WO2000001862A1 - Pretreating agent for metal plating, and method for metal plating using the same - Google Patents

Pretreating agent for metal plating, and method for metal plating using the same Download PDF

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Publication number
WO2000001862A1
WO2000001862A1 PCT/JP1999/002180 JP9902180W WO0001862A1 WO 2000001862 A1 WO2000001862 A1 WO 2000001862A1 JP 9902180 W JP9902180 W JP 9902180W WO 0001862 A1 WO0001862 A1 WO 0001862A1
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Prior art keywords
plating
solution
minutes
electroless
powder
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PCT/JP1999/002180
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French (fr)
Japanese (ja)
Inventor
Hideyuki Mori
Masashi Kumagai
Original Assignee
Japan Energy Corporation
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Filing date
Publication date
Application filed by Japan Energy Corporation filed Critical Japan Energy Corporation
Priority to JP54029899A priority Critical patent/JP3277463B2/en
Priority to TW088111492A priority patent/TW438905B/en
Publication of WO2000001862A1 publication Critical patent/WO2000001862A1/en
Priority to HK00108303A priority patent/HK1028907A1/en

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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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers

Definitions

  • the present invention relates to a method for metal plating by electroless plating on a surface of a material having low conductivity or a mirror-like object or powder, and The present invention relates to a pretreatment agent for metal plating.
  • the electroless metal plating method is one of the methods of forming a metal film on a non-conductive substrate, and as a pretreatment for electroless plating, a noble metal such as palladium is used as a catalyst to adhere to the substrate in advance.
  • a method called activation is generally used.
  • Previously, or to adsorb the P d and immersed in a P d C 1 2 aqueous solution was processed by S n C 1 2 hydrochloric acid aqueous solution,
  • the present invention provides a new metallization by electroless plating that is conventionally not applicable to electroless plating and that can be suitably applied to powder and mirror-like objects.
  • An object of the present invention is to provide a plating method and a metal plating pretreatment agent therefor.
  • the present inventor has found that the problem can be solved by selecting a specific silane coupling agent as the silane coupling agent having the ability to form a complex with the noble metal ion, and reached the present invention. That is, the present invention
  • a metal plating pretreatment agent comprising a silane coupling agent obtained by reacting an azole compound having an active functional group that forms a complex with a noble metal ion with an epoxysilane compound;
  • the present invention relates to a silane coupling agent used to support a noble metal such as Pd, which is a catalyst for electroless plating, on a surface to be covered, that is, the ability to form a complex with a noble metal. It is important to use, as the silane coupling agent having a functional group, a reaction product of an azole compound having an active functional group which forms a complex with the noble metal ion and an epoxysilane compound.
  • Examples of the azo compound include, but are not limited to, pyrrole, indole, imidazole, pyrazole, benzimidazole, indazole and the like.
  • the epoxysilane-based compound is a compound having an epoxy group and an alkoxysilyl group in a molecule, and a general one is ⁇ -glycidoxypropylpyralkoxysilane, but is not limited thereto.
  • the silane coupling agent itself obtained by the reaction of the azole compound and the epoxysilane compound is already known.
  • Japanese Patent Application Laid-Open No. Hei 6-25663 / 58 discloses that an imidazole compound and an epoxysilane are reacted to obtain an imidazole silane compound.
  • the silane coupling agent of this reaction product may be obtained in a state containing intermolecular and intramolecular condensates, but it is not necessary to separate them, and they can be used in a mixture state.
  • This silane coupling agent has characteristics such as high reactivity, the ability to adjust the concentration of the aqueous solution by adjusting the acidity of the aqueous solution, and the ability to give the dissolved solution a certain degree of viscosity. . These things Therefore, a film can be formed with a certain thickness under the substrate of the object to be coated and uniformly using the silane coupling agent.
  • electroless plating can be easily applied to various types of bases, including mirrors and powders that could not be processed without evaporating the solvent, which were difficult with conventional coupling agents represented by conventional aminosilanes.
  • the noble metal include palladium, silver, platinum, and gold that exhibit a catalytic effect when depositing a metal such as copper or nickel on the surface of an object to be plated from an electroless plating solution, with palladium being particularly preferred.
  • the properties of the adherend are not limited.
  • inorganic materials such as glass and ceramics, plastic materials such as polyester, polyamide, polyimide, and fluororesin; insulating plates such as epoxy resin reinforced with films, sheets, fibers, and, if necessary, glass substrates
  • insulators with low conductivity such as insulators such as semiconductors and semiconductors such as Si wafers
  • the objects to be coated are mirror-like objects such as transparent glass plates, Si wafers, and other semiconductor substrates.
  • the method of the present invention can be preferably applied to powders and powders.
  • Such powders include, for example, glass beads, molybdenum disulfide powder, magnesium oxide powder, graphite powder, SiC powder, zirconium oxide powder, alumina powder, gay oxide powder, mica flake, glass fiber, gay nitride Element and Teflon powder.
  • the silane coupling agent When the base to be electrolessly deposited is treated with a silane coupling agent which is a reaction product of the azole compound and the epoxysilane compound as described above, the silane coupling agent may be treated with an appropriate solvent such as water, It can be used for solutions dissolved in methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycol, polyethylene glycol, or a mixture thereof.
  • a method of volatilizing the solvent after coating the surface by dipping or brushing is generally used, but the method is not limited to this, and the silane coupling is uniformly applied to the surface. Any method can be used as long as it is a method of attaching an agent.
  • the solvent is volatilized to force
  • the uniform film-forming property of the silane coupling agent allows the silane coupling agent to be adsorbed on the base surface in the re-dipping state
  • a method of filtering off the solvent and drying the wet powder is also possible.
  • the concentration of the silane coupling agent in the solution to be treated is not limited to this, but 0.001 to 10% by weight is easy to use. If the amount is less than 0.001% by weight, the amount of the coupling agent adhering to the surface of the base material tends to be low, and the effect is hardly obtained. On the other hand, if it exceeds 10% by weight, it is difficult to dry the powder due to an excessively large amount of adhesion, and it is easy to cause powder agglomeration. In order to volatilize the solvent used after surface treatment, it is sufficient if the surface can be dried by heating to a temperature higher than the volatilization temperature of this solvent. Heat drying is preferred.
  • the method of chemically plating the surface treated as described above is a known method. That is, it is brought into contact with a solution containing a noble metal ion such as palladium, and the noble metal is captured by the azole group of the coupling agent treated on the base surface. After washing out the solubilizing agents such as excess noble metal salts such as halides and hydrochloric acid, perform chemical plating such as electroless plating.
  • a noble metal ion such as palladium
  • solubilizing agents such as excess noble metal salts such as halides and hydrochloric acid
  • metals such as copper, nickel, 'cobalt, tin, and gold can be plated by electroless plating.
  • electroless plating solution used in the present invention are as follows. There is something.
  • Plating temperature 70 ⁇ 90 ° C 2 Typical example of low temperature electroless copper plating composition
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxyprovirtrimethoxysilane, is added to the surface of the glass plate.
  • spin coating was performed at 500 R R. Thereafter, the plate was dried at 105 ° C for 30 minutes. Furthermore, after immersing for 1 minute at room temperature in Pd activation solution CG-535A (activator I.
  • Nikko Metal Plating Co., Ltd. manufactured by Nikko Metal Plating Co., Ltd.
  • Nicom 7N electroless nickel plating solution manufactured by Nikko Metal Plating Co., Ltd.
  • the electroless nickel plating solution uniformly deposited a glossy film on the entire surface of the glass, and it was confirmed that the electroless nickel plating solution had good adhesion without peeling off with a cellophane tape.
  • a 1 mm thick slide glass plate was immersed in a mixture of fluorine and nitric acid (100 ml / L hydrofluoric acid, 100 ml / L nitric acid) at 25 ° C for 10 minutes to roughen the surface.
  • This glass plate is treated with an alkaline degreasing solution, immersed in a Pd activation treatment solution CG-535A for 1 minute at room temperature, washed with about 100 ml of deionized water, and washed at 105 ° C After drying for 30 minutes, the precious metal activation treatment was performed on the glass plate surface. Next, it was immersed in 7 N of an electroless nickel plating solution at 80 ° C for 4 minutes. Electroless nickel plating hardly precipitated on the glass plate.
  • an aminosilane coupling agent KBM-903 ( ⁇ -aminoprovir trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the surface of the glass plate.
  • Spin coating was performed at 500 RPM using a 2-propanol solution containing 4% by weight. Thereafter, the plate was dried at 105 ° C. for 30 minutes.
  • Pd activation solution CG-535A for 1 minute at room temperature, washing with about 100 ml of deionized water and drying with 105 for 30 minutes, precious metal activation treatment on the glass plate surface was done. Next, it was immersed for 4 minutes at 80 ° C in 2N 7N, an electroless nickel plating solution. Electroless nickel The plating was deposited only on a part of the glass plate.
  • Example 2 To promote the hydrolysis-condensation reaction, a solution of a mixture of water and an equal amount of 2-propanol to which a trace amount of hydrochloric acid is added is added with 0.4% by weight of the aminosilane coupling agent KBM-903 and a concentration of 10%. A solution in which 4% by weight (Comparative Example 5) was dissolved was prepared, and a noble metal activation treatment was performed in the same manner as in Comparative Example 3, followed by electroless nickel plating. In all cases, electroless nickel plating was sparsely deposited on about half of the glass plate.
  • Example 2 A solution in which 4% by weight (Comparative Example 5) was dissolved was prepared, and a noble metal activation treatment was performed in the same manner as in Comparative Example 3, followed by electroless nickel plating. In all cases, electroless nickel plating was sparsely deposited on about half of the glass plate.
  • Comparative Example 5 A solution in which 4% by weight (Comparative Example 5) was dissolved was prepared, and a
  • the PET film (trade name: Diafoil) was ultrasonically cleaned in 2-propanol for 5 minutes to degrease the surface, and then dried at 105 ° C for 10 minutes.
  • this film was coated with 4 weight parts of a silane coupling agent, which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltriethoxysilane. After immersion in a 2-propanol solution containing / 0 for 1 minute, the mixture was dried at 105 with agitation for 10 minutes.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltriethoxysilane.
  • this laminate was immersed in Pd activation treatment solution CG-5335A for 1 minute at room temperature, washed with deionized water, dried at 105 ° C for 60 minutes, and the noble metal was placed on the laminate surface.
  • An activation process was performed.
  • this plate was immersed for 2 minutes at 80 ° C in 2N 7N, an electroless Nigel plating solution, electroless nickel plating was uniformly deposited on the laminate.
  • the same precious metal activation treatment When the laminated board was immersed in electroless copper plating solution KC-500 at 70 ° C for 30 minutes, copper was uniformly deposited on the surface.
  • Glass beads of about 1.5 mm in diameter are dissolved in a 2-propanol solution containing 0.08 g of a 2-propanol solution containing 0.4% by weight of aminosilane coupling agent K BM-903 for 1 minute. Immerse. After filtering the liquid, it is dried at 105 ° C for 30 minutes. Next, this glass bead is immersed in 50 ml of Pd activation solution CG-535A at room temperature for 1 minute, and the activation solution is filtered and further washed with 50 ml of deionized water. Dry at 30 ° C for 30 minutes and apply precious metal sexualized. This glass bead is electroless nickel plating solution
  • molybdenum disulfide powder having an average particle diameter of 50 microns was dissolved in 0.1 g of a silane coupling agent, which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane. Stir for 10 minutes at room temperature in 0 ml of 2-propanol solution. After distilling off the solvent, 2-propanol, dry at 105 ° C for 60 minutes. Next, the molybdenum disulfide powder is stirred in 50 ml of Pd activation solution CG-5335A at room temperature for 20 minutes, and the activated solution is removed by filtration and further washed with 50 ml of deionized water.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane.
  • the molybdenum disulfide powder was plated at 72 ° C using an electroless copper plating solution KC-500. A 1 wt% electroless copper plating resulted in a uniform copper plating film on the powder surface and completely covered the underlying molybdenum disulfide.
  • molybdenum disulfide powder having an average particle diameter of 50 microns was stirred in 50 ml of Pd activation solution CG-535A at room temperature for 20 minutes, the activation solution was removed by filtration and another 50 ml of After washing with deionized water, the powder was dried at 105 ° C. for 60 minutes to activate the noble metal on the powder surface.
  • the molybdenum disulfide powder was plated at 72 ° C. using an electroless copper plating solution KC'-500, but almost no copper plating film was formed due to the electroless copper plating.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltriethoxysilane
  • the surface was precious metal activated.
  • the magnesium oxide powder was plated at 72 ° C. using an electroless copper plating solution KC-500. A uniform copper plating film was formed on the powder surface by electroless copper plating of only 1 wt%, and the underlying magnesium oxide was completely covered.
  • 25 g of natural graphite powder having an average particle size of 100 microns is used as a silane coupling agent which is an equimolar reaction product of 2-ethyl-4-methylimidazole and ⁇ -glycidoxypropyltrimethoxysilane 0.1 Stir at room temperature for 10 minutes in 50 ml of ethanol solution of g dissolved. After distilling off 2-propanol as the solvent, the residue is dried at 105 ° C for 30 minutes. Next, this graphite powder was stirred at room temperature for 20 minutes in a Pd activation treatment solution CG-535A at 100 m1, and the activation treatment solution was filtered off to remove 50 ml of deionized water.
  • a silane coupling agent which is an equimolar reaction product of 2-ethyl-4-methylimidazole and ⁇ -glycidoxypropyltrimethoxysilane 0.1
  • the powder After washing with water, the powder was dried at 105 ° C for 30 minutes, and the surface of the powder was activated with a noble metal.
  • This graphite powder was plated at 72 ° C. using an electroless copper plating liquid KC-500. A uniform copper plating film was formed on the powder surface by electroless copper plating at 6 wt%.
  • the graphite powder, which has been activated with a noble metal is immersed in the electroless nickel plating solution Ncom 7 N at 80 ° C for 4 minutes, the electroless nickel plating precipitates almost uniformly on the surface and the color of the powder changes. The color changed from black to gray, and the base was completely covered with Nigel.
  • SiC powder having an average particle size of 70 microns dissolved in 0.2 g of a silane coupling agent, which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane Is stirred at room temperature for 10 minutes. After distilling off the solvent methanol, it is dried at 105 ° C for 30 minutes. Next, the SiC powder was stirred at room temperature for 20 minutes in a Pd activation treatment solution CG-5335A100 ml, and the activation treatment solution was filtered and a further 100 ml of desiccant was removed. Washed with ionized water Thereafter, drying was performed at 105 ° C.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane Is stirred at room temperature for 10 minutes. After distilling off the solvent methanol, it is dried at 105 ° C for 30 minutes. Next
  • the SiC powder was plated at 72 ° C using an electroless copper plating solution KC-500. With only 1 wt% of electroless copper plating, a uniform copper plating film was formed on the powder surface, resulting in a complete copper powder and complete coverage of the green SiC.
  • the activated solution is filtered. Further, the powder surface was washed with 100 ml of deionized water, dried at 105 ° C. for 30 minutes, and the surface of the powder was activated with a noble metal.
  • the SiC powder was plated at 72 ° C. using an electroless copper plating solution KC-500. Electroless copper plating was formed on the powder surface, but could not cover more than 20% of the SiC powder.
  • zirconium oxide powder having an average particle diameter of 30 microns is dissolved in 0.2 g of a silane coupling agent which is an equimolar reaction product of 2-methylimidazole and ⁇ -glycidoxypropyltriethoxysilane.
  • a silane coupling agent which is an equimolar reaction product of 2-methylimidazole and ⁇ -glycidoxypropyltriethoxysilane.
  • the mixture was stirred for 10 minutes at room temperature in a 100 ml methanol solution. After evaporating the solvent methanol, dry at 105 ° C for 30 minutes.
  • the zirconium oxide powder was stirred in 100 ml of Pd activation treatment solution CG-5335A at room temperature for 20 minutes, and the activation treatment solution was filtered, followed by further deionization of 1 ⁇ 0 m1.
  • the powder surface was dried at 105 ° C for 3 minutes, and the surface of the powder was activated with a precious metal.
  • this zirconium oxide powder was immersed in the electroless nickel plating solution 2N 7N at 80 ° C for 4 minutes, the electroless nickel plating was deposited almost uniformly on the zirconium oxide surface, and the base was completely covered.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane.
  • a silane coupling agent which is an equimolar reaction product of imidazole and ⁇ -glycidoxypropyltrimethoxysilane.
  • the yarn was immersed in 50 ml of Pd activation treatment solution CG-135A at room temperature for 20 minutes, and the activation treatment solution was filtered and further washed with 50 ml of deionized water.
  • the yarn was dried at 05 ° C for 30 minutes to activate the noble metal on the surface of the yarn.
  • the electroless nickel plating method can be suitably applied to mirror-like objects and powders which are difficult to be applied by the conventional method. Electroless plating can be performed, and there is no restriction on the properties and shape of the object to be plated.

Abstract

A method for an electroless metal plating which can be easily applied to a powder or mirror substrate, and a pretreating agent for use in the method. The pretreating agent comprises a silane coupling agent obtained by the reaction of an azole type compound having an active functional group capable of forming a complex with a noble metal with an epoxysilane compound. A substrate to be metal-plated is subjected to a surface preparation using the pretreating agent, is then treated with a solution containing a noble metal ion, and thereafter is subjected to an electroless plating, to thereby provide a metal-plated product.

Description

糸田 金属めつき前処理剤、 およびそれを用いる金属めつき方法 技術分野 本発明は、 導電性の低い材料や鏡面物や粉体などの表面上に無電 解めつきにより金属めつきする方法、 およびそのための金属めつき 前処理剤に関する。 背景技術 無電解金属めつき法は導電性のない下地に金属被膜を形成する方 法の一つであリ、 無電解めつきの前処理としてパラジウムなどの貴 金属を触媒としてあらかじめ下地に付着させておく活性化と呼ばれ る方法が一般的である。 これまで、 S n C 1 2の塩酸性水溶液で処 理した後 P d C 1 2水溶液に浸漬処理して P dを吸着させたり、Itoda Pretreatment agent for metal plating and metal plating method using the same Technical field The present invention relates to a method for metal plating by electroless plating on a surface of a material having low conductivity or a mirror-like object or powder, and The present invention relates to a pretreatment agent for metal plating. Background Art The electroless metal plating method is one of the methods of forming a metal film on a non-conductive substrate, and as a pretreatment for electroless plating, a noble metal such as palladium is used as a catalyst to adhere to the substrate in advance. A method called activation is generally used. Previously, or to adsorb the P d and immersed in a P d C 1 2 aqueous solution was processed by S n C 1 2 hydrochloric acid aqueous solution,
5 nと P dを含んだコロイ ド溶液により P dを表面に担持させる方 法が使われてきた。 これらの方法は S nを使用することや処理工程 が複雑であるなど問題が多い。 そこで最近、 無電解めつきの触媒で ある P dなどの貴金属を表面に担持させる方法としてこれら貴金属 類と錯体を形成できる官能基を有するシランカツプリング剤を使つ た方法が色々と提案されている （特公昭 5 9— 5 2 7 0 1、 特開昭A method of supporting Pd on the surface with a colloid solution containing 5n and Pd has been used. These methods have many problems, such as the use of Sn and complicated processing steps. Recently, various methods using silane coupling agents having a functional group capable of forming a complex with these noble metals have been proposed as a method for supporting a noble metal such as Pd, which is an electroless plating catalyst, on the surface. (Japanese Patent Publication No. 59-52710,
6 0— 1 8 1 2 9 4、 特開昭 6 1— 1 9 4 1 8 3、 特開平 3— 4 4 1 4 9 ) 。 しかしながら、 この中で示されているシランカップリン グ剤を下地に均一に吸着させようとすると一般的なァミノシラン力 ップリング剤やエポキシシランカツプリング剤は、 水溶液中で脱水 縮合反応によりゲル化しやすく高濃度に溶解できない。 また、 有機 溶剤中では加水分解縮合が起こりにくく、 大半がモノマーで存在す るため液の粘性が低い。 このために、 鏡面物上に均一に塗布しても 膜厚の調整が難しく、 カップリング剤の膜が薄膜でしか形成できな かった。 このため、 貴金属を捕獲する官能基が表面に少量しか存在 できないため、 後工程でのめっき触媒の働きをもつ貴金属の付着が 不均一となる。 この結果として無電解めつき膜が均一に形成するこ とが難しかった。 このため鏡面ガラスへの無電解めつきは、 表面を フッ化水素酸や熱した強アル力リ液によリ表面を粗化する方法が現 在も行われている。 また、 粉体への処理でも、 一般的なアミノシラ ンカップリング剤やエポキシシランカップリング剤は表面への付着 が少ないため、 処理液の溶媒を完全に揮発させて強制的に表面に付 着させた後、 加熱乾燥して加水分解縮合させねばならなかった。 発明の開示 本発明はこうした実情の下に従来無電解めつきが適用しにくかつ た粉体や鏡面物に対しても好適に無電解めつきが可能な新規な無電 解めつきによる金属めつき方法、 およびそのための金属めつき前処 理剤を提供することを目的とするものである。 60-181281, JP-A-61-194183, JP-A-3-414149). However, when trying to uniformly adsorb the silane coupling agent shown in the above, the general aminosilane coupling agent and epoxysilane coupling agent tend to gel by dehydration condensation reaction in an aqueous solution and have high performance. Insoluble in concentration. In addition, hydrolysis and condensation hardly occur in an organic solvent, and the viscosity of the liquid is low because most of the monomer is present. For this reason, even if it is applied evenly on a mirror It was difficult to adjust the film thickness, and the coupling agent film could only be formed as a thin film. For this reason, only a small amount of functional groups for capturing the noble metal are present on the surface, and the adhesion of the noble metal, which acts as a plating catalyst, in the subsequent process becomes uneven. As a result, it was difficult to form a uniform electroless plating film. For this reason, electroless plating on mirror glass is currently performed by roughening the surface with hydrofluoric acid or a heated strong solution. In addition, even when treating powder, general aminosilane coupling agents and epoxysilane coupling agents adhere little to the surface, so the solvent in the treatment liquid is completely volatilized and forced to adhere to the surface. After that, it had to be dried by heating and subjected to hydrolysis and condensation. DISCLOSURE OF THE INVENTION Under such circumstances, the present invention provides a new metallization by electroless plating that is conventionally not applicable to electroless plating and that can be suitably applied to powder and mirror-like objects. An object of the present invention is to provide a plating method and a metal plating pretreatment agent therefor.
本発明者は、 鋭意検討した結果、 前記貴金属イオンと錯体形成能 を有するシランカップリング剤として特定のシランカップリング剤 を選択することにより解決し得ることを知見し、 本発明に至った。 すなわち、 本発明は、  As a result of intensive studies, the present inventor has found that the problem can be solved by selecting a specific silane coupling agent as the silane coupling agent having the ability to form a complex with the noble metal ion, and reached the present invention. That is, the present invention
( 1 ) 貴金属イオンと錯体を形成する活性官能基を有するァゾール 系化合物とエポキシシラン系化合物との反応により得られたシラ ンカツプリング剤からなる金属めつき前処理剤、  (1) a metal plating pretreatment agent comprising a silane coupling agent obtained by reacting an azole compound having an active functional group that forms a complex with a noble metal ion with an epoxysilane compound;
( 2 ) 貴金属イオンと錯体を形成する活性官能基を有するァゾール 系化合物とエポキシシラン系化合物との反応によリ得られたシラ ンカツプリング剤で表面処理した被めつき物を貴金属イオンを含 む溶液で処理した後、 無電解めつきすることを特徴とする金属め つき方法、  (2) A solution containing a noble metal ion on an adherend surface-treated with a silane coupling agent obtained by the reaction of an azole compound having an active functional group that forms a complex with a noble metal ion and an epoxysilane compound. Metal plating method characterized by electroless plating after treatment with
( 3 ) ァゾール系化合物がイミダゾール類である前記 （ 2 ) 記載の 金属めつき方法、 P JP (3) The metal plating method according to (2), wherein the azole compound is an imidazole. P JP
3  Three
( 4 ) 貴金属イオンがパラジウムイオンである前記 （ 2 ) 記載の金 属めっき方法、 (4) The metal plating method according to the above (2), wherein the noble metal ion is a palladium ion,
( 5 ) 無電解めつきが銅またはニッケルである前記 （ 2 ) 記載の金 属めっき方法、  (5) The metal plating method according to (2), wherein the electroless plating is copper or nickel.
に関する。 発明を実施するための最良の形態 本発明は、 無電解めつきの触媒である P dなどの貴金属を被めつ き面に担持させるために使用するシランカツプリング剤、 すなわち 貴金属と錯体形成能を有する官能基を有するシランカップリング剤 として、 前記貴金属イオンと錯体を形成する活性官能基を有するァ ゾール系化合物とエポキシシラン系化合物との反応生成物を使用す ることが重要である。 About. BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a silane coupling agent used to support a noble metal such as Pd, which is a catalyst for electroless plating, on a surface to be covered, that is, the ability to form a complex with a noble metal. It is important to use, as the silane coupling agent having a functional group, a reaction product of an azole compound having an active functional group which forms a complex with the noble metal ion and an epoxysilane compound.
前記ァゾ一ル系化合物としては、 ピロ一ル、 インドール、 イミダ ゾ一ル、 ピラゾール、 ベンズイミダゾ一ル、 インダゾール等があげ られるが、 これらに制限されるものではない。 また前記エポキシシ ラン系化合物としては、 分子内にエポキシ基とアルコキシシリル基 を有する化合物であり、 一般的なものとしては γ—グリシドキシプ 口ピルアルコキシシランがあるが、 これに制限されるものではない。 ァゾール系化合物とエポキシシラン系化合物との反応で得られたシ ランカップリング剤自体は、 すでに公知である。 例'えば特開平 6— 2 5 6 3 5 8号公報にィミダゾール化合物とエポキシシランとの反 応によリイミダゾールシラン化合物を得ることが開示されているが、 他のァゾ一ル系化合物との反応もこれと同様にして行うことができ る。 この反応生成物のシランカップリング剤は、 分子間および分子 内縮合物を含んだ状態で得られることがあるが、 とくにこれらを分 別する必要はなく混合物の状態で使用できる。 このシランカツプリ ング剤は反応性が高く、 また、 水溶液の酸性度を調節することで任 意の水溶液濃度に調整ができること、 溶解した溶液にある程度の粘 性を持たせることができることなどの特性を有する。 こうしたこと から、 このシランカツプリング剤を用いて被めつき物の下地にある 程度の厚みでかつ均一に被膜形成することができる。 しかも従来の ァミノシランに代表される一般的なカツプリング剤では難しかった 鏡面物上や溶媒を揮発しなければ処理できなかった粉体物上なども 含め各種の下地に対して容易に無電解めつきが可能である。 前記貴 金属としては、 無電解めつき液から被めつき物表面に銅やニッケル などの金属を析出させる際の触媒効果を示すパラジウム、 銀、 白金、 金などがあげられるが、 特にパラジウムが好ましい。 Examples of the azo compound include, but are not limited to, pyrrole, indole, imidazole, pyrazole, benzimidazole, indazole and the like. The epoxysilane-based compound is a compound having an epoxy group and an alkoxysilyl group in a molecule, and a general one is γ-glycidoxypropylpyralkoxysilane, but is not limited thereto. The silane coupling agent itself obtained by the reaction of the azole compound and the epoxysilane compound is already known. For example, Japanese Patent Application Laid-Open No. Hei 6-25663 / 58 discloses that an imidazole compound and an epoxysilane are reacted to obtain an imidazole silane compound. Can be carried out in the same manner. The silane coupling agent of this reaction product may be obtained in a state containing intermolecular and intramolecular condensates, but it is not necessary to separate them, and they can be used in a mixture state. This silane coupling agent has characteristics such as high reactivity, the ability to adjust the concentration of the aqueous solution by adjusting the acidity of the aqueous solution, and the ability to give the dissolved solution a certain degree of viscosity. . These things Therefore, a film can be formed with a certain thickness under the substrate of the object to be coated and uniformly using the silane coupling agent. In addition, electroless plating can be easily applied to various types of bases, including mirrors and powders that could not be processed without evaporating the solvent, which were difficult with conventional coupling agents represented by conventional aminosilanes. It is possible. Examples of the noble metal include palladium, silver, platinum, and gold that exhibit a catalytic effect when depositing a metal such as copper or nickel on the surface of an object to be plated from an electroless plating solution, with palladium being particularly preferred. .
本発明の金属めつき方法によれば、 被めつき物はその性状に制限 されない。 例えばガラス、 セラミックなどの無機材料、 ポリエステ ル、 ポリアミ ド、 ポリイミ ド、 フッ素樹脂などのプラスチック材料、 そのフィルム、 シート、 繊維、 必要によリガラス布基材などで補強 されたエポキシ樹脂などの絶縁板などの絶縁物や S i ウェハーなど の半導体などの導電性の低い被めつき物に適用されるが、 被めつき 物は透明ガラス板、 S iウェハー、 その他半導体基板のような鏡面 物であっても、 また粉体であっても本発明の方法を好ましく適用す ることができる。 このような粉体としては、 例えばガラスビーズ、 二硫化モリブデン粉末、 酸化マグネシウム粉末、 黒鉛粉末、 S i C 粉末、 酸化ジルコニウム粉末、 アルミナ粉末、 酸化ゲイ素粉末、 マ イカフレーク、 ガラス繊維、 窒化ゲイ素、 テフロン粉末などがあげ られる。  According to the metal plating method of the present invention, the properties of the adherend are not limited. For example, inorganic materials such as glass and ceramics, plastic materials such as polyester, polyamide, polyimide, and fluororesin; insulating plates such as epoxy resin reinforced with films, sheets, fibers, and, if necessary, glass substrates It is applied to insulators with low conductivity such as insulators such as semiconductors and semiconductors such as Si wafers, but the objects to be coated are mirror-like objects such as transparent glass plates, Si wafers, and other semiconductor substrates. The method of the present invention can be preferably applied to powders and powders. Such powders include, for example, glass beads, molybdenum disulfide powder, magnesium oxide powder, graphite powder, SiC powder, zirconium oxide powder, alumina powder, gay oxide powder, mica flake, glass fiber, gay nitride Element and Teflon powder.
無電解めつきする下地を前記したようなァゾール系化合物とェポ キシシラン系化合物との反応生成物であるシランカツプリング剤で 処理する場合、 このシランカップリング剤を適当な溶媒、 例えば、 水、 メチルアルコール、 ェチルアルコ一ノレ、 2—プロパノール、 ァ セトン、 トルエン、 エチレングリコール、 ポリエチレングリコール やこれらを混合した溶液などに溶解させた溶液に使用できる。 板状 の下地に対しては、 浸漬処理や刷毛塗り等で表面コ一トした後に溶 媒を揮発させる方法が一般的であるが、 これに限定されるものでは なく表面に均一にシランカツプリング剤を付着させる方法であれば よい。 また、 粉体に対しては、 浸漬処理後溶媒を揮発させて強制的 に溶液中に含まれるシランカップリング剤を下地表面に付着させる 方法の他にこのシランカップリング剤の均一な成膜性によリ浸漬処 理状態で下地表面に吸着が可能であることから、 処理後溶媒を瀘過 分離して湿った粉体を乾燥させる方法も可能である。 When the base to be electrolessly deposited is treated with a silane coupling agent which is a reaction product of the azole compound and the epoxysilane compound as described above, the silane coupling agent may be treated with an appropriate solvent such as water, It can be used for solutions dissolved in methyl alcohol, ethyl alcohol, 2-propanol, acetone, toluene, ethylene glycol, polyethylene glycol, or a mixture thereof. For a plate-shaped substrate, a method of volatilizing the solvent after coating the surface by dipping or brushing is generally used, but the method is not limited to this, and the silane coupling is uniformly applied to the surface. Any method can be used as long as it is a method of attaching an agent. For powders, after immersion, the solvent is volatilized to force In addition to the method of adhering the silane coupling agent contained in the solution to the base surface, the uniform film-forming property of the silane coupling agent allows the silane coupling agent to be adsorbed on the base surface in the re-dipping state After the treatment, a method of filtering off the solvent and drying the wet powder is also possible.
処理する溶液中のシランカップリング剤濃度はこれに限ったもの ではないが、 0. 00 1〜 1 0重量％が使いやすい。 0. 00 1重 量％未満の場合、 基材の表面に付着するカップリング剤量が低くな りやすく、 効果が得にくい。 また、 1 0重量％を超えると付着量が 多すぎて乾燥しにくかったり、 粉末の凝集を起こしやすくなる。 表 面処理後に使用した溶媒を揮発させるには、 この溶媒の揮発温度以 上に加熱して表面を乾燥できれば充分であるが、 さらに 6 0〜 1 2 0°Cで 1 0〜 6 0分間の加熱乾燥することが好ましい。  The concentration of the silane coupling agent in the solution to be treated is not limited to this, but 0.001 to 10% by weight is easy to use. If the amount is less than 0.001% by weight, the amount of the coupling agent adhering to the surface of the base material tends to be low, and the effect is hardly obtained. On the other hand, if it exceeds 10% by weight, it is difficult to dry the powder due to an excessively large amount of adhesion, and it is easy to cause powder agglomeration. In order to volatilize the solvent used after surface treatment, it is sufficient if the surface can be dried by heating to a temperature higher than the volatilization temperature of this solvent. Heat drying is preferred.
前記のようにして表面処理したものに対して化学めつきする方法 は公知の方法である。 すなわち、 パラジウムなどの貴金属イオンを 含んだ溶液と接触させて、 下地表面に処理されたカツプリング剤の ァゾール基に貴金属を捕捉させる。 余分なハロゲン化物などの可溶 性貴金属塩や塩酸等の可溶化剤を洗浄後、 無電解めつきなどの化学 めっき処理を行う。  The method of chemically plating the surface treated as described above is a known method. That is, it is brought into contact with a solution containing a noble metal ion such as palladium, and the noble metal is captured by the azole group of the coupling agent treated on the base surface. After washing out the solubilizing agents such as excess noble metal salts such as halides and hydrochloric acid, perform chemical plating such as electroless plating.
また、 無電解めつきを最初に行って金属薄膜を形成させ、 導電性 のない下地にある程度の導電性を持たせた後、 電気めつきゃ卑なる 金属との置換めつきを行うことも可能である。  It is also possible to perform electroless plating first to form a metal thin film, and to give a certain degree of conductivity to a non-conductive base, and then perform replacement plating with a metal that is less conductive. is there.
本発明により無電解めつきにより銅、 ニッケル、 'コバルト、 スズ、 金などの金属をめつきすることができるが、 本発明に使用する無電 解めつき液の代表的なものを記すと以下のものがある。  According to the present invention, metals such as copper, nickel, 'cobalt, tin, and gold can be plated by electroless plating. Typical examples of the electroless plating solution used in the present invention are as follows. There is something.
①高速厚付用無電解銅めつき組成代表例. (1) Typical example of electroless copper plating composition for high-speed thickening.
C u S 04. 5 H2〇 0. 04〜0. 06 mo l/ l C u S 0 4. 5 H 2 〇 0. 04~0. 06 mo l / l
EDTA. 2 N a 0. 04〜0. 1 2 mo l/lEDTA. 2 Na 0.04 to 0.12 mol / l
H C H 0 (37 %) 0. 08〜0. 5 mo l Z l p H 1 2〜 1 2. 5 H C H 0 (37%) 0.08 to 0.5 mol z lp H 12 to 12.5
めっき温度 7 0〜9 0°C ②低温無電解銅めつき組成代表例 Plating temperature 70 ~ 90 ° C ② Typical example of low temperature electroless copper plating composition
C u S 04. 5 H20 1 2. 5〜 1 4. 5 g/ 1 C u S 0 4. 5 H 2 0 1 2. 5~ 1 4. 5 g / 1
H C H 0 (37 %) 20〜2 5 g/ l H C H 0 (37%) 20-25 g / l
口ッセル塩 2 5〜4 0 g 1  Mouth tassel salt 25 to 40 g 1
p H 1 2. 2〜 1 2.  pH 12.2 ~ 1 2.
めっき温度 20〜30°C  Plating temperature 20-30 ° C
③高温タイプ酸性浴無電解 N iめっき組成代表例  ③ Typical example of high temperature type acidic bath electroless Ni plating composition
硫酸ニッケル 20〜 2 2 g/ 1  Nickel sulfate 20-22 g / 1
乳酸 2 5〜 3 0 g Z 1  Lactic acid 25 to 30 g Z 1
プロピオン酸 2〜3 gノ 1  Propionic acid 2-3 g
次亜りん酸ナトリウム 20〜2 2 g/ l Sodium hypophosphite 20-22 g / l
H 4. 5〜 5. 5  H 4.5 to 5.5
めっき温度 80〜9 0°C  Plating temperature 80 ~ 90 ° C
④低温タイプアンモニアアルカリ性浴無電解 N iめっき組成代表例 硫酸ニッケル 24〜 26 1 ④Low temperature type ammonia alkaline bath electroless Ni plating composition typical example Nickel sulfate 24-26 1
ピロリン酸ナトリウム 48〜52 gZl  Sodium pyrophosphate 48-52 gZl
次亜りん酸ナトリウム 24〜26 1  Sodium hypophosphite 24-26 1
p H 1 0〜 1 1  p H 10 ~ 1 1
めっき温度 5 5〜6 5°C 実施例 実施例 1  Plating temperature 55 ~ 65 ° C Example 1
厚さ l mmのスライ ドガラス板をアルカリ脱脂液で処理した後、 このガラス板表面上にィミダゾールと γ—グリシドキシプロビルト リメ 卜キシシランとの等モル反応生成物であるシランカツプリング 剤を 0. 4重量％含んだ 2—プロパノ一ル溶液を用いて 5 0 0 R Ρ Μにてスピンコートした。 その後、 この板を 1 0 5°Cで 30分間乾 燥した。 さらに P d活性化処理液 CG— 53 5 A (ァクチベータ一. 日鉱メタルプレーティング （株） 製） に室温で 1分間浸漬した後、 脱イオン水約 1 00 m lで水洗し 1 0 5°Cで 3 0分間乾燥してガラ ス板表面に貴金属活性化処理を行った。 次に無電解ニッケルめっき 液二コム 7 N (日鉱メタルプレーティング （株） 製） 中に 80°Cで 4分間浸漬した。 無電解ニッケルめっき液はガラス全面に均一に光 沢のある膜が析出しており、 セロハンテープによる剥離もなく良好 な密着性を持つことが確認された。 After treating a slide glass plate having a thickness of l mm with an alkaline degreasing solution, a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxyprovirtrimethoxysilane, is added to the surface of the glass plate. Using a 2-propanol solution containing 4% by weight, spin coating was performed at 500 R R. Thereafter, the plate was dried at 105 ° C for 30 minutes. Furthermore, after immersing for 1 minute at room temperature in Pd activation solution CG-535A (activator I. manufactured by Nikko Metal Plating Co., Ltd.), it was washed with about 100 ml of deionized water and washed at 105 ° C. Dried for 30 minutes A noble metal activation treatment was performed on the surface of the metal plate. Next, it was immersed in Nicom 7N electroless nickel plating solution (manufactured by Nikko Metal Plating Co., Ltd.) at 80 ° C for 4 minutes. The electroless nickel plating solution uniformly deposited a glossy film on the entire surface of the glass, and it was confirmed that the electroless nickel plating solution had good adhesion without peeling off with a cellophane tape.
比較例 1 Comparative Example 1
厚さ l mmのスライ ドガラス板をアル力リ脱脂液で処理した後、 表面にカップリング剤処理せずに P d活性化処理液 CG— 5 3 5 A に室温で 1分間浸潰した後、 脱イオン水約 1 0 0 m lで水洗し 1 0 5°Cで 30分間乾燥してガラス板表面に貴金属活性化処理を行った。 次に無電解ニッケルめっき液二コム 7 N中に 8 0°Cで 4分間浸潰し た。 無電解二ッケルめつきはガラス板にほとんど析出しなかった。 比較例 2  After treating a lmm-thick slide glass plate with a degreasing solution, it was immersed in a Pd activation solution CG-535A for 1 minute at room temperature without treating the surface with a coupling agent. The glass plate surface was washed with about 100 ml of deionized water and dried at 105 ° C. for 30 minutes to perform a precious metal activation treatment. Next, it was immersed in the electroless nickel plating solution 2N 7N at 80 ° C for 4 minutes. Electroless nickel plating hardly precipitated on the glass plate. Comparative Example 2
厚さ 1 mmのスライ ドガラス板をフッ素 ·硝酸混合液 （フッ酸 1 00 m l/L、 硝酸 1 00m l /L) 中に 2 5 °Cで 1 0分間浸漬 して表面を粗化処理した。 このガラス板をアル力リ脱脂液で処理し て、 P d活性化処理液 CG— 53 5 Aに室温で 1分間浸潰した後、 脱イオン水約 1 00 m lで水洗し 1 0 5°Cで 3 0分間乾燥してガラ ス板表面に貴金属活性化処理を行った。 次に無電解ニッケルめっき 液二コム 7 N中に 8 0°Cで 4分間浸漬した。 無電解ニッケルめっき はガラス板にほとんど析出しなかつた。  A 1 mm thick slide glass plate was immersed in a mixture of fluorine and nitric acid (100 ml / L hydrofluoric acid, 100 ml / L nitric acid) at 25 ° C for 10 minutes to roughen the surface. This glass plate is treated with an alkaline degreasing solution, immersed in a Pd activation treatment solution CG-535A for 1 minute at room temperature, washed with about 100 ml of deionized water, and washed at 105 ° C After drying for 30 minutes, the precious metal activation treatment was performed on the glass plate surface. Next, it was immersed in 7 N of an electroless nickel plating solution at 80 ° C for 4 minutes. Electroless nickel plating hardly precipitated on the glass plate.
比較例 3 Comparative Example 3
厚さ l mmのスライ ドガラス板をアルカリ脱脂液で処理した後、 このガラス板表面上にアミノシランカップリング剤 KBM— 903 (信越化学工業 （株） 製 γ—ァミノプロビルトリメ トキシシラン） を 0. 4重量％含んだ 2—プロパノール溶液を用いて 5 00 RPM にてスピンコートした。 その後、 この板を 1 0 5°Cで 3 0分間乾燥 した。 さらに P d活性化処理液 CG— 5 3 5 Aに室温で 1分間浸漬 した後、 脱イオン水約 1 00m lで水洗し 1 0 5 で 3 0分乾燥し てガラス板表面に貴金属活性化処理を行った。 次に無電解ニッケル めっき液二コム 7 N中に 8 0°Cで 4分間浸漬した。 無電解ニッケル めっきはガラス板の一部にしか析出していなかった。 After treating a slide glass plate having a thickness of l mm with an alkaline degreasing solution, an aminosilane coupling agent KBM-903 (γ-aminoprovir trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the surface of the glass plate. Spin coating was performed at 500 RPM using a 2-propanol solution containing 4% by weight. Thereafter, the plate was dried at 105 ° C. for 30 minutes. Furthermore, after immersing in Pd activation solution CG-535A for 1 minute at room temperature, washing with about 100 ml of deionized water and drying with 105 for 30 minutes, precious metal activation treatment on the glass plate surface Was done. Next, it was immersed for 4 minutes at 80 ° C in 2N 7N, an electroless nickel plating solution. Electroless nickel The plating was deposited only on a part of the glass plate.
比較例 4， 5 Comparative Examples 4 and 5
加水分解縮合反応を促進させるために水と 2—プロパノール等量 の混合液に微量の塩酸を加えた溶液にァミノシランカツプリング剤 K B M— 9 0 3を 0 . 4重量％と濃度を 1 0倍とした4重量％ (比 較例 5 ) を溶解した液を作り比較例 3と同様にして貴金属活性化処 理を行った後、 無電解ニッケルめっきを行った。 無電解ニッケルめ つきはいずれもガラス板の半分程度にまばらにしか析出しなかった。 実施例 2  To promote the hydrolysis-condensation reaction, a solution of a mixture of water and an equal amount of 2-propanol to which a trace amount of hydrochloric acid is added is added with 0.4% by weight of the aminosilane coupling agent KBM-903 and a concentration of 10%. A solution in which 4% by weight (Comparative Example 5) was dissolved was prepared, and a noble metal activation treatment was performed in the same manner as in Comparative Example 3, followed by electroless nickel plating. In all cases, electroless nickel plating was sparsely deposited on about half of the glass plate. Example 2
ペッ トフィルム （商品名ダイヤホイル） を 2—プロパノール中で 5分間超音波洗浄して表面を脱脂処理したあと、 1 0 5 °Cで 1 0分 間乾燥した。 次にこのフィルムをィミダゾ一ルと γ -グリシドキシ プロビルトリエトキシシランとの等モル反応生成物であるシラン力 ップリング剤を 4重量。 /0含んだ 2 —プロパノール溶液中に 1分間浸 漬した後 1 0 5でで 1 0分間乾燥した。 さらに P d活性化処理液 C G - 5 3 5 Aに室温で 1分間浸漬した後、 脱イオン水で水洗し 1 0 5 °Cで 1 0分間乾燥してぺッ 卜フィルム表面にに貴金属活性化処理 を行った。 次に無電解銅めつき液 K C— 5 0 0 (日鉱メタルプレー ティング （株） 製商品名） 中に 7 2 °Cで 2 0分間浸潰した。 無電解 銅めつきがぺッ トフイルム全面に均一に光沢のある膜を析出した。 実施例 3 The PET film (trade name: Diafoil) was ultrasonically cleaned in 2-propanol for 5 minutes to degrease the surface, and then dried at 105 ° C for 10 minutes. Next, this film was coated with 4 weight parts of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltriethoxysilane. After immersion in a 2-propanol solution containing / 0 for 1 minute, the mixture was dried at 105 with agitation for 10 minutes. Furthermore, after immersing in Pd activation solution CG-535A for 1 minute at room temperature, washing with deionized water, drying at 105 ° C for 10 minutes, and activating the noble metal on the surface of the pet film Processing was performed. Next, it was immersed in an electroless copper plating solution KC-500 (trade name, manufactured by Nikko Metal Plating Co., Ltd.) at 72 ° C for 20 minutes. Electroless copper plating uniformly deposited a glossy film on the entire surface of the hot film. Example 3
ィミダゾ一ルと γ—グリシドキシプロビルトリメ'トキシシランと の等モル反応生成物であるシランカツプリング剤を 0 . 4重量％含 んだ 2—プロパノール溶液中にガラス布基材エポキシ樹脂絶縁板 Epoxy resin insulation board based on glass cloth in a 2-propanol solution containing 0.4% by weight of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane.
(松下電工 （株） 製銅張積層板 F R— 4から銅を化学エッチングに より除去した板） を 1分間浸潰した後 1 0 5 °Cで 6 0分間乾燥した。 次にこの積層板を P d活性化処理液 C G— 5 3 5 Aに室温で 1分間 浸漬した後、 脱イオン水で水洗し 1 0 5 °Cで 6 0分間乾燥して積層 板表面に貴金属活性化処理を行った。 この板を無電解二ッゲルめつ き液二コム 7 N中に 8 0 °Cで 2分間浸漬すると、 無電解ニッケルめ つきが積層板に均一に析出した。 また、 同様な貴金属活性化処理し た積層板を無電解銅めつき液 KC一 50 0中に 7 0°Cで 3 0分間浸 漬すると、 銅が表面に均一に析出した。 The copper-clad laminate FR-4 manufactured by Matsushita Electric Works, Ltd., which had copper removed by chemical etching, was immersed for 1 minute and then dried at 105 ° C for 60 minutes. Next, this laminate was immersed in Pd activation treatment solution CG-5335A for 1 minute at room temperature, washed with deionized water, dried at 105 ° C for 60 minutes, and the noble metal was placed on the laminate surface. An activation process was performed. When this plate was immersed for 2 minutes at 80 ° C in 2N 7N, an electroless Nigel plating solution, electroless nickel plating was uniformly deposited on the laminate. The same precious metal activation treatment When the laminated board was immersed in electroless copper plating solution KC-500 at 70 ° C for 30 minutes, copper was uniformly deposited on the surface.
比較例 6 Comparative Example 6
実施例 3と同様なガラス布基材エポキシ樹脂絶縁板を水と 2—プ ロパノール等量の混合液に微量の塩酸を加えた溶液にァミノシラン カップリング剤 KBM— 9 03を 0. 4重量％溶解した溶液中に 1 分間浸潰した後 1 0 5°Cで 6 0分間乾燥した。 さらに P d活性化処 理液 CG— 5 3 5 Aに室温で 1分間浸潰した後、 脱イオン水で水洗 した後 1 05°Cで 6 0分間乾燥して積層板表面に貴金属活性化処理 を行った。 この板を無電解ニッケルめっき液二コム 7 N中に 80°C で 2分間浸漬すると、 無電解ニッケルめっきが積層板上に析出した が全体の 8割程度であった。  0.4% by weight of an aminosilane coupling agent KBM-903 was dissolved in a solution obtained by adding a small amount of hydrochloric acid to a mixture of water and 2-propanol in the same glass cloth-based epoxy resin insulating plate as in Example 3. The solution was immersed in the solution for 1 minute and then dried at 105 ° C. for 60 minutes. Furthermore, after immersing in Pd activation treatment solution CG-5335A for 1 minute at room temperature, washing with deionized water, drying at 105 ° C for 60 minutes, the laminate surface was activated with precious metal. Was done. When this plate was immersed in the electroless nickel plating solution 2COM 7N at 80 ° C for 2 minutes, electroless nickel plating precipitated on the laminated plate, but about 80% of the total.
実施例 4 Example 4
約 1. 5 mm径のガラスビーズ 20 gをイミダゾールと γ—グリ シドキシプロピルメチルジェトキシシランとの等モル反応生成物で あるシランカップリング剤 0. 08 gを溶解した 5 0 m 1の 2—プ ロパノ一ル溶液に 1分間浸漬する。 液を濾過した後 1 0 5°Cで 30 分間乾燥する。 次にこのガラスビーズを P d活性化処理液 C G— 5 3 5 Aに室温で 1分間浸潰した後、 この活性化処理液を瀘過しさら に 5 0 m 1の脱イオン水で水洗し 1 05°Cで 3 0分間乾燥を行いガ ラスビーズ表面に貴金属活性化処理した。 このガラスビーズを無電 解ニッケルめっき液二コム 7 N中に 80°Cで 4分間浸漬すると無電 解ニッケルめっきがビーズ全面にほぼ均一に析出した。  20 g of glass beads with a diameter of about 1.5 mm was dissolved in 0.08 g of a silane coupling agent, an equimolar reaction product of imidazole and γ-glycidoxypropylmethyljetoxysilane. — Immerse in propanol solution for 1 minute. After filtering the solution, it is dried at 105 ° C for 30 minutes. Next, the glass beads were immersed in a Pd activation treatment solution CG-5335A for 1 minute at room temperature, and then the activation treatment solution was filtered and washed with 50 ml of deionized water. After drying at 105 ° C for 30 minutes, the surface of the glass beads was activated with a noble metal. When the glass beads were immersed in the electroless nickel plating solution 2N 7N at 80 ° C for 4 minutes, the electroless nickel plating was deposited almost uniformly on the entire surface of the beads.
比較例 7 Comparative Example 7
約 1. 5 mm径のガラスビーズをアミノシランカツプリング剤 K BM— 903を 0. 4重量％含んだ 2—プロパノール溶液 0. 08 gを溶解した 50 m 1の 2—プロパノ一ル溶液に 1分間浸漬する。 液を濾過した後 1 0 5°Cで 30分間乾燥する。 次にこのガラスビー ズを P d活性化処理液 C G— 5 3 5 A 5 0 m 1に室温で 1分間浸漬 した後、 この活性化処理液を瀘過しさらに 50 m lの脱イオン水で 水洗し 1 05°Cで 3 0分間乾燥を行いガラスビーズ表面に貴金属活 性化処理した。 このガラスビーズを無電解ニッケルめっき液二コムGlass beads of about 1.5 mm in diameter are dissolved in a 2-propanol solution containing 0.08 g of a 2-propanol solution containing 0.4% by weight of aminosilane coupling agent K BM-903 for 1 minute. Immerse. After filtering the liquid, it is dried at 105 ° C for 30 minutes. Next, this glass bead is immersed in 50 ml of Pd activation solution CG-535A at room temperature for 1 minute, and the activation solution is filtered and further washed with 50 ml of deionized water. Dry at 30 ° C for 30 minutes and apply precious metal Sexualized. This glass bead is electroless nickel plating solution
7 N中に 8 0°Cで 4分間浸漬すると無電解ニッケルめっきはビーズ 面に析出したが、 析出しない部分が 3割以上あった。 When immersed in 7N at 80 ° C for 4 minutes, electroless nickel plating precipitated on the bead surface, but more than 30% did not deposit.
実施例 5 Example 5
平均粒径 5 0ミクロンの二硫化モリブデン粉末 2 5 gをイミダゾ ールと γ—グリシドキシプロビルトリメ トキシシランとの等モル反 応生成物であるシランカップリング剤 0. 1 gを溶解した 5 0 m 1 の 2—プロパノール溶液に室温で 1 0分間撹拌する。 溶媒の 2—プ ロパノ一ルを留去した後 1 05°Cで 6 0分間乾燥する。 次にこの二 硫化モリブデン粉末を P d活性化処理液 C G— 5 3 5 A 50m lに 室温で 2 0分間撹拌した後、 この活性化処理液を濾過除去しさらに 50m lの脱イオン水で水洗した後 1 0 5でで 6 0分間乾燥を行い 粉体表面に貴金属活性化処理した。 この二硫化モリブデン粉末を無 電解銅めつき液 KC— 50 0を用いて 7 2 °Cでめつきを行った。 1 w t %の無電解銅めつきにより粉体表面に均一な銅めつき膜が形成 でき、 下地の二硫化モリブデンを完全に覆うことができた。  25 g of molybdenum disulfide powder having an average particle diameter of 50 microns was dissolved in 0.1 g of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane. Stir for 10 minutes at room temperature in 0 ml of 2-propanol solution. After distilling off the solvent, 2-propanol, dry at 105 ° C for 60 minutes. Next, the molybdenum disulfide powder is stirred in 50 ml of Pd activation solution CG-5335A at room temperature for 20 minutes, and the activated solution is removed by filtration and further washed with 50 ml of deionized water. After that, drying was performed at 105 at 60 minutes, and the surface of the powder was activated with a noble metal. The molybdenum disulfide powder was plated at 72 ° C using an electroless copper plating solution KC-500. A 1 wt% electroless copper plating resulted in a uniform copper plating film on the powder surface and completely covered the underlying molybdenum disulfide.
比較例 8 Comparative Example 8
平均粒径 5 0ミクロンの二硫化モリブデン粉末を P d活性化処理 液 CG— 5 3 5 A 5 0m lに室温で 2 0分間撹拌した後、 この活性 化処理液を濾過除去しさらに 50 m lの脱イオン水で水洗した後 1 05°Cで 6 0分間乾燥を行い粉体表面に貴金属活性化処理した。 この二硫化モリブデン粉末を無電解銅めつき液 KC'— 5 00を用い て 7 2°Cでめつきを行ったが、 無電解銅めつきにより銅めつき膜は ほとんど形成できなかった。  After molybdenum disulfide powder having an average particle diameter of 50 microns was stirred in 50 ml of Pd activation solution CG-535A at room temperature for 20 minutes, the activation solution was removed by filtration and another 50 ml of After washing with deionized water, the powder was dried at 105 ° C. for 60 minutes to activate the noble metal on the powder surface. The molybdenum disulfide powder was plated at 72 ° C. using an electroless copper plating solution KC'-500, but almost no copper plating film was formed due to the electroless copper plating.
実施例 6 Example 6
平均粒径 1 00ミクロンの酸化マグネシウム粉末 5 0 gをイミダ ゾールと γ—グリシドキシプロピルトリエトキシシランとの等モル 反応生成物であるシランカツプリング剤 0. 2 gを溶解した 1 00 in 1の 2—プロパノール溶液に室温で 1 0分間撹拌する。 溶媒の 2 一プロパノールを瀘過した後 1 05°Cで 3 0分間乾燥する。 次にこ の酸化マグネシウム粉末を P d活性化処理液 C G— 5 3 5 A 1 00 m 1に室温で 2 0分間撹拌した後、 この活性化処理液を瀘過除去し さらに 1 00 m 1の脱イオン水で水洗した後 1 0 5°Cで 3 0分間乾 燥を行い粉体表面に貴金属活性化処理した。 この酸化マグネシウム 粉末を無電解銅めつき液 KC— 5 00を用いて 7 2 °Cでめつきを行 つた。 わずか 1 w t %の無電解銅めつきによリ粉体表面に均一な銅 めっき膜が形成でき、 下地の酸化マグネシウムを完全に覆うことが できた。 A solution of 50 g of magnesium oxide powder having an average particle diameter of 100 microns and 0.2 g of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltriethoxysilane, was dissolved in 100 in 1 Stir in 2-propanol solution at room temperature for 10 minutes. After filtering off the solvent, 2-propanol, it is dried at 105 ° C for 30 minutes. Next, this magnesium oxide powder was treated with Pd activation solution CG-5 35 A 100 After stirring at room temperature for 20 minutes at room temperature, the activated solution was removed by filtration, washed with 100 ml of deionized water, dried at 105 ° C for 30 minutes, and powdered. The surface was precious metal activated. The magnesium oxide powder was plated at 72 ° C. using an electroless copper plating solution KC-500. A uniform copper plating film was formed on the powder surface by electroless copper plating of only 1 wt%, and the underlying magnesium oxide was completely covered.
実施例 7 Example 7
平均粒径 1 00ミクロンの天然黒鉛粉 2 5 gを 2—ェチルー 4 - メチルイミダゾ一ルと γ—グリシドキシプロピル卜リメ トキシシラ ンとの等モル反応生成物であるシランカップリング剤 0. 1 gを溶 解した 50m lのェタノール溶液に室温で 1 0分間撹拌する。 溶媒 の 2—プロパノ一ルを留去した後 1 0 5°Cで 3 0分間乾燥する。 次 にこの黒鉛粉末を P d活性化処理液 C G— 5 3 5 A 1 00 m 1に室 温で 2 0分間撹拌した後、 この活性化処理液を瀘過除去しさらに 5 0m lの脱イオン水で水洗した後 1 0 5°Cで 30分間乾燥を行い 粉体表面に貴金属活性化処理した。 この黒鉛粉末を無電解銅めつき 液 KC一 500を用いて 7 2 °Cでめつきを行った。 6 w t %の無電 解銅めつきにより粉体表面に均一な銅めつき膜が形成できた。 また、 同様に貴金属活性化処理した黒鉛粉末を無電解ニッケルめっき液二 コム 7 N中に 8 0°Cで 4分間浸漬すると、 無電解ニッケルめっきが 表面にほぼ均一に析出し粉体の色が黒色から灰色と'なり、 下地を二 ッゲルで完全に覆うことができた。  25 g of natural graphite powder having an average particle size of 100 microns is used as a silane coupling agent which is an equimolar reaction product of 2-ethyl-4-methylimidazole and γ-glycidoxypropyltrimethoxysilane 0.1 Stir at room temperature for 10 minutes in 50 ml of ethanol solution of g dissolved. After distilling off 2-propanol as the solvent, the residue is dried at 105 ° C for 30 minutes. Next, this graphite powder was stirred at room temperature for 20 minutes in a Pd activation treatment solution CG-535A at 100 m1, and the activation treatment solution was filtered off to remove 50 ml of deionized water. After washing with water, the powder was dried at 105 ° C for 30 minutes, and the surface of the powder was activated with a noble metal. This graphite powder was plated at 72 ° C. using an electroless copper plating liquid KC-500. A uniform copper plating film was formed on the powder surface by electroless copper plating at 6 wt%. Similarly, when the graphite powder, which has been activated with a noble metal, is immersed in the electroless nickel plating solution Ncom 7 N at 80 ° C for 4 minutes, the electroless nickel plating precipitates almost uniformly on the surface and the color of the powder changes. The color changed from black to gray, and the base was completely covered with Nigel.
実施例 8 Example 8
平均粒径 7 0ミクロンの S i C粉末 5 0 gをイミダゾ一ルと γ― グリシドキシプロピルトリメ トキシシランとの等モル反応生成物で あるシランカップリング剤 0. 2 gを溶解した 1 00m lのメタノ —ル溶液に室温で 1 0分間撹拌する。 溶媒のメタノールを留去した 後 1 0 5°Cで 3 0分間乾燥する。 次にこの S i C粉末を P d活性化 処理液 CG— 5 3 5 A 1 0 0 m 1に室温で 20分間撹拌した後、 こ の活性化処理液を瀘過しさらに 1 00 m lの脱イオン水で水洗した 後 1 0 5°Cで 30分間乾燥を行い粉体表面に貴金属活性化処理した。 この S i C粉末を無電解銅めつき液 KC一 50 0を用いて 7 2 °Cで めっきを行った。 わずか 1 w t %の無電解銅めつきにより粉体表面 に均一な銅めつき膜が形成でき、 完全な銅色粉末となり、 緑色の S i Cを完全に覆うことができた。 100 ml of 50 g of SiC powder having an average particle size of 70 microns dissolved in 0.2 g of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane Is stirred at room temperature for 10 minutes. After distilling off the solvent methanol, it is dried at 105 ° C for 30 minutes. Next, the SiC powder was stirred at room temperature for 20 minutes in a Pd activation treatment solution CG-5335A100 ml, and the activation treatment solution was filtered and a further 100 ml of desiccant was removed. Washed with ionized water Thereafter, drying was performed at 105 ° C. for 30 minutes, and the surface of the powder was subjected to a precious metal activation treatment. The SiC powder was plated at 72 ° C using an electroless copper plating solution KC-500. With only 1 wt% of electroless copper plating, a uniform copper plating film was formed on the powder surface, resulting in a complete copper powder and complete coverage of the green SiC.
比較例 9 Comparative Example 9
平均粒径 7 0ミクロンの S i C粉末 5 0 gを P d活性化処理液 C G- 5 3 5 A 1 00m lに室温で 2 0分間撹拌した後、 この活性化 処理液を瀘過しさらに 1 0 0m lの脱イオン水で水洗した後 1 05 °Cで 3 0分間乾燥を行い粉体表面に貴金属活性化処理した。 この S i C粉末を無電解銅めつき液 KC一 5 00を用いて 7 2 °Cでめつ きを行った。 無電解銅めつきが粉体表面に形成できたが、 2割以上 の S i C粉を覆うことができなかった。  After stirring 50 g of SiC powder having an average particle diameter of 70 μm in 100 ml of Pd activation solution CG-535A at room temperature for 20 minutes, the activated solution is filtered. Further, the powder surface was washed with 100 ml of deionized water, dried at 105 ° C. for 30 minutes, and the surface of the powder was activated with a noble metal. The SiC powder was plated at 72 ° C. using an electroless copper plating solution KC-500. Electroless copper plating was formed on the powder surface, but could not cover more than 20% of the SiC powder.
実施例 8 Example 8
平均粒径 3 0ミクロンの酸化ジルコニウム粉末 5 0 gを 2—メチ ルイミダゾ一ルと γ—グリシドキシプロピルトリエトキシシランと の等モル反応生成物であるシランカツプリング剤 0. 2 gを溶解し た 1 0 0 m 1のメタノール溶液に室温で 1 0分間撹拌する。 溶媒の メタノールを留去した後 1 05°Cで 3 0分間乾燥する。 次にこの酸 化ジルコニウム粉末を P d活性化処理液 CG— 5 3 5 A 1 00m l に室温で 20分間撹拌した後、 この活性化処理液を瀘過しさらに 1 〇 0 m 1の脱イオン水で水洗した後 1 05 °Cで 3 Ό分間乾燥を行 い粉体表面に貴金属活性化処理した。 この酸化ジルコニウム粉末を 無電解ニッケルめっき液二コム 7 N中に 80°Cで 4分間浸漬すると、 無電解ニッケルめっきが酸化ジルコニウム表面にほぼ均一に析出し、 下地を完全に覆うことができた。  50 g of zirconium oxide powder having an average particle diameter of 30 microns is dissolved in 0.2 g of a silane coupling agent which is an equimolar reaction product of 2-methylimidazole and γ-glycidoxypropyltriethoxysilane. The mixture was stirred for 10 minutes at room temperature in a 100 ml methanol solution. After evaporating the solvent methanol, dry at 105 ° C for 30 minutes. Next, the zirconium oxide powder was stirred in 100 ml of Pd activation treatment solution CG-5335A at room temperature for 20 minutes, and the activation treatment solution was filtered, followed by further deionization of 1〇0 m1. After washing with water, the powder surface was dried at 105 ° C for 3 minutes, and the surface of the powder was activated with a precious metal. When this zirconium oxide powder was immersed in the electroless nickel plating solution 2N 7N at 80 ° C for 4 minutes, the electroless nickel plating was deposited almost uniformly on the zirconium oxide surface, and the base was completely covered.
実施例 9 Example 9
直径 0. 3 mmのテフ口ン製糸約 1 gをイミダゾールと γ—グリ シドキシプロビルトリメ 卜キシシランとの等モル反応生成物である シランカップリング剤 0. 0 2 gを溶解した 2 5 0m lのェタノ一 ル溶液に室温で 1 0分間浸漬する。 溶媒のエタノールを留去した後 1 0 5°Cで 3 0分間乾燥する。 次にこの糸を P d活性化処理液 CG 一 5 3 5A 5 0m lに室温で 20分間浸漬した後、 この活性化処理 液を瀘過しさらに 5 0m lの脱イオン水で水洗した後 1 0 5°Cで 30分間乾燥を行い糸の表面に貴金属活性化処理した。 このテフ口 ン製糸を無電解ニッケルめっき液二コム 7 N中に 8 0°Cで 4分間浸 漬すると、 無電解ニッケルめっきが糸表面に均一に析出し、 下地を 完全に覆って糸が灰色になった。 産業上の利用可能性 以上説明したように本発明の新規な金属めつき前処理剤を用いる 無電解めつき法によれば、 従来法では適応しにくい鏡面物や粉体に 対しても好適に無電解めつきを行うことができ、 被めつき物の性状、 形状に制限されることがない。 Approximately 1 g of a 0.3 mm-diameter teflon yarn is dissolved in 0.02 g of a silane coupling agent, which is an equimolar reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane. Immerse in ethanol solution at room temperature for 10 minutes. After distilling off the solvent ethanol Dry at 105 ° C for 30 minutes. Next, the yarn was immersed in 50 ml of Pd activation treatment solution CG-135A at room temperature for 20 minutes, and the activation treatment solution was filtered and further washed with 50 ml of deionized water. The yarn was dried at 05 ° C for 30 minutes to activate the noble metal on the surface of the yarn. When this teflon yarn is immersed in the electroless nickel plating solution 2N 7N at 80 ° C for 4 minutes, the electroless nickel plating is uniformly deposited on the yarn surface, and the yarn is completely covered with the base and gray. Became. INDUSTRIAL APPLICABILITY As described above, according to the electroless plating method using the novel metal plating pretreatment agent of the present invention, the electroless plating method can be suitably applied to mirror-like objects and powders which are difficult to be applied by the conventional method. Electroless plating can be performed, and there is no restriction on the properties and shape of the object to be plated.

Claims

言青求の範囲 . 貴金属イオンと錯体を形成する活性官能基を有するァゾール系 化合物とエポキシシラン系化合物との反応により得られたシラン カツプリング剤からなる金属めつき前処理剤。A metal plating pretreatment agent comprising a silane coupling agent obtained by reacting an azole compound having an active functional group that forms a complex with a noble metal ion with an epoxysilane compound.
. 貴金属イオンと錯体を形成する活性官能基を有するァゾール系 化合物とエポキシシラン系化合物との反応により得られたシラン カツプリング剤で表面処理した被めつき物を貴金属イオンを含む 溶液で処理した後、 無電解めつきすることを特徴とする金属めつ き方法。After treating the adherend surface-treated with a silane coupling agent obtained by the reaction of an azole compound having an active functional group that forms a complex with a noble metal ion with an epoxysilane compound, with a solution containing the noble metal ion, A metal plating method characterized by electroless plating.
. ァゾール系化合物がィミダゾール類である請求項 2記載の金属 めっき方法。 3. The metal plating method according to claim 2, wherein the azole compound is an imidazole.
. 貴金属イオンがパラジウムイオンである請求項 2記載の金属め つき方法。 3. The method according to claim 2, wherein the noble metal ion is a palladium ion.
. 無電解めつきが銅またはニッケルである請求項 2記載の金属め つき方法。 3. The metal plating method according to claim 2, wherein the electroless plating is copper or nickel.
PCT/JP1999/002180 1998-07-07 1999-04-23 Pretreating agent for metal plating, and method for metal plating using the same WO2000001862A1 (en)

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JP2002047573A (en) * 2000-08-01 2002-02-15 Nikko Materials Co Ltd Pretreatment agent for silver plating and silver plating method
WO2004024984A1 (en) * 2002-09-10 2004-03-25 Nikko Materials Co., Ltd. Method for metal plating and pre-treating agent
WO2006135113A1 (en) * 2005-06-17 2006-12-21 Sumitomo Metal Mining Co., Ltd. Coating liquid for nickel film formation, nickel film and method for producing same
KR100779334B1 (en) 2000-11-08 2007-11-23 제이에프이 스틸 가부시키가이샤 Surface treated tin-plated steel sheet and chemical treatment solution
JP2010168612A (en) * 2009-01-21 2010-08-05 Fujitsu Ltd Method for manufacturing electroless-plated product
JP2012007244A (en) * 2004-09-10 2012-01-12 Jx Nippon Mining & Metals Corp Electroless plating pretreatment agent and copper-clad laminate for flexible substrate
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05239657A (en) * 1992-02-27 1993-09-17 Mitsubishi Gas Chem Co Inc Production of moisture resistant copper clad substrate
JPH07102380A (en) * 1993-09-30 1995-04-18 Nisshinbo Ind Inc Pretreatment for plating of glass fiber
JPH0839728A (en) * 1994-07-27 1996-02-13 Sumitomo Metal Mining Co Ltd Production of metal-clad laminate substrate

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2780373B2 (en) * 1989-09-07 1998-07-30 三菱瓦斯化学株式会社 Method for producing α-hydroxycarboxylic acid amide
JPH06256358A (en) * 1993-03-01 1994-09-13 Japan Energy Corp New imidazolesilane compound and its production, and metal surface treating agent using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05239657A (en) * 1992-02-27 1993-09-17 Mitsubishi Gas Chem Co Inc Production of moisture resistant copper clad substrate
JPH07102380A (en) * 1993-09-30 1995-04-18 Nisshinbo Ind Inc Pretreatment for plating of glass fiber
JPH0839728A (en) * 1994-07-27 1996-02-13 Sumitomo Metal Mining Co Ltd Production of metal-clad laminate substrate

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* Cited by examiner, † Cited by third party
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JP2002047573A (en) * 2000-08-01 2002-02-15 Nikko Materials Co Ltd Pretreatment agent for silver plating and silver plating method
KR100779334B1 (en) 2000-11-08 2007-11-23 제이에프이 스틸 가부시키가이샤 Surface treated tin-plated steel sheet and chemical treatment solution
WO2004024984A1 (en) * 2002-09-10 2004-03-25 Nikko Materials Co., Ltd. Method for metal plating and pre-treating agent
US7867564B2 (en) 2002-09-10 2011-01-11 Nippon Mining & Metals Co., Ltd. Metal plating method and pretreatment agent
JP2012007244A (en) * 2004-09-10 2012-01-12 Jx Nippon Mining & Metals Corp Electroless plating pretreatment agent and copper-clad laminate for flexible substrate
WO2006135113A1 (en) * 2005-06-17 2006-12-21 Sumitomo Metal Mining Co., Ltd. Coating liquid for nickel film formation, nickel film and method for producing same
US8007692B2 (en) 2005-06-17 2011-08-30 Sumitomo Metal Mining Co., Ltd. Coating liquid for nickel film formation, nickel film, and production method thereof
US8697233B2 (en) 2006-03-07 2014-04-15 Nara Institute Of Science And Technology Metal-coated lipid bilayer vesicles and process for producing same
JP2010168612A (en) * 2009-01-21 2010-08-05 Fujitsu Ltd Method for manufacturing electroless-plated product
JP2019529710A (en) * 2016-09-16 2019-10-17 アトテック ドイチェランド ゲーエムベーハー Method for providing a multilayer coating on a surface of a substrate
JP2020023734A (en) * 2018-08-07 2020-02-13 株式会社豊光社 Manufacturing method of plated glass substrate
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