the vicinity of the surface of the resin molded body, the component (A) which is the sea forms a swelling layer, and the plating metal penetrates into the swelling layer, The plating metal is not substantially permeated into the component (B).
(Heat cycle test 1)
Using a plated resin molded body having a length of 100 mm, a width of 50 mm, and a thickness of 3 mm as a test piece, held at −30 ° C. for 60 minutes, held at room temperature (20 ° C.) for 30 minutes, held at 75 ° C. for 60 minutes, and at room temperature (20 ° C.) A heat cycle test of a total of 3 cycles is performed with 30 minutes holding as one cycle.
(Heat cycle test 2)
Using a plated resin molded body having a length of 100 mm, a width of 50 mm, and a thickness of 3 mm as a test piece, held at −30 ° C. for 60 minutes, held at room temperature (20 ° C.) for 30 minutes, held at 85 ° C. for 60 minutes, and at room temperature (20 ° C.) A heat cycle test of a total of 3 cycles is performed with 30 minutes holding as one cycle.   In (1-2) of Requirement (1), the area of the island (B-2) compared by observation with a transmission electron microscope (TEM) is at least twice the area of the island (B-1) The plated resin molded product according to claim 5.   The plating resin molding according to claim 5 or 6, wherein, in the requirement (2), the plating metal permeates the swelling layer of at least 10 nm from the surface of the resin molding. After the step of forming a conductive layer by the direct plating method on the surface of the thermoplastic resin molded body,
The thickness of the conductive layer on the surface of the thermoplastic resin molded body is 10 nm to 1000 nm, and a conductive metal forms a layer in the thickness direction of the thermoplastic resin molded body continuously with the conductive layer. The plating resin molding in any one of Claims 5-7 currently disperse | distributing and existing.   The plated resin molded article according to claim 8, wherein the conductive metal is dispersed and formed without forming a uniform layer in a thickness range of 10 nm to 1000 nm from the surface of the thermoplastic resin molded article. In the thickness range from 10 nm to 1000 nm from the surface of the thermoplastic resin molded body, the conductive metal is present in a dispersed manner so as to partially surround the island made of the component (B) without forming a uniform layer. The plated resin molded product according to claim 8 or 9, wherein