WO2007043337A1 - ACTIVATEUR D’ADSORPTION DE TYPE CATALYSEUR COLLOÏDAL Pd/Sn - Google Patents

ACTIVATEUR D’ADSORPTION DE TYPE CATALYSEUR COLLOÏDAL Pd/Sn Download PDF

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Publication number
WO2007043337A1
WO2007043337A1 PCT/JP2006/319151 JP2006319151W WO2007043337A1 WO 2007043337 A1 WO2007043337 A1 WO 2007043337A1 JP 2006319151 W JP2006319151 W JP 2006319151W WO 2007043337 A1 WO2007043337 A1 WO 2007043337A1
Authority
WO
WIPO (PCT)
Prior art keywords
bromide
catalyst
palladium
bromine
plating
Prior art date
Application number
PCT/JP2006/319151
Other languages
English (en)
Japanese (ja)
Inventor
Kazuo Ibata
Akira Yokoyama
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 KR1020087007599A priority Critical patent/KR101295578B1/ko
Publication of WO2007043337A1 publication Critical patent/WO2007043337A1/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
    • 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

Definitions

  • the present invention relates to a rare-earths colloid for promoting adsorption of a palladium-tin colloid catalyst on the surface of a non-conductive material when a metal film is formed on a non-conductive material such as plastic by electroplating.
  • the present invention relates to a catalyst adsorption accelerator, a catalyst imparting liquid containing the same, and a method for plating a non-conductive material.
  • a so-called palladium-tin colloidal catalyst (hereinafter referred to as "PdZSn colloidal catalyst") is deposited on the surface of the nonconductive material.
  • PdZSn colloidal catalyst a so-called palladium-tin colloidal catalyst
  • a so-called plastic plating method has been carried out in which a metalizing process is performed after carrying out a catalyzing process, followed by a conductive process such as electroless plating or metallizing process if necessary.
  • plating technology on non-conductive materials such as plastics is often used.
  • the PdZSn colloidal catalyst is sufficiently and uniformly adsorbed and deposited in the catalyzing process in order to accurately form a metal film at the target portion in the subsequent process. It is needed.
  • the concentration of the PdZSn colloidal catalyst solution to be used must be above a certain level.
  • Patent Document 1 Japanese Patent Laid-Open No. 2003-13244
  • Patent Document 2 JP 2001-152353 A
  • the present invention has been made in view of the current state of the prior art described above, and forms a metal film on a surface of a nonconductive material, particularly a nonconductive polymer material such as plastic, using a plating technique.
  • the purpose of the present invention is to provide a catalyst adsorption accelerator capable of increasing the adsorption and precipitation of the PdZSn colloidal catalyst on the material surface, a catalyst application liquid containing this adsorption accelerator, and a method for plating a non-conductive material. It is what.
  • the present inventors have added a substance that generates bromide ions to the catalyst application liquid itself in the catalyst application process, thereby eliminating non-conductive materials.
  • the present invention was completed by finding that the amount of adsorption of the PdZSn colloidal catalyst was greatly increased.
  • the gist of the present invention is as follows.
  • PdZSn colloidal catalyst adsorption promoter containing a bromine compound that generates bromine ions as an active ingredient.
  • the bromine compound is either a typical metal element, a typical nonmetal element or a transition metal element
  • Bromine compound is lithium bromide, sodium bromide, aluminum bromide, potassium bromide, calcium bromide, strontium bromide, odorous tin (11), cesium bromide, odorous barium, odorization Hydroacid, Cyanide bromide (IV), Vanadium bromide (III), Manganese bromide (II), Iron bromide (II), Cobalt bromide (II), Nickel bromide (II), Palladium bromide ( The PdZSn colloidal catalyst adsorption promoter according to (1) or (2) above, wherein the compound consisting of II) and gold bromide (III) is also selected.
  • a PdZSn colloid catalyst-imparting solution comprising a PdZSn colloid catalyst and the PdZSn colloid catalyst adsorption accelerator described in any one of (1) to (3) above.
  • a metal film is formed by plating on the surface of the non-conductive material using the catalyst application liquid in which the PdZSn colloid catalyst adsorption accelerator described in any one of (1) to (3) is added to the PdZSn colloid catalyst application liquid.
  • the amount of PdZSn colloidal catalyst adsorbed on the surface of a non-conductive material such as plastic can be increased.
  • a uniform and good conductive film on the non-conductive material in the subsequent conductive plating treatment process, and further improve the deposition properties such as copper sulfate plating in the subsequent electric plating. And good plating can be performed.
  • the present invention provides a surface of a non-conductive material such as a plastic by adding a compound capable of generating bromide ions to the PdZSn colloid catalyst application liquid in the catalyst application process, that is, the catalyzing process. This is based on the finding that the amount of PdZSn colloidal catalyst adsorbed on the catalyst increases significantly.
  • Examples of the plating method on the surface of non-conductive materials such as plastic include talit nitrile butadiene styrene resin (hereinafter referred to as “ ABS resin”), polycarbonate resin, and the like.
  • ABS resin talit nitrile butadiene styrene resin
  • ABS-based alloy polymer an oil blend 'acrylonitrile' butadiene 'styrene-resin-based alloy polymer
  • the surface of a non-conductive material such as plastic is chemically etched using a mixed solution of chromic anhydride and sulfuric acid, a permanganate solution, or the like.
  • the surface is roughened.
  • a mixed solution of chromic anhydride and sulfuric acid is used for the etching process, the etched material is washed thoroughly with water, and then neutralized with a neutralizing solution (for example, ENILEX RD, manufactured by Ebara Eugleite Co., Ltd.). Reduce the hexavalent chromium used for etching.
  • a PdZSn colloid catalyst is adsorbed by immersing a non-conductive material such as a plastic whose surface is roughened in a solution containing noradium and tin. Furthermore, Pd (II) ions on the nonconductive material with the PdZSn colloidal catalyst adsorbed on the surface are reduced to Pd metal with a reducing agent, and this is subjected to electroless plating or metallizing treatment on the surface. V, so-called conductive conductivity treatment, and the surface is plated with various metals by electroplating non-conductive materials such as plastic. Can be applied.
  • PdZSn colloidal catalyst adsorption accelerator (hereinafter referred to as "PdZSn adsorption accelerator”) of the present invention is added to the catalyst application liquid containing palladium and tin in the catalyst application process in the series of processes described above.
  • PdZSn adsorption accelerator specifically includes a typical metal element, a typical nonmetallic element or a transition metal element as a compound capable of producing bromide (hereinafter referred to as “bromine compound”). And a bromine compound.
  • the compounds of typical metal elements and bromine include lithium bromide, sodium bromide, magnesium bromide, aluminum bromide, bromide Potassium, calcium bromide, germanium bromide (IV), rubidium bromide, strontium bromide, cadmium bromide, indium bromide (1), indium bromide (III), tin bromide (11), antimony bromide (111), cesium bromide, barium bromide, mercury bromide (1), mercury bromide (II), thallium bromide (I), lead bromide (II), bismuth bromide (III), etc. .
  • compounds of atypical metal elements and bromine include hydrobromic acid, silicon bromide (IV), phosphorus bromide (V ) And tellurium bromide (IV).
  • transition metal element and bromine compounds include titanium bromide (IV), vanadium bromide (111), chromium bromide ( III), manganese bromide (II), iron bromide (II), cobalt bromide (II), nickel bromide ( ⁇ ), zirconium bromide (IV), ruthenium bromide (III), rhodium bromide ( III), palladium bromide (II), silver bromide, tantalum bromide (V), iridium bromide (111), platinum bromide (11), platinum bromide (IV), gold bromide (III), odor Lanthanum bromide (111), praseodymium bromide (111), neodymium bromide (111), samarium bromide, gadolinium bromide (III), terbium bromide (III), dysprosium bromide (
  • compounds of typical metal elements and bromine include lithium bromide, sodium bromide, potassium bromide, calcium bromide, strontium bromide, tin bromide (11), cesium bromide.
  • Hydrobromic acid is a compound of bromine, barium bromide, etc.
  • C (IV) bromide examples include vanadium bromide, manganese bromide (11), iron bromide (11), cobalt bromide (11), nickel bromide. (11) Palladium bromide ( ⁇ ), gold bromide (III), etc. are preferred.
  • a compound of a typical metal element, a typical nonmetal element or a transition metal element and bromine as described above is added to a general PdZSn colloidal catalyst solution (hereinafter referred to as "catalyst solution”) to add a bromine compound.
  • the PdZSn colloid catalyst-imparting liquid of the invention hereinafter referred to as “PdZSn catalyst-imparting liquid”.
  • This catalyst solution has already been described in the literature or is commercially available, and usually a solution in which palladium metal and tin metal are dissolved in an acidic solution, particularly an aqueous hydrochloric acid solution in hydrochloric acid is preferred.
  • the composition of the catalyst solution contains 10 to 500 ppm, preferably 150 to 300 ppm as palladium metal, and 1 to 50 gZL, preferably 10 to 30 gZL as tin metal, in an acidic solution such as hydrochloric acid.
  • an acidic solution such as hydrochloric acid.
  • the Pd / Sn catalyst application solution of the present invention is obtained. Can do.
  • a catalyst application process (catalyzing process) is performed using the PdZSn catalyst application liquid as described above.
  • the treatment conditions for the catalyst application treatment are a temperature of 10 to 50 ° C, preferably 25 to 45 ° C, and a treatment time (immersion time) of 1 to 10 minutes, preferably 2 to 5 minutes.
  • a PdZSn colloid catalyst on the surface of a non-conductive material such as plastic is used in the catalyst application process (catalyzing process).
  • the amount of adsorption of the catalyst is increased, and the amount of adsorption of the catalyst can be increased by about 1.1 to 2 times compared to the case where the PdZSn adsorption promoter of the present invention is not used. Therefore, the PdZSn colloidal catalyst can uniformly adhere to the surface of a non-conductive material such as plastic, and in the subsequent conductive treatment process by electroless plating or metalizing treatment, very good conductivity can be achieved.
  • An adhesive film can be formed.
  • the next object to be treated was subjected to a catalyst application treatment using the present invention bath and the comparative bath described below, and the surface was plated.
  • An automotive ABS mirror cover with a surface area of about 8 dm 2 was used.
  • the plating jig was supported at three points of contact with the workpiece, and other than the contacts, a jig that was baked and coated with a salty vinyl sol was used.
  • ABS molding parts for automobiles with a surface area of approximately 6dm 2 were used.
  • the plating jig was supported at two contact points with the workpiece, and other than the contact points, a jig that was baked and coated with a sol made of vinyl chloride and vinyl was used.
  • the workpiece set in the jig was charged with 400 gZL of chromic anhydride and 400 gZL of sulfuric acid.
  • the resin surface was roughened by immersing it in an etching solution containing aqueous solution at 68 ° C for 10 minutes.
  • this material to be treated is washed with water and then immersed in a hexavalent chromium reducing solution (trade name: ENILEX RD, manufactured by Ebara Eugelite Co., Ltd.) for 2 minutes at room temperature. Was removed.
  • a hexavalent chromium reducing solution (trade name: ENILEX RD, manufactured by Ebara Eugelite Co., Ltd.) for 2 minutes at room temperature. Was removed.
  • the object to be treated was immersed in an aqueous solution containing 35% hydrochloric acid 3 OOmlZL for 2 minutes as a pre-dip treatment.
  • the PdZSn colloid catalyst was applied on the object to be processed according to the catalyst application liquids and treatment conditions of the present invention and comparative baths shown in Tables 1 and 2.
  • D-POP ACT-MU (trade name, manufactured by Ebara Eugilite Co., Ltd.) is a concentrated solution of a catalyst imparting solution mainly composed of palladium chloride, tin chloride and hydrochloric acid.
  • the bromine ion concentration of each bromine compound in the inventive baths of Tables 1 and 2 above is 6 gZL.
  • the treated material that has been subjected to the catalyst application treatment is further washed with water, and these non-conductive plastics are used.
  • a metallizer solution (trade name: D—POP ME, manufactured by Ebara Eugleite Co., Ltd.) containing copper sulfate, alkali metal hydroxide and complexing agent as the main components Using this, the object to be treated was immersed in this metallizer for 3 minutes at 45 ° C to conduct a conductive treatment (metalizing).
  • the electrolytic copper plating solution was prepared by adding the following to 1 liter of water.
  • Brightener is the product name, and the product is a product name manufactured by Ebara Eugelite Co., Ltd.
  • the liquid temperature was 25 ° C, and the current density was 3AZdm 2 after 5 minutes.
  • the electroplating process was performed for a total of 25 minutes.
  • the PdZSn catalyst of the present invention in which the PdZSn adsorption accelerator composed of the bromine compound of the present invention is added to a catalyst solution for conducting a conductive material such as plastic.
  • the application bath showed much better performance than conventional catalyst solutions.
  • plastics with a conductive coating on the surface can be used in various electronic parts, printed wiring boards, automotive front grills and emblems, and various decorative parts such as buttons used in mobile phones. It can also be used to improve the mechanical properties and appearance of products.
  • FIG. 1 is a drawing showing general steps of a method for plating a surface of a non-conductive material.

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

Abstract

La présente invention concerne : un activateur d’adsorption de type catalyseur colloïdal Pd/Sn qui peut être utilisé pour la formation d'un film de revêtement métallique sur la surface d'un matériau non-conducteur (par exemple, un plastique) par un dépôt métallique de grande efficacité ; une solution d’addition de catalyseur comprenant l’activateur d’adsorption ; et un procédé de dépôt métallique sur un matériau non-conducteur. L’activateur d’adsorption peut être utilisé pour le dépôt métallique sur un matériau non-conducteur et comprend un quelconque composé à base de brome choisi parmi un élément métallique typique, un élément non-métallique typique et un élément de métal de transition avec un atome de brome. Le composé à base de brome peut être le bromure de lithium, le bromure de sodium, le bromure d’aluminium, le bromure de potassium, le bromure de calcium, le bromure de strontium, le bromure d’étain (II), le bromure de césium, le bromure de baryum, l’acide bromhydrique, le bromure de silicium (IV), le bromure de vanadium (III), le bromure de manganèse (II), le bromure de fer (II), le bromure de cobalt (II), le bromure de nickel (II), le bromure de palladium (II), le bromure d’or (III) ou analogues. Le matériau non-conducteur peut être une résine ABS, une résine ABS mélangée à une résine PC ou analogues.
PCT/JP2006/319151 2005-10-11 2006-09-27 ACTIVATEUR D’ADSORPTION DE TYPE CATALYSEUR COLLOÏDAL Pd/Sn WO2007043337A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020087007599A KR101295578B1 (ko) 2005-10-11 2006-09-27 Ｐｄ／Ｓｎ 콜로이드 촉매 흡착 촉진제

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-296163 2005-10-11
JP2005296163A JP4740711B2 (ja) 2005-10-11 2005-10-11 Ｐｄ／Ｓｎコロイド触媒吸着促進剤

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JP (1) JP4740711B2 (fr)
KR (1) KR101295578B1 (fr)
CN (1) CN101283120A (fr)
WO (1) WO2007043337A1 (fr)

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Publication number Priority date Publication date Assignee Title
SG11201610462WA (en) * 2014-07-10 2017-02-27 Okuno Chem Ind Co Resin plating method
CN106245105B (zh) * 2016-08-05 2018-07-13 广州三孚新材料科技股份有限公司 Pa10t工程塑料的无铬表面微蚀方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2747321B2 (ja) * 1989-04-19 1998-05-06 日清紡績株式会社 金属被覆された合成樹脂製構造物の製造方法
JP3054746B2 (ja) * 1997-02-03 2000-06-19 奥野製薬工業株式会社 非導電性材料への電気めっき方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2747321B2 (ja) * 1989-04-19 1998-05-06 日清紡績株式会社 金属被覆された合成樹脂製構造物の製造方法
JP3054746B2 (ja) * 1997-02-03 2000-06-19 奥野製薬工業株式会社 非導電性材料への電気めっき方法

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KR20080060230A (ko) 2008-07-01
KR101295578B1 (ko) 2013-08-09
JP2007107022A (ja) 2007-04-26
JP4740711B2 (ja) 2011-08-03
CN101283120A (zh) 2008-10-08

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