JP4649666B2 - Electroless gold plating solution - Google Patents
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- JP4649666B2 JP4649666B2 JP2006190056A JP2006190056A JP4649666B2 JP 4649666 B2 JP4649666 B2 JP 4649666B2 JP 2006190056 A JP2006190056 A JP 2006190056A JP 2006190056 A JP2006190056 A JP 2006190056A JP 4649666 B2 JP4649666 B2 JP 4649666B2
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- 229910052737 gold Inorganic materials 0.000 title claims description 37
- 239000010931 gold Substances 0.000 title claims description 37
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 35
- 238000007747 plating Methods 0.000 title claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- -1 gold (III) halide salt Chemical class 0.000 claims description 21
- 238000007772 electroless plating Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000218202 Coptis Species 0.000 description 2
- 235000002991 Coptis groenlandica Nutrition 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910003767 Gold(III) bromide Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- OVWPJGBVJCTEBJ-UHFFFAOYSA-K gold tribromide Chemical compound Br[Au](Br)Br OVWPJGBVJCTEBJ-UHFFFAOYSA-K 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Description
本発明は、基材表面に金の被膜を形成するために好適に用いられる無電解金メッキ液及び該メッキ液を利用した、装飾品や電気製品の部品として有用な金メッキ製品の製造方法に関する。 The present invention relates to an electroless gold plating solution suitably used for forming a gold film on a substrate surface, and a method for producing a gold-plated product useful as a decorative article or a part of an electrical product using the plating solution.
金メッキ製品は、特有の美しい金属光沢を持ち、耐腐食性に優れ高い電気伝導度を示すことから、ネックレスやブローチ、金糸などの装飾品、または電子回路、接点など電気製品の部品において利用されている。
一般に、このような金メッキ製品は、金属塩と還元剤による化学的な還元反応を利用し、基材表面に金属被膜を形成させる、所謂、無電解メッキ法によって製造されている。
ところで、従来の無電解金メッキ液は、その多くは金属塩として、毒性の強いシアン化金化合物を用いるものであり、また、還元剤としても、環境に悪影響を与える、ホウ素化合物、リン化合物やヒドラジンなどを用いるため、作業環境や排水処理への負荷が大きいという問題があった（特許文献１）。
Gold-plated products have a beautiful and beautiful metallic luster, and have excellent corrosion resistance and high electrical conductivity, so they are used in decorative parts such as necklaces, brooches, and gold threads, or in electrical parts such as electronic circuits and contacts. Yes.
In general, such a gold-plated product is manufactured by a so-called electroless plating method in which a metal film is formed on the surface of a substrate using a chemical reduction reaction by a metal salt and a reducing agent.
By the way, many of the conventional electroless gold plating solutions use a highly toxic gold cyanide compound as a metal salt. Also, as a reducing agent, boron compounds, phosphorus compounds and hydrazine which have an adverse effect on the environment. Therefore, there is a problem that the load on the work environment and wastewater treatment is large (Patent Document 1).
本発明は、こうした従来技術の欠点を克服するため、安全で、環境に優しくかつ簡便な組成の無電解金メッキ液およびこのものを利用した無電解メッキ法による金メッキ製品の簡便かつ効率的な製造方法を提供することを目的とする。 In order to overcome the disadvantages of the prior art, the present invention provides an electroless gold plating solution having a safe, environmentally friendly and simple composition and a simple and efficient method for producing a gold plating product by an electroless plating method using the same. The purpose is to provide.
本発明者らは、金メッキ製品を簡便に得るための環境に優しい無電解メッキ液について、種々の検討を行った結果、塩化金（III）酸等の水溶性金（III）ハロゲン化塩が、意外にも過酸化水素により還元されて金属状の金を生成することを知見し、本発明を完成するに至った。
すなわち、この出願によれば、以下の発明が提供される。
〈１〉過酸化水素と金（III）ハロゲン化塩を含有する無電解金メッキ液。
〈２〉金（III）ハロゲン化塩が、塩化金（III）酸又は塩化金（III）酸のアルカリ金属塩であることを特徴とする〈１〉に記載の無電解メッキ液。
〈３〉基材を用意する工程と、該基材上に無電解メッキ用触媒を付着させる工程と、該触媒を付着させた基材を〈１〉又は〈２〉に記載の無電解メッキ液に浸漬させる工程とを備えたことを特徴とする金メッキ製品の製造方法。
〈４〉無電解メッキ用触媒が、パラジウム又は金であることを特徴とする〈３〉に記載の金メッキ製品の製造方法。
〈５〉基材が樹脂であることを特徴とする〈３〉又は〈４〉に記載の金メッキ製品の製造方法。
As a result of various studies on the environment-friendly electroless plating solution for easily obtaining a gold-plated product, the present inventors have found that a water-soluble gold (III) halide salt such as chloroauric (III) acid is Surprisingly, it was found that it was reduced by hydrogen peroxide to produce metallic gold, and the present invention was completed.
That is, according to this application, the following invention is provided.
<1> An electroless gold plating solution containing hydrogen peroxide and a gold (III) halide salt.
<2> The electroless plating solution according to <1>, wherein the gold (III) halide salt is an alkali metal salt of gold chloride (III) acid or gold chloride (III) acid.
<3> A step of preparing a substrate, a step of depositing an electroless plating catalyst on the substrate, and an electroless plating solution according to <1> or <2> A method for producing a gold-plated product, comprising:
<4> The method for producing a gold-plated product according to <3>, wherein the electroless plating catalyst is palladium or gold.
<5> The method for producing a gold-plated product according to <3> or <4>, wherein the base material is a resin.
本発明に係る無電解金メッキ液は、還元剤として、オキシドールとして医薬分野等で利用され、使用後は容易に分解して無害な酸素と水に変換する過酸化水素を用いたことから、安全性が高く、また、水溶性金塩として、塩化金（III）酸などに還元されて金と塩酸等に変換する水溶性の金（III）ハロゲン化塩を用いたことから、メッキ処理後の排水はこれを中和するだけで無害化できるといった、安全で、環境に優しくかつ簡便な組成のものである。
したがって、この無電解金メッキ液を利用することにより、ネックレスやブローチ、金糸などの装飾品、または電子回路、接点など電気製品の部品として有用な金メッキ製品を、環境汚染を惹起せずに安全かつ効率的に製造することができる。
The electroless gold plating solution according to the present invention is used in the pharmaceutical field as an oxidol as a reducing agent, and since it uses hydrogen peroxide that easily decomposes and converts to harmless oxygen and water after use, it is safe. In addition, water-soluble gold (III) halide salt that is reduced to gold chloride (III) acid and converted to gold and hydrochloric acid is used as water-soluble gold salt. Is a safe, environmentally friendly and simple composition that can be rendered harmless simply by neutralizing it.
Therefore, by using this electroless gold plating solution, it is possible to safely and efficiently produce gold plating products that are useful as ornaments such as necklaces, brooches, and gold threads, or electrical parts such as electronic circuits and contacts, without causing environmental pollution. Can be manufactured automatically.
本発明の無電解金メッキ液は、過酸化水素と金（III）ハロゲン化塩を含有することを特徴としている。
過酸化水素は、使用後は容易に分解して無害な酸素と水に変換し、オキシドールとして医薬分野等で利用されているものである。
過酸化水素は通常その水溶液として用いられる。その濃度の特に制限はないが、通常、0.1〜30%である。
本発明では、過酸化水素それ自体だけでなく、メッキ反応系では、過酸化水素を生成する組成物や混合物も使用することができる。このような組成物や混合物としては、アントラハイドロキノン類と酸素の混合物などが挙げられる。
金ハロゲン化塩としては、塩化金（III）酸、臭化金（III）酸およびこれらのアルカリ金属（Ｋ，Ｎａ）塩が挙げられる。
本発明で好ましく使用される金（III）ハロゲン化塩は、還元されて金と塩化水素酸や臭化水素酸に変換する水溶性の金（III）ハロゲン化塩が用いられ、特に塩化金（III）酸および塩化金（III）酸塩が好ましく使用される。塩としては、カリウム、ナトリウムなどアルカリ金属塩が好ましい。
The electroless gold plating solution of the present invention is characterized by containing hydrogen peroxide and a gold (III) halide salt.
Hydrogen peroxide is easily decomposed after use and converted into harmless oxygen and water, and is used as an oxidol in the pharmaceutical field and the like.
Hydrogen peroxide is usually used as the aqueous solution. Although there is no restriction | limiting in particular in the density | concentration, Usually, it is 0.1 to 30%.
In the present invention, not only hydrogen peroxide itself but also a composition or a mixture that generates hydrogen peroxide can be used in the plating reaction system. Examples of such a composition or mixture include a mixture of anthrahydroquinones and oxygen.
Gold halide salts include gold chloride (III) acid, gold bromide (III) acid and alkali metal (K, Na) salts thereof.
The gold (III) halide salt preferably used in the present invention is a water-soluble gold (III) halide salt that is reduced and converted to gold and hydrochloric acid or hydrobromic acid. III) Acids and gold chloride (III) salts are preferably used. The salt is preferably an alkali metal salt such as potassium or sodium.
過酸化水素と金ハロゲン化塩の使用割合に特に制限はないが、金（III）ハロゲン化塩の全てを金に還元する場合には、金（III）ハロゲン化塩に対して過酸化水素をモル比で1.5以上用いることが好ましい。 There are no particular restrictions on the ratio of hydrogen peroxide and gold halide salt used, but when all of the gold (III) halide salt is reduced to gold, hydrogen peroxide should be added to gold (III) halide salt. The molar ratio is preferably 1.5 or more.
本発明の無電解金メッキ液は、上記過酸化物と金（III）ハロゲン化塩を必須成分とするが、その機能を阻害しない範囲で、この種のメッキ液に用いられる補助添加剤などを添加することができる。このような補助添加剤としては、ドデシルベンゼンスルホン酸ナトリウム、ポリエチレングリコールエーテルなどの界面活性剤、ゼラチン、ポリビニルアルコールなどの水溶性ポリマー、塩酸、水酸化ナトリウムなどのpH調整剤などを挙げることができる。 The electroless gold plating solution of the present invention contains the above peroxide and gold (III) halide as essential components, but adds auxiliary additives used in this type of plating solution as long as the functions thereof are not hindered. can do. Examples of such auxiliary additives include surfactants such as sodium dodecylbenzenesulfonate and polyethylene glycol ether, water-soluble polymers such as gelatin and polyvinyl alcohol, and pH adjusters such as hydrochloric acid and sodium hydroxide. .
つぎに、本発明の無電解金メッキ液を利用して無電解メッキ法により金メッキ製品を製造する方法について説明する。
本発明の金メッキ製品の製造方法は、基材を用意する工程と、該基材上に無電解メッキ用触媒を付着させる工程と、該触媒を付着させた基材を上記（１）〜（３）の何れかに記載の無電解メッキ液に浸漬させる工程とを備えたことを特徴としている。
Next, a method for producing a gold-plated product by an electroless plating method using the electroless gold plating solution of the present invention will be described.
The method for producing a gold-plated product of the present invention includes the steps of preparing a substrate, a step of attaching a catalyst for electroless plating on the substrate, and a substrate on which the catalyst is attached (1) to (3 And a step of immersing in the electroless plating solution according to any one of the above.
基材としては、この種の分野に用いられているものが全て使用でき、セルロース、フィブロイン、ポリエステル、ポリイミドなどの高分子、銅、ニッケル、鉄などの金属、アルミナ、チタニア、シリカなどの金属酸化物が挙げられる。
また、基材の形状も特に制約されず、粉末、繊維、フィルム、成形体のいずれであってもよいが、導電性フィルムや導電性繊維などの製品を得るために、フィルム状、繊維状としておくことが好ましい。
As the base material, all materials used in this type of field can be used. Polymers such as cellulose, fibroin, polyester and polyimide, metals such as copper, nickel and iron, metal oxides such as alumina, titania and silica Things.
In addition, the shape of the substrate is not particularly limited and may be any of powder, fiber, film, and molded body, but in order to obtain a product such as a conductive film or conductive fiber, a film or fiber It is preferable to keep it.
用意された基材に無電解メッキ用触媒を付着させる工程は、金属コロイドの吸着とその応用，表面，２４，４１３−４１９（１９８６）などに記載されている、それ自体公知の付着方法がいずれも適用できる。このような方法としては、たとえば金属コロイドを用いる方法、基材を還元剤と触媒となる金属塩で順次処理する方法等が挙げられる。
無電解メッキ用触媒としては、従来公知のものが使用できるが、パラジウム又は金を用いることが好ましい。
The step of adhering the electroless plating catalyst to the prepared substrate may be any of the known adhesion methods described in Adsorption of metal colloid and its application, Surface, 24, 413-419 (1986), etc. Is also applicable. As such a method, for example, a method using a metal colloid, a method in which a substrate is sequentially treated with a reducing agent and a metal salt as a catalyst, and the like can be mentioned.
Conventionally known catalysts can be used as the electroless plating catalyst, but palladium or gold is preferably used.
付着させた基材に上記無電解メッキ液に浸漬させる工程は、原料としての前記金（III）ハロゲン化塩および還元剤としての過酸化水素を含む無電解金メッキ液中に、少量の触媒を表面に付着させた基材を浸漬することにより行われる。 The step of immersing the substrate in the electroless plating solution includes a small amount of catalyst in the electroless gold plating solution containing the gold (III) halide salt as a raw material and hydrogen peroxide as a reducing agent. It is carried out by immersing the base material adhered to.
無電解金メッキ液は、処理の直前に調製することが望ましく、そのためには、たとえば塩化金（III）酸水溶液と過酸化水素水溶液を別々につくっておき、この両者を使用直前に混合するのが便利である。このメッキ液に、パラジウムまたは金などを含む触媒を付与した基材を０℃ないし８０℃、好ましくは１５℃ないし３０℃において浸漬してメッキを行う。メッキの終点は、基材が金色に着色し、また、塩化金（III）酸によるメッキ液の黄色が退色することで判断される。 It is desirable to prepare the electroless gold plating solution immediately before the treatment. For this purpose, for example, a gold chloride (III) acid aqueous solution and a hydrogen peroxide aqueous solution are separately prepared, and both are mixed immediately before use. Convenient. Plating is performed by immersing a base material provided with a catalyst containing palladium or gold in this plating solution at 0 ° C. to 80 ° C., preferably 15 ° C. to 30 ° C. The end point of the plating is determined by the fact that the base material is colored in gold and the yellow color of the plating solution due to chloroauric (III) acid is faded.
以下、本発明を実施例により更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
20mM−塩化パラジウム(II)と0.1M−塩化ナトリウムを含む水溶液(2.5ml)を純水で94mlに希釈し、室温下で撹拌しながら、1%−塩化ステアリルトリメチルアンモニウム水溶液(1ml)および40mM−水素化ホウ素ナトリウム水溶液(5ml)を順次加え、一夜放置して、暗褐色透明なパラジウムヒドロゾル(100ml)を得た。
ポリエステル板(ダイヤホイル#350、12mm×19mm)を1M−水酸化ナトリウム水溶液中に室温下で1夜浸漬したのち水洗し、さらに、上記のパラジウムヒドロゾル(20ml)中に25℃、１時間浸漬したのち水洗して表面にパラジウムを付与した。つぎに、20mM−塩化金(III)酸水溶液(1ml)と0.5M−過酸化水素水溶液(1ml)を混合して得られる無電解金メッキ液中に、パラジウムを付与したポリエステル板を加え、時々撹拌しながら25℃、５分間浸漬したのち水洗・乾燥して、外観が金色のポリエステル板を得た。このポリエステル板は0.7％の金を含み、良好な導電性を示した。
Example 1
An aqueous solution (2.5 ml) containing 20 mM palladium (II) chloride and 0.1 M sodium chloride was diluted to 94 ml with pure water, and while stirring at room temperature, 1% -stearyltrimethylammonium chloride aqueous solution (1 ml) and 40 mM- Aqueous sodium borohydride solution (5 ml) was sequentially added and allowed to stand overnight to obtain a dark brown transparent palladium hydrosol (100 ml).
A polyester plate (Diafoil # 350, 12mm x 19mm) is immersed in 1M-sodium hydroxide aqueous solution at room temperature overnight, then washed with water, and further immersed in the above palladium hydrosol (20ml) at 25 ° C for 1 hour. After that, it was washed with water to give palladium on the surface. Next, a polyester plate provided with palladium is added to an electroless gold plating solution obtained by mixing a 20 mM aqueous solution of gold chloride (III) (1 ml) and a 0.5 M aqueous solution of hydrogen peroxide (1 ml), and stirred occasionally. Then, after dipping at 25 ° C. for 5 minutes, it was washed with water and dried to obtain a golden polyester plate. This polyester plate contained 0.7% gold and showed good conductivity.
実施例２
20mM−塩化金(III)酸水溶液(2.5ml)を純水で94mlに希釈し、室温下で撹拌しながら、1%−塩化ステアリルトリメチルアンモニウム水溶液(1ml)および40mM−水素化ホウ素ナトリウム水溶液(5ml)を順次加え、一夜放置して、赤色透明な金ヒドロゾル(100ml)を得た。
絹布(日本規格協会、染色堅牢度試験用白布、2cm×4cm)を、上記の金ヒドロゾル(20ml)中に25℃、30分間浸漬したのち水洗・乾燥して、絹布の繊維表面に金を付与した。つぎに、20mM−塩化金(III)酸ナトリウム水溶液(2.5ml)と0.5M−過酸化水素水溶液(2.5ml)を混合して得られる無電解金メッキ液中に、金を付与した絹布を加え、時々撹拌しながら25℃、1時間浸漬したのち、水洗・乾燥して、外観が金色の金メッキ絹布を得た。このメッキ布は14.5％の金を含み、良好な導電性を示した。
Example 2
A 20% aqueous solution of gold chloride (III) chloride (2.5 ml) was diluted to 94 ml with pure water, and while stirring at room temperature, 1% aqueous stearyltrimethylammonium chloride solution (1 ml) and 40 mM aqueous sodium borohydride solution (5 ml) ) Were sequentially added and left overnight to obtain a red transparent gold hydrosol (100 ml).
Silk fabric (Japanese Standards Association, white fabric for dyeing fastness test, 2cm × 4cm) is immersed in the above gold hydrosol (20ml) at 25 ° C for 30 minutes, then washed and dried to give gold to the fiber surface of the silk fabric did. Next, in an electroless gold plating solution obtained by mixing 20 mM sodium chloride (III) chloride aqueous solution (2.5 ml) and 0.5 M hydrogen peroxide aqueous solution (2.5 ml), a silk cloth provided with gold is added, After being immersed for 1 hour at 25 ° C. with occasional stirring, it was washed with water and dried to obtain a gold-plated silk cloth having a golden appearance. This plated cloth contained 14.5% gold and showed good conductivity.
実施例３
ポリイミドフィルム(カプトン、厚さ25μm、12mm×19mm)を1M−水酸化ナトリウム水溶液中に室温下で1分間浸漬したのち水洗し、さらに、上記のパラジウムヒドロゾル(20ml)中に25℃、５分間浸漬したのち水洗して表面にパラジウムを付与した。つぎに、20mM−塩化金(III)酸水溶液(1ml)と0.1M−過酸化水素水溶液(1ml)を混合して得られる無電解金メッキ液中に、パラジウムを付与したポリイミドフィルムを加え、時々撹拌しながら25℃、30分間浸漬したのち水洗・乾燥して、外観が金色のポリイミドフィルムを得た。このポリイミドフィルムは8.4％の金を含み、良好な導電性を示した。
Example 3
A polyimide film (Kapton, thickness 25 μm, 12 mm × 19 mm) was immersed in a 1M-sodium hydroxide aqueous solution for 1 minute at room temperature, washed with water, and further washed in the above-mentioned palladium hydrosol (20 ml) at 25 ° C. for 5 minutes. After immersion, the surface was washed with water to give palladium to the surface. Next, in the electroless gold plating solution obtained by mixing 20mM-gold chloride (III) acid aqueous solution (1ml) and 0.1M-hydrogen peroxide solution (1ml), add a polyimide film to which palladium is added, and occasionally stir While being immersed at 25 ° C. for 30 minutes, it was washed with water and dried to obtain a polyimide film having a golden appearance. This polyimide film contained 8.4% gold and showed good conductivity.
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| KR20160075622A (en) | 2014-07-17 | 2016-06-29 | 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 | Pretreatment solution for electroless plating and electroless plating method |
| JP2018048382A (en) * | 2016-09-23 | 2018-03-29 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Laminated structure of metal films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010248663A (en) * | 2009-04-16 | 2010-11-04 | Du Pont Toray Co Ltd | Gold coated fiber or structure thereof, and method for producing the same |
| US8721773B2 (en) * | 2011-10-26 | 2014-05-13 | Shell Oil Company | Method for preparing a palladium-gold alloy gas separation membrane system |
| CN111420655A (en) * | 2020-04-18 | 2020-07-17 | 云南正邦科技有限公司 | Method for chemically plating metal catalyst on tube pass inner wall of continuous flow reaction module |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002004060A (en) * | 2000-06-21 | 2002-01-09 | Ishihara Chem Co Ltd | Electroless gold plating bath |
| JP2004091918A (en) * | 2002-07-12 | 2004-03-25 | Japan Exlan Co Ltd | Discoloration prevention material for metal |
| JP2004332037A (en) * | 2003-05-06 | 2004-11-25 | Hitachi Chem Co Ltd | Electroless gold plating method |
| JP2006135206A (en) * | 2004-11-09 | 2006-05-25 | Sumitomo Metal Mining Co Ltd | Plating method |
| JP2006144095A (en) * | 2004-11-24 | 2006-06-08 | Mitsubishi Paper Mills Ltd | Electroless plating method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61195935A (en) * | 1985-02-26 | 1986-08-30 | Nippon Herusu Kogyo Kk | Manufacture of reduced silver |
| JPS6299477A (en) * | 1985-10-25 | 1987-05-08 | C Uyemura & Co Ltd | Electroless gold plating solution |
| JP2538461B2 (en) * | 1991-02-22 | 1996-09-25 | 奥野製薬工業株式会社 | Electroless gold plating method |
| JPH05163579A (en) * | 1991-12-11 | 1993-06-29 | Hitachi Chem Co Ltd | Gold plating method |
| JP3117614B2 (en) * | 1995-03-06 | 2000-12-18 | 一郎 新井 | Method for producing sterilizing purifying agent |
-
2006
- 2006-07-11 JP JP2006190056A patent/JP4649666B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002004060A (en) * | 2000-06-21 | 2002-01-09 | Ishihara Chem Co Ltd | Electroless gold plating bath |
| JP2004091918A (en) * | 2002-07-12 | 2004-03-25 | Japan Exlan Co Ltd | Discoloration prevention material for metal |
| JP2004332037A (en) * | 2003-05-06 | 2004-11-25 | Hitachi Chem Co Ltd | Electroless gold plating method |
| JP2006135206A (en) * | 2004-11-09 | 2006-05-25 | Sumitomo Metal Mining Co Ltd | Plating method |
| JP2006144095A (en) * | 2004-11-24 | 2006-06-08 | Mitsubishi Paper Mills Ltd | Electroless plating method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160075622A (en) | 2014-07-17 | 2016-06-29 | 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 | Pretreatment solution for electroless plating and electroless plating method |
| US9932676B2 (en) | 2014-07-17 | 2018-04-03 | Electroplating Engineers Of Japan Limited | Pretreatment solution for electroless plating and electroless plating method |
| JP2018048382A (en) * | 2016-09-23 | 2018-03-29 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Laminated structure of metal films |
| KR20180095041A (en) | 2016-09-23 | 2018-08-24 | 니혼 엘렉트로플레이팅 엔지니어스 가부시키가이샤 | Laminated structure of metal film |
| US10306774B2 (en) | 2016-09-23 | 2019-05-28 | Electroplating Engineers Of Japan Limited. | Laminate structure of metal coating |
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