JP2017066499A - Plating resin composition, and plating molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plating rubber-reinforced styrene resin composition excellent in a plating appearance after a cold heat cycle, and a plated molding.SOLUTION: A plating rubber-reinforced styrene composition or a flat plate molding (length×width×thickness=100 mm×50 mm×3 mm) obtained by molding the plating rubber-reinforced styrene composition is plated. After this, 10 cycles are repeated by exemplifying 1 cycle by one hour of-30°C, 30 minutes of → 23°C, 1 hour of 80°C, and 1 hour of 23°C repeatedly is characterized in that the point is 1 or less when the plated molding surface is evaluated in the following manner: (1) a point is applied according to the size of the bulging portion of the plated film. The maximum one longer side of one bulging portion is 1 cm or more: the maximum longer side of one portion of the bulging portion is 1 cm or more: the maximum longer side of one portion of 2 points is less than 1 cm: no one point bulging portion; 0 point; (2) The point is decided at the bulging portion of all plating films; and (3) The points are aggregated.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a rubber-reinforced styrene-based resin composition for plating and a plated molded article having a good appearance in cold cycle plating. The present invention also relates to a method for improving the plating appearance of the plated molded article.

ABS resin is used in various applications including automobile parts, home appliances, and office equipment parts because of its excellent impact resistance, heat resistance, and workability. In particular, there are many examples in which automobile parts are used after being plated. Such a plating process generally comprises steps of degreasing, chemical etching, neutralization, catalyst application, activation, electroless plating, acid activation, and electroplating. As a solvent used for chemical etching, a mixed chromic anhydride-concentrated sulfuric acid solution is generally used. By roughening the surface of the resin molded product, fine irregularities suitable for the plating base are formed, and the metal film plated with the resin Good adhesion can be added between the two.

In recent years, from the viewpoint of weight reduction and the like, an increase in the size of a plating application site and a complicated design have been demanded. Along with this, with respect to plating adhesion strength, there has been a demand for higher plating adhesion strength than ever before, and there has been a problem that plating appearance defects frequently occur with complicated design.

  As a method for improving the plating adhesion strength, Patent Document 1 discloses a method of pre-treating a resin material with ozone gas, and then performing electroless plating treatment. Further, Patent Document 2 discloses an unsaturated bond. In the electroless plating treatment of the resin material having, there is disclosed a method of performing an ultraviolet treatment that irradiates the resin material with ultraviolet rays. However, even if good plating adhesion strength is obtained, it is still insufficient as to whether a good plating appearance (hereinafter referred to as “plating appearance after cooling cycle”) can be maintained in an environment where temperature fluctuation is severe. Is.

Japanese Unexamined Patent Publication No. 01-092377

JP 2004-263224 A

An object of the present invention is to provide a rubber-reinforced styrene-based resin composition for plating and a plated molded article having a good plating appearance after a thermal cycle. Furthermore, the objective of this invention is providing the method of improving the plating external appearance of a plating molded product.

That is, after plating a rubber-reinforced styrene-based resin composition for plating, which is obtained by molding the rubber-reinforced styrene-based resin composition (length × width × thickness = 100 mm × 50 mm × 3 mm) 1 hour at −30 ° C. → 30 minutes at 23 ° C. → 1 hour at 80 ° C. → 1 hour at 23 ° C. is repeated 10 cycles, and when the surface of the plated product is evaluated as follows, the point is 1 point Provided is a rubber-reinforced styrene-based resin composition for plating characterized by the following.
(1) A point is given according to the size of the swelling portion of the plating film.
The maximum long side of one bulging part is 1 cm or more: 2 points The maximum long side of one bulging part is less than 1 cm: 1 point
No swelling portion: 0 points (2) Points are determined at the swelling locations of all plating films.
(3) Sum the points.

  The present invention also provides a plated product using the rubber-reinforced styrene resin composition for plating.

  In the plated molded article, the area of the catalyst adsorption layer having a thickness of 10 nm or more is preferably 70% or more in the plated molded article, and the area of the catalyst adsorption layer having a thickness of 15 nm or more in the plated molded article is 70%. It is more preferable to have the above.

  Furthermore, the present invention provides a method for improving the plating appearance of a plated molded article.

  ADVANTAGE OF THE INVENTION According to this invention, the rubber reinforcement | strengthening styrene-type resin composition for plating and plating molded article which are excellent in the plating external appearance after a thermal cycle can be provided. Moreover, the method of improving the plating external appearance of a plating molded product can be provided.

Hereinafter, the present invention will be described in detail.

  The rubber-reinforced styrene resin composition for plating used in the present invention is a rubber-like polymer comprising an aromatic vinyl monomer and a vinyl monomer copolymerizable with an aromatic vinyl monomer. A graft copolymer (A) obtained by graft polymerization or the graft copolymer (A), an aromatic vinyl monomer, and a vinyl monomer copolymerizable with the aromatic vinyl monomer are polymerized. Is a mixture containing the copolymer (R).

  Examples of the rubbery polymer constituting the graft copolymer (A) include conjugated diene rubbers such as polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-nonconjugated diene rubber, and the like. Examples thereof include ethylene-propylene rubbers, acrylic ester rubbers such as polybutyl acrylate, polyorganosiloxane rubbers, and composite rubbers composed of two or more of these rubbers. Of these, conjugated diene rubbers are particularly preferable.

  Although there is no restriction | limiting in particular in the weight average particle diameter of a rubber-like polymer, 0.01-2.0 micrometers is preferable from a physical property balance, such as impact resistance, fluidity | liquidity, and color development property, and 0.1-1.0 micrometer is more. preferable. Moreover, it can also adjust by agglomerating and enlarging the rubber-like polymer whose weight average particle diameter is 0.05-0.3 micrometer.

  The graft copolymer (A) of the present invention grafts an aromatic vinyl monomer and a vinyl monomer copolymerizable with the aromatic vinyl monomer in the presence of the rubber-like polymer described above. Obtained by polymerization.

  Examples of the aromatic vinyl monomer constituting the graft copolymer (A) include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.

  As a vinyl monomer copolymerizable with the aromatic vinyl monomer constituting the graft copolymer (A), a vinyl cyanide monomer, a (meth) acrylic acid ester monomer, a maleimide monomer A monomer, an amide-type monomer, an unsaturated carboxylic acid monomer, etc. are mentioned, It can use 1 type (s) or 2 or more types. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and examples of (meth) acrylic acid ester monomers include methyl (meth) acrylate and (meth) acrylic acid. Ethyl, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, (di) bromo (meth) acrylate Examples thereof include phenyl and chlorophenyl (meth) acrylate, examples of the maleimide monomer include N-phenylmaleimide and N-cyclohexylmaleimide, and examples of the amide monomer include acrylamide and methacrylamide. Unsaturated carboxylic acid monomers include acrylic acid and methacrylic acid Maleic acid, fumaric acid, and itaconic acid can be exemplified.

  There is no particular limitation on the composition ratio of the above-mentioned monomer graft-polymerized on the rubber-like polymer, but aromatic vinyl monomer 60 to 90% by weight, vinyl cyanide monomer 10 to 40% by weight Composition ratio of 0 to 30% by weight of other monomers, 30 to 80% by weight of aromatic vinyl monomers, 20 to 70% by weight of (meth) acrylate monomers and other copolymerizable monomers Composition ratio of 0 to 50% by weight of vinyl monomer, 20 to 70% by weight of aromatic vinyl monomer, 20 to 70% by weight of (meth) acrylate monomer, vinyl cyanide monomer The composition ratio is preferably from 10 to 60% by weight and from 0 to 50% by weight of another copolymerizable vinyl monomer (the total amount of monomers grafted onto the rubbery polymer is 100% by weight). To do).

The graft ratio of the graft copolymer (A) and the weight average molecular weight of the acetone-soluble component can be determined as follows. From the viewpoint of balance of physical properties such as impact resistance, fluidity and color development, the graft ratio is 10 It is preferably ˜150%, more preferably 20 to 100%. From the viewpoint of balance of physical properties such as impact resistance and fluidity, the acetone-soluble part preferably has a weight average molecular weight of 50,000 to 200,000.
Graft rate (%) = (XY) / Y × 100
X: Acetone-insoluble amount of graft copolymer Y: Amount of rubbery polymer in graft copolymer
Weight average molecular weight of acetone-soluble matter An acetone-soluble part is precipitated in methanol to obtain a polymer, and then dissolved in tetrahydrofuran and measured using liquid chromatography. The weight average molecular weight (Mw) is determined using polystyrene having a known molecular weight as a standard solution.

  Examples of the aromatic vinyl monomer composing the copolymer (R) and the vinyl monomer copolymerizable with the aromatic vinyl monomer are those exemplified for the graft copolymer (A) described above. And the same monomers.

  Although there is no restriction | limiting in particular in the composition ratio of the monomer which comprises a copolymer (R), The composition ratio similar to what was illustrated by the graft copolymer (A) mentioned above as a preferable composition ratio is mentioned.

The weight average molecular weight of the copolymer (R) can be determined as follows, and is preferably 5 to 200,000 from the viewpoint of balance of physical properties such as impact resistance and fluidity.
The weight average molecular weight is dissolved in tetrahydrofuran and measured using liquid chromatography. The weight average molecular weight (Mw) is determined using polystyrene having a known molecular weight as a standard solution.

  The polymerization method of the graft copolymer (A) and the copolymer (R) constituting the rubber-reinforced styrene resin composition is not particularly limited, and for example, emulsion polymerization method, suspension polymerization method, solution polymerization method, block shape It can be produced by a polymerization method or a combination of these methods.

  Other thermoplastic resin compositions can also be mixed with the rubber-reinforced styrene resin composition. Examples of such other thermoplastic resins that can be used include acrylic resins such as polymethyl methacrylate, polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyamide resins, and polylactic acid resins.

  Further, the rubber-reinforced styrene-based resin composition includes a hindered amine light stabilizer, a hindered phenol-based, a sulfur-containing organic compound-based, a phosphorus-containing organic compound-based antioxidant, a phenol-based, an acrylate-based, etc. Stabilizers, benzoate, benzotriazole, benzophenone, salicylate UV absorbers, organic nickel, lubricants such as higher fatty acid amides, plasticizers such as phosphate esters, polybromophenyl ether, tetrabromobisphenol A, brominated epoxy oligomers, halogenated compounds such as brominated compounds, phosphorus compounds, flame retardants and flame retardants such as antimony trioxide, odor masking agents, carbon black, titanium oxide, pigments, and dyes You can also Furthermore, reinforcing agents and fillers such as talc, calcium carbonate, aluminum hydroxide, glass fiber, glass flake, glass bead, carbon fiber, and metal fiber can be added.

  The mixing of the resin containing the rubber-reinforced styrene resin composition can be performed by a known method such as a commonly used roll, Banbury mixer, extruder, kneader.

  The rubber-reinforced styrene-based resin composition thus obtained is molded by injection molding, extrusion molding, compression molding, injection compression molding, blow molding, etc., and the resulting resin molded product is obtained by a known plating method, for example, Plating can be performed under the same conditions as plating conditions for ordinary ABS resin.

The plating rubber-reinforced styrene-based resin composition of the present invention is obtained by plating a flat plate product (vertical × horizontal × thickness = 100 mm × 50 mm × 3 mm) obtained by molding the rubber-reinforced styrene-based resin composition, 1 hour at -30 ° C. → 30 minutes at 23 ° C. → 1 hour at 80 ° C. → 1 hour at 23 ° C. is repeated 10 cycles (hereinafter referred to as “cooling cycle”). It is a rubber-reinforced styrene-based resin composition for plating having a point of 1 or less when evaluated. If the point exceeds 1, the appearance of plating after the cooling and heating cycle is inferior.
(1) A point is given according to the size of the swelling portion of the plating film.
The maximum long side of one bulging part is 1 cm or more: 2 points The maximum long side of one bulging part is less than 1 cm: 1 point
No swelling portion: 0 points (2) Points are determined at the swelling locations of all plating films.
(3) Sum the points.

  In order to make the point 1 or less, the area of the catalyst adsorption layer having a thickness of 10 nm or more in the plated molded article is preferably 70% or more, and the area of the catalyst adsorption layer having a thickness of 15 nm or more in the plating molded article. Is more preferably 70% or more. In the molded product, when the area of the catalyst adsorption layer having a thickness of 10 nm or more is less than 70%, the plating appearance after the cooling and heating cycle tends to be inferior. The upper limit of the catalyst adsorption layer is preferably as thick as possible, but is preferably less than 40 nm from the viewpoint of palladium cost and catalyst efficiency.

  The plating process generally includes degreasing, chemical etching, neutralization, catalyst application, activation, electroless plating, acid activity, and electroplating processes, and palladium or tin is used in the catalyst application process. When the catalyst palladium or tin is adsorbed on the resin surface, the metal ions are precipitated as a metal to form a metal coating (hereinafter referred to as a plating layer). That is, the catalyst adsorption layer means a layer in which palladium, tin or the like formed in the catalyst application step is present.

  As a method for increasing the area of the catalyst adsorption layer having a thickness of 10 nm or more in the plated molded product, an increase in the content of the rubbery polymer in the rubber-reinforced styrene resin composition used in the resin molded product, a graft copolymer (A) and the method of increasing the weight average molecular weight of an acetone soluble part, and the increase of vinyl cyanide-type monomer content which comprises a copolymer (R) are mentioned from a viewpoint of balance with various physical properties. There is a preferable range, which will be described in the following paragraph. Moreover, the adjustment by the treatment time in a catalyst provision process and the palladium concentration of a process liquid is also mentioned.

  The rubber-like polymer content in the rubber-reinforced styrene resin composition is preferably 9 to 25% by weight, and more preferably 11 to 21% by weight.

  The content of the vinyl cyanide monomer constituting the graft copolymer (A) and the copolymer (R) of the rubber-reinforced styrene resin composition is preferably 20 to 30% by weight, and 21 to 29% by weight. Is more preferable.

  The weight average molecular weight of the acetone soluble part of the rubber-reinforced styrene resin composition is preferably 8 to 150,000, and more preferably 9 to 140,000.

  The method for adjusting the weight average molecular weight of the acetone soluble part is not particularly limited, but can be appropriately adjusted depending on the chain transfer agent used at the time of polymerization.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these. In addition, the part and% which are shown in an Example are based on a weight.

Production of Graft Copolymer (A-1) In a pressure-resistant polymerization reactor, charged with 138 parts of polymerized water and 65 parts by weight of polybutadiene latex (weight average particle size 0.39 μm) (solid content), nitrogen substitution was performed, When the temperature in the tank reached 61 ° C., an aqueous solution in which 0.16 parts by weight of potassium persulfate was dissolved in 11 parts by weight of deionized water was added. After reaching 65 ° C., a mixture of 9.4 parts by weight of acrylonitrile, 25.6 parts by weight of styrene and 0.15 parts by weight of t-dodecyl mercaptan, 20 parts by weight of deionized water and 1.5 parts by weight of sodium dehydroabietate An aqueous emulsifier solution in which was dissolved was added continuously over 4.5 hours. Thereafter, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Thereafter, salting out, dehydration, and drying were performed to obtain a powder of the graft copolymer (A-1). When the graft ratio and the weight average molecular weight of the acetone soluble part of the obtained graft copolymer (A-1) were measured by the following method, the graft ratio was 37.0% and the weight average molecular weight of the acetone soluble part. Was 116,000.
<Measurement of graft ratio of graft copolymer (A-1)>
About 2 g of the graft copolymer (A-1) powder weighed is immersed in 60 mL of acetone for 24 hours, and then separated into an acetone insoluble part and an acetone soluble part with a glass filter. The separated acetone insoluble part was vacuum-dried for 24 hours, and then its weight was measured.
Graft rate (%) = (XY) / Y × 100
X: Acetone insoluble part after vacuum drying (g)
Y: amount of rubbery polymer in the graft copolymer (g)
<Measurement of weight average molecular weight of acetone soluble part of graft copolymer (A-1)>
About 1 g of the graft copolymer (A-1) powder is immersed in reagent-grade acetone for at least 24 hours. The solution is separated into a soluble part and an insoluble part with a centrifuge. The acetone soluble part separated by the centrifuge is precipitated in reagent-grade methanol to obtain a polymer. The obtained polymer is dissolved in reagent-grade tetrahydrofuran to prepare a sample for liquid chromatography. This sample was subjected to liquid chromatography (Agilent 1260 Infinity manufactured by Agilent Technologies), and the molecular weight (Mw) was calculated using polystyrene with a known molecular weight as a standard solution.

Production of copolymer (R-1) 27 parts of acrylonitrile, 73 parts of styrene, 10 parts of ethylbenzene as a solvent, 1,1-di (t-hexylperoxy) cyclohexane as an initiator (10 hours and half) A mixed solution was prepared using 0.184 parts of the initial temperature (86.7 ° C.) and 0.42 parts of t-dodecyl mercaptan as the chain transfer agent, and stored at 5 ° C. or lower. The prepared mixed solution was continuously supplied at a rate of 1.52 kg / hr to a reactor with a double helical ribbon blade having a volume of 20 L maintained at a reaction temperature of 118 ° C. to perform polymerization. The mixed solution containing the copolymer was continuously extracted by a pump at the same rate as the supply rate, and was sent to a gas-liquid separator maintained at 283 ° C. and 45 torr to separate the copolymer and the unreacted solution. . A copolymer (R-1) was obtained by pelletizing the separated copolymer. When the polymerization was stabilized, the polymerization rate was 49%, and the copolymer when the polymerization rate was reached was used for evaluation of physical properties and the like. When the weight average molecular weight of the obtained copolymer (R-1) was measured by the method shown below, the weight average molecular weight was 111,000.

<Measurement of weight average molecular weight of copolymer (R-1)>
About 1 g of the copolymer (R-1) powder is dissolved in reagent-grade tetrahydrofuran to prepare a sample for liquid chromatography. This sample was subjected to liquid chromatography (Agilent 1260 Infinity manufactured by Agilent Technologies), and the molecular weight (Mw) was calculated using polystyrene with a known molecular weight as a standard solution.

Production of Copolymers (R-2) to (R-3) Copolymers (R-2) to (R-2) to (R-3) were produced in the same manner as the copolymer (R-1) except that the raw materials shown in Table 1 were changed. R-3) was obtained. Moreover, the weight average molecular weights of the obtained copolymers (R-2) to (R-3) were measured in the same manner as the copolymer (R-1), and the results are shown in Table 1.

[Examples 1-6 and Comparative Examples 1-3]
After mixing the graft copolymer (A-1) and the copolymers (R-1) to (R-3) at the blending ratios shown in Table 2, a cylinder temperature of 250 is used using a 50 mm extruder (manufactured by Tanabe Seiki). After melt-kneading at 0 ° C., the mixture was pelletized. Using the rubber-reinforced styrene-based resin pellets obtained, the weight average molecular weight (Mw) of the acetone soluble part was measured by the following method. Moreover, about the obtained rubber reinforced styrene-type resin pellet, the flat plate test piece was created with the injection molding machine, and the plating external appearance after a thermal cycle was evaluated.

<Measurement of weight average molecular weight (Mw) of acetone soluble part>
About 1 g of rubber-reinforced styrene resin pellets are immersed in a reagent grade acetone solution for at least 24 hours. The solution is separated into a soluble part and an insoluble part with a centrifuge. The acetone soluble part separated by the centrifuge is precipitated in reagent-grade methanol to obtain a polymer. The obtained polymer is dissolved in reagent-grade tetrahydrofuran to prepare a sample for liquid chromatography. This sample was subjected to liquid chromatography (Agilent 1260 Infinity manufactured by Agilent Technologies), and the molecular weight (Mw) was calculated using polystyrene with a known molecular weight as a standard solution.

  After forming a flat plate product for plating (vertical x horizontal x thickness = 100 mm x 50 mm x 3 mm) using a pin gate mold with an injection molding machine, and plating with the following method, observation of the catalyst adsorption layer and cooling The appearance of plating after the cycle was measured. Moreover, the comparative example 3 performed the plating process similarly to others except having changed into the catalyst (Palladium chloride-stannic chloride-hydrochloric acid aqueous solution, room temperature x 1 minute) of the plating process.

<Plating method>
Degreasing (surfactant aqueous solution, 55 ° C. × 5 minutes), etching (sulfuric acid-chromic anhydride mixed solution, 67 ° C. × 10 minutes), neutralization (hydrochloric acid aqueous solution, room temperature × 2 minutes), catalyst (palladium chloride-chloride chloride) Monotin-hydrochloric acid aqueous solution, room temperature x 3 minutes), accelerator (sulfuric acid aqueous solution, 45 ° C x 4 minutes), electroless plating (nickel sulfate-sodium hypophosphite-sodium citrate nickel plating solution), electricity Plating (copper sulfate bath → nickel sulfate bath → chromic anhydride bath).

<Observation of catalyst adsorption layer>
After polishing the cross section of the plated resin molded product obtained above using a CP processing apparatus (cross section polisher, manufactured by JEOL Ltd.), the FE-SEM (electron emission electron gun mounted scanning electron microscope) Elemental mapping of palladium was performed using a STEM-EDS detector to define a band-like region where palladium was present as a catalyst adsorption layer. Furthermore, the thickness of the catalyst adsorption layer was measured in the range of about 1000 nm using the measurement function attached to the apparatus, and the ratio of the catalyst adsorption layer having a thickness of 10 nm or more was determined from the following. Moreover, it calculated | required similarly about the ratio of the catalyst adsorption layer of thickness 15nm or more.
Ratio (%) = total amount of catalyst adsorption layer region having a thickness of 10 nm or more (nm) / total measurement distance (nm) × 100

<Evaluation after cooling cycle>
The plated resin molded product obtained above was repeated 10 cycles with 1 cycle at −30 ° C. for 1 hour → 23 ° C. for 30 minutes → 80 ° C. for 1 hour → 23 ° C. for 1 hour. It was evaluated as follows.
(1) A point is given according to the size of the swelling portion of the plating film.
The maximum long side of one bulging part is 1 cm or more: 2 points The maximum long side of one bulging part is less than 1 cm: 1 point
No swelling portion: 0 points (2) Points are determined at the swelling locations of all plating films.
(3) The plating appearance after the cooling and heating cycle was evaluated by the total of points.
Point 0: ○ (Plating appearance after cooling cycle is good)
Point 1: △ (Plating appearance after cooling cycle is slightly inferior)
Point 2 or more: × (Plating appearance after cooling cycle is inferior)

These evaluation results are shown in Table 2.

  As is apparent from Table 2, Examples 1 to 6 using the rubber-reinforced styrene resin composition of the present invention were all excellent in plating appearance after the cooling and heating cycle. In comparisons 1 to 3, the total points exceeded 1 in the evaluation after the cooling and heating cycle, and no excellent plating appearance after the cooling and heating cycle was obtained.

As described above, since the rubber-reinforced styrene-based resin composition and the plated molded product of the present invention have excellent plating appearance after the thermal cycle, a plated molded product that can be used even in an environment with severe temperature fluctuations. Can be provided.

Claims (5)

It is a rubber-reinforced styrene-based resin composition for plating, and after plating a flat plate product (vertical × horizontal × thickness = 100 mm × 50 mm × 3 mm) obtained by molding the rubber-reinforced styrene-based resin composition, 1 hour at 30 ° C → 30 minutes at 23 ° C → 1 hour at 80 ° C → 1 hour at 23 ° C is repeated 10 cycles. When the surface of the plated product is evaluated as follows, the total number of points is 1 point or less. A rubber-reinforced styrene-based resin composition for plating, characterized in that
(1) A point is given according to the size of the swelling portion of the plating film.
The maximum long side of one bulging part is 1 cm or more: 2 points The maximum long side of one bulging part is less than 1 cm: 1 point
No swelling portion: 0 points (2) Points are determined at the swelling locations of all plating films.
(3) Sum the points.   A plated molded article using the rubber-reinforced styrene-based resin composition for plating according to claim 1.   The plated molded article according to claim 2, wherein a region of the catalyst adsorption layer having a thickness of 10 nm or more has 70% or more in the plated molded article.   The plated molded article according to claim 2, wherein the area of the catalyst adsorption layer having a thickness of 15 nm or more has 70% or more in the plated molded article. The method to improve the plating external appearance of the plating molded product in any one of Claim 3 or 4.