WO2008012984A1 - Procédé de métallisation de surfaces en plastique - Google Patents

Procédé de métallisation de surfaces en plastique Download PDF

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Publication number
WO2008012984A1
WO2008012984A1 PCT/JP2007/060332 JP2007060332W WO2008012984A1 WO 2008012984 A1 WO2008012984 A1 WO 2008012984A1 JP 2007060332 W JP2007060332 W JP 2007060332W WO 2008012984 A1 WO2008012984 A1 WO 2008012984A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
plastic surface
metallizing
surface according
plastic
Prior art date
Application number
PCT/JP2007/060332
Other languages
English (en)
Japanese (ja)
Inventor
Yasuyuki Kuramochi
Kaori Nakayama
Original Assignee
Ebara-Udylite Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ebara-Udylite Co., Ltd. filed Critical Ebara-Udylite Co., Ltd.
Priority to CN2007800273670A priority Critical patent/CN101490310B/zh
Priority to KR1020097002064A priority patent/KR101365970B1/ko
Publication of WO2008012984A1 publication Critical patent/WO2008012984A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics

Definitions

  • the present invention relates to a method for metallizing a plastic surface. More specifically, the present invention provides high adhesion only to a plastic surface without plating and depositing on the surface of a jig for holding the product to be stuck. The present invention relates to a method for forming a plating film.
  • ABS acrylonitrile butadiene styrene
  • PCZABS polycarbonate Z atari mouth-tolyl butadiene styrene
  • the object of the present invention is that the metallization process of the chromium-free plastic surface can be performed with sufficient adhesion to the plastic surface, and the force does not deposit on the jig! It is highly practical! To provide a metallization method for plastic surfaces. Means for solving the problem
  • the present inventors have determined that a catalyst containing a specific compound after treating a plastic surface with an etching treatment solution containing a permanganate or the like. It has been found that the treatment with the application-enhancing liquid allows the catalyst metal to be selectively adsorbed on the plastic surface in the subsequent application of the catalyst, and also increases the amount of adsorption. Furthermore, even if a plating process is performed subsequent to the catalyst application process, it is possible to perform plating with sufficient adhesion to the plastic surface, and it has been found that plating does not deposit on the jig coating surface. Completed.
  • the present invention treats a plastic with an etching treatment solution containing a permanganate and an inorganic acid, and then selectively treats the treated plastic with a functional group exposed on the surface thereof.
  • a catalyst is applied to the plastic treated with the catalyst application-enhancing liquid, and a catalyst is applied to the plastic applied with the catalyst application-enhancing liquid. It is a metallization method for a plastic surface characterized by applying a metal plating.
  • the method for metallizing a plastic surface of the present invention it is a highly practical method that can sufficiently adhere to and squeeze the plastic surface and does not deposit plating on the jig. Moreover, according to the metallization method of the plastic surface of the present invention, the plastic surface Since the amount of catalyst metal adsorbed can be increased, it can be applied to plastics that are difficult to adsorb catalyst metal by conventional methods.
  • the method for metallizing a plastic surface of the present invention is an excellent method as a metallizing process for a chromium-free plastic surface.
  • the plastic to be metallized is not particularly limited.
  • ABS polycarbonate Z acrylonitrile' Butadiene 'styrene
  • PCZABS polycarbonate Z acrylonitrile' Butadiene 'styrene
  • ASA acrylonitrile styrene acrylate
  • SAS silicon composite rubber —acrylonitrile monostyrene
  • PC polycarbonate
  • the plastic surface is treated with an etching treatment solution containing a permanganate and an inorganic acid.
  • the permanganate contained in the etching solution is not particularly limited, and for example, metal salts of permanganate such as potassium permanganate and sodium permanganate can be used.
  • the concentration of this permanganate in the etching solution is 0.0005 molZL or more, preferably 0.005 to 0.5 molZL.
  • the inorganic acid contained in the etching solution is not particularly limited, and examples thereof include at least one selected from the group of inorganic acids selected from phosphoric acid, sulfuric acid, and nitric acid, preferably phosphoric acid. is there.
  • the concentration of these inorganic acids in the etching treatment solution is 2 molZL or more, preferably 6 to 12 molZL.
  • the liquid temperature is set to 0 to 50 ° C, preferably 25 to 40 ° C, and the plastic is immersed in the solution for 1 to 30 minutes, preferably 5 to 15 minutes. do it.
  • the surface of the plastic is treated with functional groups, specifically hydroxyl groups, A hydrophilic functional group such as a xyl group is exposed.
  • the plastic surface subjected to the above etching treatment is then subjected to a compound having a selective adsorption property to the functional group exposed on the plastic surface by the above treatment (hereinafter referred to as "selective adsorption compound" t, And a catalyst application enhancing solution containing
  • the selective adsorption compound contained in the catalyst imparting enhancement liquid is not particularly limited as long as it is a compound having selective adsorption on the functional group as described above.
  • a compound containing a nitrogen atom, a nitrogen atom, etc. Or a compound having a molecular weight of 100 or more, preferably a compound having 3 or more nitrogen atoms and a molecular weight of 100 or more.
  • the selective adsorptive compound include ethylenediamine compounds such as ethylenetriamine and triethylenetetramine (excluding ethylenediamine); Epomin SP-003, Epomin SP-012, Epomin SP-200 ( Ethyleneimine polymer compounds such as Nippon Shokubai Co., Ltd .; arylamine polymer compounds such as PAA-03, PAA-D41-HC1 (both manufactured by Nitto Boseki Co., Ltd.); PAS-92, PAS — Diallylamine polymer compounds such as M-1, PAS-880 (all manufactured by Nitto Boseki Co., Ltd.); vinylamine polymer compounds such as PVAM-0570-B (manufactured by Mitsubishi Chemical Corporation).
  • ethylenediamine compounds such as ethylenetriamine and triethylenetetramine (excluding ethylenediamine); Epomin SP-003, Epomin SP-012, Epomin SP-200 ( Ethyleneimine polymer compounds such as Nippon Shokubai Co.,
  • ethyleneimine polymer compounds, arylamine polymer compounds and diallylamine polymer compounds are particularly preferred.
  • concentration of these selective adsorptive compounds in the catalyst application enhancing liquid is 10 mgZL or more, preferably 100 to 1000 mgZL.
  • the liquid temperature is set to 0 to 70 ° C., preferably 25 to 35 ° C., and the plastic is immersed in the solution for 1 to 20 minutes, preferably 2 to 3 minutes. What is necessary is to process.
  • a catalyst is applied to the plastic surface subjected to the above-described catalyst application enhancing treatment with a catalyst application treatment liquid.
  • the catalyst application treatment liquid is not particularly limited as long as it is generally used for the catalyst application in the plating process, but the one containing noble metal is preferred, and the one containing palladium is more preferred, especially palladium Z tin mixed colloidal catalyst.
  • a solution is preferred.
  • the temperature of the catalyst application treatment solution is 10 to 60 ° C, preferably 20 to 50 ° C, and the plastic is immersed in the solution for 1 to 20 minutes, preferably 2 to 5 minutes. The Processing.
  • the plastic surface thus provided with the catalyst is then metallized by metal plating such as electroless metal plating (direct plating).
  • the catalyst When electroless metal plating is used for metallization of the plastic surface, the catalyst may be applied with a catalyst application treatment solution and then further treated with an activation treatment solution containing hydrochloric acid or sulfuric acid. Good.
  • the concentration of hydrochloric acid or sulfuric acid in this active liquid treatment solution is 0.5 molZL or more, preferably 1 to 4 molZL.
  • the liquid temperature of the active liquid treatment liquid is set to 0 to 60 ° C, preferably 30 to 45 ° C, and the plastic is preferably used for 1 to 20 minutes. Can be soaked for 2-5 minutes.
  • the plastic subjected to the application of the catalyst and subjected to the activity treatment as described above is subjected to an electroless metal plating treatment.
  • the electroless metal plating treatment can be carried out in accordance with a conventional method using an electroless metal plating such as a known electroless nickel plating solution, electroless copper plating solution, or electroless cobalt plating solution.
  • an electroless metal plating such as a known electroless nickel plating solution, electroless copper plating solution, or electroless cobalt plating solution.
  • the plastic is immersed in an electroless nickel plating solution at a pH of 8 to 10 and a temperature of 30 to 50 ° C for 5 to 15 minutes. What is necessary is to process.
  • the pH further containing copper ions is 7 or more.
  • the treatment may preferably be performed with an active soot treatment solution having a pH of 2 or more.
  • the origin of the copper ions contained in this activation treatment liquid is not particularly limited, and examples thereof include copper sulfate.
  • the temperature of the activation treatment solution is set to 0 to 60 ° C, preferably 30 to 50 ° C, and the plastic is added to the plastic for 1 to 20 minutes, preferably 2 to Soak and treat for 50 minutes.
  • the plastic that has been subjected to the application of the catalyst and treated with the activity as described above is then immersed in a general-purpose electric copper plating bath such as a copper sulfate bath, under normal conditions, for example, 1 to 5 AZdm 2 . 2 ⁇ : Process for LO minutes.
  • a general-purpose electric copper plating bath such as a copper sulfate bath
  • metal plating such as electroless plating or electrometal plating is applied to the plastic surface as described above, and various types of electrolytic copper are further applied to the metalized plastic surface according to the purpose. Plating or electro nickel plating can also be applied.
  • a 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked. Next, 200 mg / l PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) was soaked in a 30 ° C catalyzing enhancement solution adjusted to pH 10 with sodium hydroxide for 2 minutes. .
  • electroless nickel plating solution ENILEX NI-5 (made by EBARA Eugleite Co., Ltd.) at pH 8.8 and 35 ° C, so that the film thickness is 0.5 m on the ABS resin. Electrolytic nickel plating was applied. Thereafter, it was immersed in an acid active solution containing 150 g / l of V-345 (manufactured by Ebara Eugleite Co., Ltd.) at room temperature for 1 minute. Next, it was immersed in a 45 ° C. watt bath containing 0.75 molZl nickel sulfate, 0.4 molZl nickel chloride nickel and O.55 mol / 1 boric acid at 2 V / dm 2 for 3 minutes.
  • a 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked. Next, this was immersed in a catalyst solution at 50 ° C. containing 0.0024 mol / l of sodium chloride palladium for 4 minutes to give the catalyst onto the ABS resin. Next, the catalyst was activated by immersing in PC-66H (manufactured by Sakakibara Eugelite Co., Ltd.) for 4 minutes in a 35 ° C. active soot treatment solution containing 10 ml / l. Thereafter, the same treatment as in Example 1 after electroless nickel plating was performed.
  • PC-66H manufactured by Sakakibara Eugelite Co., Ltd.
  • Example 1 the adsorption amount of the palladium catalyst increased, and the depositability and adhesion strength of the electroless plating film were good. In this process, plating did not deposit on the jig coating. On the other hand, in Comparative Example 1, although there was no plating deposition on the jig, there was an undeposited portion of plating where the amount of palladium adsorbed on the ABS resin was small. Comparative Example 2 and Comparative Example 3 In this case, a sufficient amount of palladium was adsorbed on ABS resin, but plating was deposited on the jig coating.
  • a 50 x 100 x 3 mm ABS resin (UMGABS Co., Ltd.) was used as a sample, and this was placed in a 35 ° C etching solution containing O. OlmolZl potassium permanganate and 7.5 molZl phosphoric acid for 10 minutes. Soaked.
  • 200 mg / l PAA-03 Polyamylamine: manufactured by Nitto Boseki Co., Ltd.
  • PAA-03 Polyamylamine: manufactured by Nitto Boseki Co., Ltd.
  • Example 3 The depositability of the electroless plating film obtained in Example 3 and Comparative Example 4 in various types of grease and deposition on the jig coating were evaluated visually.
  • the adhesion strength of the electroless plating film obtained on each type of resin was measured in the same manner as in Test Example 1. These results are shown in Table 2.
  • Example 3 The electroless plating film obtained in Example 3 was completely applied on all the resins, and an adhesion strength equal to or higher than that of Comparative Example 4 (chromic acid etching process) was obtained. Further, in Example 3, no plating was deposited on the jig cover even when electroless plating was applied to any of the resins. On the other hand, Comparative Example 4 (chromic acid etching process) In this case, unprecipitated parts were generated in noryl and polypropylene resin, and in the case of PC resin, plating did not precipitate.
  • the active ingredient of the catalyst imparting enhancement liquid is PAA-03 (polyallylamine: manufactured by Nitto Boseki Co., Ltd.) as shown in Table 4 below, or Ade force hope, Ade force tall, Ade force bull mouth Electroless nickel plating was applied on the ABS resin in the same way except that it was changed to Nick (all manufactured by Asahi Denki Kogyo Co., Ltd.) and Energy Coal (manufactured by Lion Co., Ltd.). The depositability of the obtained electroless nickel film on ABS resin and the deposit on the jig coating were evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on ABS resin was measured in the same manner as in Test Example 1. These results are shown in Table 3.
  • Aryl amine polymer compound Good None 0. 1 0 8
  • Aryl 7-min polymer compound Good None 0. 0 7 9
  • Cialyl 7-min polymer compound Good None 0. 0 4 9
  • Cialyl 7-Mine polymer compound Good None 0. 0 6 8
  • Vinylamine polymer compound Good None 0 0 8 2
  • catalyst imparting enhancement liquid ethylenediamine compound, ethyleneimine polymer compound, arylamine polymer compound, diallylamine polymer compound, vinyl
  • active ingredients of catalyst imparting enhancement liquid ethylenediamine compound, ethyleneimine polymer compound, arylamine polymer compound, diallylamine polymer compound, vinyl
  • amine-based polymer compounds were used, the palladium adsorption amount increased, and good plating deposition properties were obtained without jig deposition.
  • compounds such as monoethanolamine, ethylenediamine, glycine, taurine, and aminoethanethiol which are compounds with less than nitrogen atoms in one molecule, did not increase the amount of palladium adsorbed.
  • Ade-powered Hope and Energy Coal which are surfactants.
  • Adekato a non-ionic surfactant
  • the amount of palladium adsorbed did not increase at the Able Bull nick, and even caused deposition on the jig coating.
  • Example 1 electroless nickel plating was performed on the ABS resin in the same manner except that the composition of the etching treatment solution was changed to that shown in Table 5 below.
  • the depositability of the obtained electroless nickel coating on ABS resin was evaluated in the same manner as in Test Example 1. These results are shown in Table 5. Further, the adhesion strength of the obtained electroless nickel plating film was measured by the following tape peeling test.
  • Cellophane tape (CT24: manufactured by Chiban Co., Ltd.) was brought into close contact with the sample surface after electroless nickel plating, and the tape was peeled upward 90 °. After the cellophane tape was peeled off, it was confirmed by visual inspection that the clinging film was not peeled off together with the tape.
  • Example 2 In the process of Example 1, all except that the ⁇ of the catalyst imparting enhancement liquid was adjusted to the values listed in Table 6 below using sodium hydroxide and sulfuric acid, the same was applied to the electroless gasket on the ABS resin. Was plated. Precipitation properties of the obtained electroless nickel coating on ABS Precipitation on the jig coating was evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on ABS resin was measured in the same manner as in Test Example 1. These results are also shown in Table 6.
  • Example 7 In the process of Example 1, except that the concentration of polyallylamine (PAA-03: manufactured by Nitto Boseki Co., Ltd.), which is an active ingredient in the catalyst application enhancing liquid, is adjusted to the values shown in Table 7, all the same Electroless nickel plating was performed on the resin.
  • the deposition of the obtained electroless nickel coating on the jig coating with ABS resin was evaluated in the same manner as in Test Example 1. Further, the amount of palladium adsorbed on the ABS resin was measured in the same manner as in Test Example 1. These results were also set to 7.
  • PAA-03 manufactured by Nitto Boseki Co., Ltd.
  • the method for metallizing a plastic surface according to the present invention is a highly practical method that can sufficiently adhere to the surface of the plastic and cause a stagnation, and that plating does not deposit on the jig.
  • the amount of catalyst metal adsorbed on the plastic surface can be increased, so that the conventional method can be applied to plastics that are difficult to adsorb catalyst metal.
  • the method of the present invention can be used as a metallization process for a chromium-free plastic surface.
  • Fig. 1 shows the result of measuring the surface of the ABS resin surface with a Fourier transform infrared spectrophotometer (1: ABS resin surface without etching treatment, 2: Etching containing chromic acid) ABS resin surface after treatment with treatment liquid, 3: ABS resin surface after treatment with etchant containing permanganic acid).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

La présente invention concerne un procédé pratique de métallisation sans chrome de surfaces en plastique permettant de produire un film de placage qui adhère fermement à la surface d'une pièce en plastique et ce, sans dépôt sur un support. Le procédé de métallisation de surfaces en plastique est caractérisé en ce qu'il consiste à traiter une pièce en plastique avec un fluide de gravure contenant un permanganate et un acide inorganique, à traiter la pièce en plastique résultante avec un fluide potentialisateur afin de transférer un catalyseur qui contient un composé à adsorption sélective à des groupes fonctionnels exposés à la surface de la pièce en plastique, à transférer un catalyseur sur la pièce en plastique traitée au moyen d'un fluide de transfert de catalyseur, puis à soumettre la pièce en plastique résultante à un placage métallique.
PCT/JP2007/060332 2006-07-27 2007-05-21 Procédé de métallisation de surfaces en plastique WO2008012984A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2007800273670A CN101490310B (zh) 2006-07-27 2007-05-21 塑料表面的金属化方法
KR1020097002064A KR101365970B1 (ko) 2006-07-27 2007-05-21 플라스틱 표면의 금속화 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-204993 2006-07-27
JP2006204993A JP4275157B2 (ja) 2006-07-27 2006-07-27 プラスチック表面の金属化方法

Publications (1)

Publication Number Publication Date
WO2008012984A1 true WO2008012984A1 (fr) 2008-01-31

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PCT/JP2007/060332 WO2008012984A1 (fr) 2006-07-27 2007-05-21 Procédé de métallisation de surfaces en plastique

Country Status (5)

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JP (1) JP4275157B2 (fr)
KR (1) KR101365970B1 (fr)
CN (1) CN101490310B (fr)
TW (1) TW200811311A (fr)
WO (1) WO2008012984A1 (fr)

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CN102409320A (zh) * 2011-11-29 2012-04-11 沈阳工业大学 一种abs塑料表面电镀前处理的方法
JP2015190056A (ja) * 2014-03-31 2015-11-02 株式会社サーテックカリヤ 無電解めっき方法および無電解めっき物

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