JPH0553873B2 - - Google Patents
Info
- Publication number
- JPH0553873B2 JPH0553873B2 JP62223708A JP22370887A JPH0553873B2 JP H0553873 B2 JPH0553873 B2 JP H0553873B2 JP 62223708 A JP62223708 A JP 62223708A JP 22370887 A JP22370887 A JP 22370887A JP H0553873 B2 JPH0553873 B2 JP H0553873B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- chemical
- plating
- solution
- plating solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 58
- 229910052709 silver Inorganic materials 0.000 claims description 58
- 239000004332 silver Substances 0.000 claims description 58
- 238000007747 plating Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 26
- 239000000084 colloidal system Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 229920003169 water-soluble polymer Polymers 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 description 14
- 239000000123 paper Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000002932 luster Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- CKQAOGOZKZJUGA-UHFFFAOYSA-N 1-nonyl-4-(4-nonylphenoxy)benzene Chemical compound C1=CC(CCCCCCCCC)=CC=C1OC1=CC=C(CCCCCCCCC)C=C1 CKQAOGOZKZJUGA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- FGJLAJMGHXGFDE-UHFFFAOYSA-L disodium;2,3-dihydroxybutanedioate;dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O FGJLAJMGHXGFDE-UHFFFAOYSA-L 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZMLDXWLZKKZVSS-UHFFFAOYSA-N palladium tin Chemical compound [Pd].[Sn] ZMLDXWLZKKZVSS-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940092162 sodium tartrate dihydrate Drugs 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、銀ヒドロゾルを用いた金属めつき方
法に関するものであり、詳しくは、銀ヒドロゾル
を用いて被めつき物に銀コロイドを付与した後、
付与された銀コロイドを触媒として化学めつきす
ることによつて、均一かつ強固に金属めつき被膜
を形成することを可能とした金属めつき方法に関
するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a metal plating method using a silver hydrosol, and more specifically, a metal plating method using a silver hydrosol to impart silver colloid to a plated object. rear,
The present invention relates to a metal plating method that makes it possible to form a uniform and strong metal plating film by chemical plating using applied silver colloid as a catalyst.
本発明に係る金属めつき方法の主な用途は、プ
リント配線板、導電材料等である。 The main applications of the metal plating method according to the present invention are printed wiring boards, conductive materials, and the like.
紙や不織布等の繊維組成物、ガラス、セラミツ
クス及びプラステイツクスは本来絶縁体である
が、金属材料に比べて軽量でかつ安価であること
から、これらに種々の加工を施して各種金属を付
与することにより、導電性などの電気的性質を持
たせることが行われている。
Fiber compositions such as paper and nonwoven fabrics, glass, ceramics, and plastics are originally insulators, but because they are lighter and cheaper than metal materials, they can be processed in various ways to add various metals. By doing so, it is possible to impart electrical properties such as conductivity.
従来、これら絶縁体に対し金属を付与する方法
として、例えば、米国特許第2702253号公報及び
米国特許第3011920号公報に記載の方法が知られ
ている。 Conventionally, methods described in US Pat. No. 2,702,253 and US Pat. No. 3,011,920 are known as methods for applying metal to these insulators.
米国特許第2702253号公報に記載の方法は、被
めつき物を強酸性の塩化第一錫溶液に浸漬したの
ち、水洗し、次いで、強酸性の塩化パラジウム溶
液に浸漬することにより、被めつき物表面にパラ
ジウムを析出させ、さらに、原料金属塩および還
元剤を含む化学めつき液中に浸漬することによ
り、該パラジウムを触媒として化学めつきする方
法である。 The method described in U.S. Patent No. 2,702,253 involves immersing the plated object in a strongly acidic stannous chloride solution, washing it with water, and then immersing it in a strongly acidic palladium chloride solution. In this method, palladium is deposited on the surface of an object, and the object is further immersed in a chemical plating solution containing a raw metal salt and a reducing agent, thereby chemically plating the object using the palladium as a catalyst.
米国特許第3011920号公報に記載の方法は、被
めつき物を強酸性のパラジウム−錫コロイド液中
に浸漬することにより、被めつき物表面に該コロ
イドを付与した後、酸またはアルカリで処理して
触媒活性を発現させ、次いで、化学めつきする方
法である。 The method described in U.S. Patent No. 3,011,920 involves applying the colloid to the surface of the plated object by immersing the object in a strongly acidic palladium-tin colloid solution, and then treating the surface with acid or alkali. In this method, the catalytic activity is developed, and then chemical plating is carried out.
前出の従来より公知の化学めつき方法では、触
媒としてパラジウムが用いられているが、このパ
ラジウムは相当に高価な金属であり、そのため製
造コストの大きな部分を占める。また、従来の方
法では、触媒を付与するために、少なくとも二段
階の処理を必要とする為工程が非常に複雑とな
る。さらに、用いる溶液が強酸性であるため、被
めつき物が損傷を受け易いなどの問題点があつ
た。
In the previously known chemical plating method mentioned above, palladium is used as a catalyst, but palladium is a fairly expensive metal and therefore accounts for a large portion of the manufacturing cost. Further, in the conventional method, in order to apply the catalyst, at least two stages of treatment are required, making the process extremely complicated. Furthermore, since the solution used is strongly acidic, there are other problems such as the coated object being easily damaged.
本発明者は、パラジウムよりも安価な金属を触
媒として用い、しかも、触媒の付与がほぼ中性の
溶液中で一段階の処理で行えるような方法を求め
て種々検討した結果、パジウムに比べて格段に安
価な金属である銀を触媒として用いることに着目
し本発明に到達したものである。
The present inventor conducted various studies in search of a method that uses a metal that is cheaper than palladium as a catalyst and also allows the application of the catalyst to be carried out in a single step in an almost neutral solution. The present invention was achieved by paying attention to the use of silver, which is a significantly inexpensive metal, as a catalyst.
被めつき物に、0.1〜5mmol/の銀塩水溶液
を陽イオン性界面活性剤、陰イオン性界面活性
剤、非イオン性界面活性剤及び水溶性高分子の中
から選ばれた一種又は二種以上を0.005〜0.1%含
む状態で、銀塩に対して2〜4倍モルの還元剤で
還元処理して得られた銀ヒドロゾルを接触させて
銀コロイドを付与させた後、当該銀コロイドの活
性化処理を行なうことなく、化学銅めつき液、化
学銀めつき液及び化学コバルトめつき液のいずれ
か一種の化学めつき液中に浸漬することを特徴と
する金属めつき方法。 One or two selected from cationic surfactants, anionic surfactants, nonionic surfactants, and water-soluble polymers are added to the plated material with 0.1 to 5 mmol/aqueous silver salt solution. After contacting a silver hydrosol obtained by reduction treatment with a reducing agent of 2 to 4 times the molar amount of the silver salt in a state containing 0.005 to 0.1% of the above to impart silver colloid, the activity of the silver colloid is A metal plating method characterized by immersion in a chemical plating solution of any one of a chemical copper plating solution, a chemical silver plating solution, and a chemical cobalt plating solution without performing a chemical treatment.
先ず、本発明において最も重要な点は、化学め
つきのための触媒として銀コロイドを用いること
にあり、これを付与するために銀ヒドロゾルが用
いられる。
First, the most important point in the present invention is the use of silver colloid as a catalyst for chemical plating, and silver hydrosol is used to provide this.
本発明においては、用いる銀ヒドロゾルが中性
ないし弱アルカリ性であり、その分散状態は安定
で長期にわたり均一な状態を保ち、しかも触媒活
性が低下しない。そのうえ、含まれる銀コロイド
が微細かつ均斉であるため、該銀ヒドロゾル中に
浸漬するだけの一段階の処理で被めつき物の表面
に均一且つ強固に銀コロイドを付与できることに
起因して、被めつき物の表面に均一且つ強固に化
学めつきできるものである。 In the present invention, the silver hydrosol used is neutral to weakly alkaline, and its dispersion state is stable and remains uniform for a long period of time, and the catalytic activity does not decrease. Furthermore, since the contained silver colloid is fine and uniform, silver colloid can be uniformly and firmly applied to the surface of the object to be plated with a single step of immersion in the silver hydrosol. It is capable of uniformly and strongly chemically plating the surface of a plated object.
次に、本発明方法の実施に当たつての諸条件に
ついて述べる。 Next, various conditions for implementing the method of the present invention will be described.
本発明方法における銀ヒドロゾルは、次の方法
によつて調製することができる。 The silver hydrosol in the method of the present invention can be prepared by the following method.
即ち、安定で長期にわたり均一な分散状態を保
ち、しかも触媒活性が低下しないような、中性な
いし弱アルカリ性の銀ヒドロゾルは、銀塩の水溶
液を界面活性剤及び/又は水溶性高分子の存在下
に還元する方法(例えば特開昭59−120249号公
報)により得ることができる。 In other words, a neutral to weakly alkaline silver hydrosol that is stable, maintains a uniform dispersion state over a long period of time, and does not reduce catalytic activity is produced by mixing an aqueous solution of a silver salt in the presence of a surfactant and/or a water-soluble polymer. It can be obtained by a method of reducing to (for example, JP-A-59-120249).
銀塩の水溶液としては、銀()塩の水溶液、
例えば、硝酸銀()またはシアン化銀()カ
リウムの水溶液が用いられ、水溶液中での濃度は
0.1〜5mmol/が好まし。 Examples of aqueous solutions of silver salts include aqueous solutions of silver () salts,
For example, an aqueous solution of silver nitrate () or silver cyanide () potassium is used, and the concentration in the aqueous solution is
Preferably 0.1 to 5 mmol/.
還元処理にあたつては、還元剤を用いる公知の
方法によつて行うことができ、還元剤としては、
水素化ホウ素ナトリウム、水素化ホウ素カリウム
などのアルカリ金属水素化ホウ素塩、ジメチルア
ミンボランなどのホウ素系還元剤の他、次亜リン
酸ナトリウムなどのリン系還元剤、ホルムアルデ
ヒド、ヒドラジンなどが用いられる。還元剤の量
は、原料の銀塩に対し、等モル以上好ましくは、
2〜4倍モルが用いられる。 The reduction treatment can be carried out by a known method using a reducing agent.
In addition to alkali metal borohydride salts such as sodium borohydride and potassium borohydride, boron-based reducing agents such as dimethylamine borane, phosphorus-based reducing agents such as sodium hypophosphite, formaldehyde, hydrazine, and the like are used. The amount of the reducing agent is preferably at least equimolar to the raw material silver salt,
2 to 4 times the molar amount is used.
界面活性剤及び水溶性高分子としては、ステア
リルトリメチルアンモニウムクロライドなどの陽
イオン性界面活性剤、ドデシルベンゼンスルホン
酸ナトリウムなどの陰イオン性界面活性剤、ポリ
エチレングリコールモノ−p−ノニルフエニルエ
ーテルなどの非イオン性界面活性剤及びポリビニ
ルアルコール、ポリビニルピロリドンなどの水溶
性高分子が使用できる。使用に際しては、これら
界面活性剤及び水溶性高分子を単独で又は二種以
上組み合わせて使用することができる。界面活性
剤及び水溶性高分子の濃度は、0.005〜0.1の範囲
で用いられる。 Examples of surfactants and water-soluble polymers include cationic surfactants such as stearyltrimethylammonium chloride, anionic surfactants such as sodium dodecylbenzenesulfonate, and polyethylene glycol mono-p-nonyl phenyl ether. Nonionic surfactants and water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be used. When used, these surfactants and water-soluble polymers can be used alone or in combination of two or more. The concentration of surfactant and water-soluble polymer used is in the range of 0.005 to 0.1.
本発明における化学めつきは、常法により行う
ことができる。すなわち、金属イオンおよび還元
剤を含む溶液中において、銀コロイドの部分で該
金属イオンが還元されることにより金属が析出す
るものである。 Chemical plating in the present invention can be performed by a conventional method. That is, in a solution containing metal ions and a reducing agent, the metal ions are reduced in the silver colloid, thereby precipitating the metal.
本発明における化学めつきのための金属イオン
溶液としては、電気的性質を付与するために通常
使用される中性または弱アルカリ性の銅イオン、
銀イオン又はコバルトイオンの溶液を使用するこ
とができる。 The metal ion solution for chemical plating in the present invention includes neutral or weakly alkaline copper ions that are commonly used to impart electrical properties;
Solutions of silver or cobalt ions can be used.
本発明における化学めつきのための還元剤とし
ては、次亜リン酸ナトリウム、ホルムアルデヒド
などを使用することができる。 As the reducing agent for chemical plating in the present invention, sodium hypophosphite, formaldehyde, etc. can be used.
本発明における被めつき物は、紙や不織布など
の繊維成形物、ガラス、セラミツクス、プラステ
イツクス、金属及び金属酸化物などが対象とな
る。 The objects to be coated in the present invention include fiber molded articles such as paper and nonwoven fabrics, glass, ceramics, plastics, metals, and metal oxides.
銀ヒドロゾル中の銀コロイドを被めつき物に付
与する手段としては、金属めつきにあたり触媒を
付与する際に通常使用される方法、即ち、被めつ
き物を銀ヒドロゾル中に浸漬させる方法または銀
ヒドロゾルを被めつき物に塗布した後乾燥する方
法がとられる。 The means for applying the silver colloid in the silver hydrosol to the plated object is the method usually used when applying a catalyst for metal plating, that is, the method of immersing the plated object in silver hydrosol, or the method of applying silver colloid to the plated object. A method is used in which the hydrosol is applied to the coated object and then dried.
次に、実施例により本発明を説明する。 Next, the present invention will be explained by examples.
尚、実施例における表面抵抗値は、三菱油化(株)
製MCP−TESTERを用いて測定したものであ
る。 In addition, the surface resistance values in the examples are those of Mitsubishi Yuka Co., Ltd.
This was measured using a manufactured MCP-TESTER.
めつきの密着性は、めつき終了1時間後にスコ
ツチメンデイングテープ(住友スリーエム(株))を
めつき物上に強く貼り付け、引きはがすことによ
り調べた。 The adhesion of the plating was examined by strongly pasting Scotch Mending Tape (Sumitomo 3M Ltd.) onto the plated object and peeling it off one hour after the completion of plating.
実施例 1
硝酸銀()50μmolを純水94mlに溶解した溶
液を激しく攪拌しながら、この溶液にステアリル
トリメチルアンモニウムクロライド10mgを含む水
溶液1ml及び水素化ホウ素ナトリウム200μmolを
含む水溶液5mlを順次注入すると、溶液の色が黄
褐色に急変し、PH9.6の均一透明な銀ヒドロゾル
100mlが得られた。Example 1 While vigorously stirring a solution of 50 μmol of silver nitrate () dissolved in 94 ml of pure water, 1 ml of an aqueous solution containing 10 mg of stearyltrimethylammonium chloride and 5 ml of an aqueous solution containing 200 μmol of sodium borohydride were sequentially poured into the solution. A homogeneous transparent silver hydrosol with a pH of 9.6 and a sudden change in color to yellowish brown.
100ml was obtained.
次いで、紙片(5cm×5cmの正方形、東洋
紙製、No.5A)を上記銀ヒドロゾル中に1時間浸
漬した後水洗した。この時紙片は吸着した銀コ
ロイドにより黄色に着色した。 Next, a piece of paper (5 cm x 5 cm square, manufactured by Toyo Paper Co., Ltd., No. 5A) was immersed in the above silver hydrosol for 1 hour and then washed with water. At this time, the paper piece was colored yellow by the adsorbed silver colloid.
別に、ロツセル塩170g、水酸化ナトリウム
50g、硫酸銅35g、炭酸ナトリウム30g及び
EDTA20gを純水に溶解して1の溶液とし、さ
らに、この溶液の1/5容の37%ホルムアルデヒド
水溶液を加えて攪拌混合し化学銅めつき液とし
た。 Separately, 170g of Lotusel salt, sodium hydroxide
50g, copper sulfate 35g, sodium carbonate 30g and
20 g of EDTA was dissolved in pure water to obtain a solution of 1, and 1/5 volume of a 37% formaldehyde aqueous solution was added and mixed with stirring to obtain a chemical copper plating solution.
この化学銅めつき液に、上記銀コロイドが付与
された紙片を5分間浸漬した後、水洗し、乾燥
して、銅の金属光沢を呈した紙片を得た。めつ
きにより付与された銅の重量は、出発の紙片に
対して24%であつた。 The piece of paper coated with the silver colloid was immersed in this chemical copper plating solution for 5 minutes, washed with water, and dried to obtain a piece of paper with copper metallic luster. The weight of copper applied by plating was 24% relative to the starting paper strip.
この紙片にメンデイングテープを強く貼り引
きはがしたところ銅被膜は剥離しなかつた。ま
た、銅めつきされた紙片の表面抵抗は0.10Ω/
□であつた。 When mending tape was strongly applied to this piece of paper and peeled off, the copper coating did not come off. Also, the surface resistance of a copper-plated piece of paper is 0.10Ω/
It was □.
実施例 2
界面活性剤であるステアリルトリメチルアンモ
ニウムクロライドの代わりにドデシルベンゼンス
ルホン酸ナトリウムを用いた以外は実施例1と同
じ方法で均一透明な銀ヒドロゾルを調製した。Example 2 A homogeneous transparent silver hydrosol was prepared in the same manner as in Example 1, except that sodium dodecylbenzenesulfonate was used instead of the surfactant stearyltrimethylammonium chloride.
次いで、木綿布(4cm×4cmの正方形)を上記
銀ヒドロゾル中に1時間浸漬した後水洗した。こ
の時木綿布は吸着した銀コロイドにより黄色に着
色した。 Next, a cotton cloth (4 cm x 4 cm square) was immersed in the above silver hydrosol for 1 hour and then washed with water. At this time, the cotton cloth was colored yellow by the adsorbed silver colloid.
続いて、実施例1で得られた化学銅めつき液
に、上記銀コロイドが付与された木綿布を5分間
浸漬した後、水洗し、乾燥して、銅の金属光沢を
呈した木綿布を得た。めつきにより付与された銅
の重量は、出発の木綿布に対して28%であつた。 Subsequently, the cotton cloth coated with silver colloid was immersed in the chemical copper plating solution obtained in Example 1 for 5 minutes, washed with water, and dried to obtain a cotton cloth with copper metallic luster. Obtained. The weight of copper applied by plating was 28% based on the starting cotton fabric.
この木綿布にメンデイングテープを強く貼り引
きはがしたところ銅被膜は剥離しなかつた。ま
た、銅めつきされた木綿布の表面抵抗は0.32Ω/
□であつた。 When mending tape was strongly applied to this cotton cloth and peeled off, the copper coating did not come off. In addition, the surface resistance of copper-plated cotton cloth is 0.32Ω/
It was □.
実施例 3
界面活性剤であるステアリルトリメチルアンモ
ニウムクロライドの代わりにポリエチレングリコ
ール−p−ノニルフエニルエーテルを用いた以外
は実施例1と同じ方法で均一透明な銀ヒドロゾル
を調製した。Example 3 A homogeneous transparent silver hydrosol was prepared in the same manner as in Example 1, except that polyethylene glycol-p-nonylphenyl ether was used instead of the surfactant stearyltrimethylammonium chloride.
次いで、石灰石粉末((株)ダイヤキヤタリスト製
100〜200mesh)を上記銀ヒドロゾル中に1時間
浸漬した後水洗した。この時石灰石粉末は吸着し
た銀コロイドにより黄色に着色した。 Next, limestone powder (manufactured by Diamond Catalyst Co., Ltd.)
100 to 200 mesh) was immersed in the above silver hydrosol for 1 hour and then washed with water. At this time, the limestone powder was colored yellow by the adsorbed silver colloid.
続いて、実施例1で得られた化学銅めつき液
に、上記銀コロイドが付与された石灰石粉末を5
分間浸漬した後、水洗し、乾燥して、銅の金属光
沢を呈した石灰石粉末を得た。 Subsequently, 50% of the limestone powder to which the silver colloid was added was added to the chemical copper plating solution obtained in Example 1.
After being immersed for a minute, it was washed with water and dried to obtain limestone powder with copper metallic luster.
実施例 4
界面活性剤であるステアリルトリメチルアンモ
ニウムクロライドの代わりにドデジルベンゼンス
ルホン酸ナトリウム5mgとポリエチレングリコー
ル−p−ノニルフエニルエーテル5mgとを含む水
溶液1mlを用いた以外は実施例1と同じ方法で均
一透明な銀ヒドロゾルを調製した。Example 4 The same method as in Example 1 was used except that 1 ml of an aqueous solution containing 5 mg of sodium dodecylbenzenesulfonate and 5 mg of polyethylene glycol-p-nonylphenyl ether was used instead of the surfactant stearyltrimethylammonium chloride. A homogeneous transparent silver hydrosol was prepared.
次いで、紙片(5cm×5cmの正方形 東洋
紙製No.5A)に上記銀ヒドロゾルを絵画用の筆で
塗布した。 Next, the above silver hydrosol was applied to a piece of paper (5 cm x 5 cm square, No. 5A manufactured by Toyo Paper Co., Ltd.) using a painter's brush.
別に、0.03molの硫酸コバルト()7水塩、
0.25molの次亜リン酸ナトリウム、0.5molの酒石
酸ナトリウム・2水塩及び0.50molのホウ酸を純
水に溶解し1とし、これに3.3mol/の水酸
化ナトリウム水溶液を加えてPH=9に調整し、化
学コバルトめつき液とした。 Separately, 0.03 mol of cobalt sulfate () heptahydrate,
Dissolve 0.25 mol of sodium hypophosphite, 0.5 mol of sodium tartrate dihydrate, and 0.50 mol of boric acid in pure water to make 1, and add 3.3 mol/aqueous sodium hydroxide solution to make pH=9. It was prepared as a chemical cobalt plating solution.
この化学コバルトめつき液に、上記銀コロイド
が付与された紙片を20分間浸漬した後、水洗
し、乾燥して、コバルトの金属光沢を呈した紙
片を得た。 The piece of paper to which the silver colloid was applied was immersed in this chemical cobalt plating solution for 20 minutes, washed with water, and dried to obtain a piece of paper with cobalt metallic luster.
この紙片にメンデイングテープを強く貼り引
きはがしたところコバルト被膜は剥離しなかつ
た。また、コバルトめつきされた紙片の表面抵
抗は12Ω/□であつた。 When mending tape was strongly applied to this piece of paper and pulled off, the cobalt film did not peel off. The surface resistance of the cobalt-plated paper piece was 12Ω/□.
実施例 5
界面活性剤であるステアリルトリメチルアンモ
ニウムクロライドの代わりに水溶性高分子である
ポリビニルピロリドンを用いた以外は実施例1と
同じ方法で均一透明な銀ヒドロゾルを調製した。Example 5 A homogeneous transparent silver hydrosol was prepared in the same manner as in Example 1, except that polyvinylpyrrolidone, a water-soluble polymer, was used instead of stearyltrimethylammonium chloride, a surfactant.
次いで、絹布(5cm×5cm)を上記銀ヒドロゾ
ル中に1時間浸漬した後水洗した。この時絹布は
吸着した銀コロイドにより黄色に着色した。 Next, a silk cloth (5 cm x 5 cm) was immersed in the above silver hydrosol for 1 hour and then washed with water. At this time, the silk cloth was colored yellow by the adsorbed silver colloid.
別に、硝酸銀()20gを含む水溶液に、該液
が無色透明になるまで28%アンモニア水を添加し
た後、更に純水を加え1の銀水溶液とし、一
方、酒石酸カリウムナトリウム4水和物100gを
700mlに溶解させ還元液を調製し、前記銀水溶液
と還元液を同容量ずつ混合して化学銀めつき液と
した。 Separately, 28% ammonia water was added to an aqueous solution containing 20 g of silver nitrate () until the solution became colorless and transparent, and then pure water was added to make a silver aqueous solution of 1. Meanwhile, 100 g of potassium sodium tartrate tetrahydrate was added.
A reducing solution was prepared by dissolving it in 700 ml, and equal volumes of the silver aqueous solution and reducing solution were mixed to prepare a chemical silver plating solution.
この化学銀めつき液に、上記銀コロイドが付与
された絹布を60分間浸漬した後、水洗し、乾燥し
て、銀の金属光沢を呈した絹布を得た。 The silk cloth coated with the silver colloid was immersed in this chemical silver plating solution for 60 minutes, washed with water, and dried to obtain a silk cloth with silver metallic luster.
めつきにより付与された銀の重量は、出発の絹
布に対して25%であつた。 The weight of silver applied by plating was 25% based on the starting silk fabric.
この絹布にメンデイングテープを強く貼り引き
はがしたところ銀被膜は剥離しなかつた。また、
銀めつきされた絹布の表面抵抗は0.02Ω/□であ
つた。 When mending tape was strongly applied to this silk cloth and peeled off, the silver coating did not come off. Also,
The surface resistance of the silver-plated silk cloth was 0.02Ω/□.
本発明に係る金属めつき方法は、前出の実施例
に示したとおり、用いられる銀ヒドロゾルが中性
ないし弱アルカリ性であるため、酸に弱い被めつ
き物でもこれを損傷することがなく、しかも、銀
ヒドロゾルに含まれる銀コロイドが微細で且つ均
斉であるために、触媒となる銀コロイドを被めつ
き物に対し強固に付与でき、その結果、密着性の
良好な金属めつき被膜が被めつき物の表面上に容
易に形成することができる。
In the metal plating method according to the present invention, as shown in the above-mentioned examples, the silver hydrosol used is neutral or weakly alkaline, so even the object to be plated, which is sensitive to acids, will not be damaged. Moreover, since the silver colloid contained in the silver hydrosol is fine and uniform, the silver colloid serving as a catalyst can be firmly applied to the plated object, resulting in a metal plating film with good adhesion. It can be easily formed on the surface of a plated object.
Claims (1)
液を陽イオン性界面活性剤、陰イオン性界面活性
剤、非イオン性界面活性剤及び水溶性高分子の中
から選ばれた一種又は二種以上を0.005〜0.1%含
む状態で、銀塩に対して2〜4倍モルの還元剤で
還元処理して得られた銀ヒドロゾルを接触させて
銀コロイドを付与させた後、当該銀の活性化処理
を行なうことなく、化学銅めつき液、化学銀めつ
き液及び化学コバルトめつき液のいずれか一種の
化学めつき液中に浸漬することを特徴とする金属
めつき方法。1. Apply 0.1 to 5 mmol of silver salt aqueous solution to the object to be coated with one or two selected from cationic surfactants, anionic surfactants, nonionic surfactants, and water-soluble polymers. After contacting a silver hydrosol obtained by reduction treatment with a reducing agent 2 to 4 times the molar amount of silver salt in a state containing 0.005 to 0.1% of silver salt or more to impart silver colloid, the activity of the silver is determined. A metal plating method characterized by immersion in a chemical plating solution of any one of a chemical copper plating solution, a chemical silver plating solution, and a chemical cobalt plating solution without performing a chemical treatment.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22370887A JPS6468478A (en) | 1987-09-07 | 1987-09-07 | Metal plating method using silver hydrosol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP22370887A JPS6468478A (en) | 1987-09-07 | 1987-09-07 | Metal plating method using silver hydrosol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6468478A JPS6468478A (en) | 1989-03-14 |
JPH0553873B2 true JPH0553873B2 (en) | 1993-08-11 |
Family
ID=16802417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP22370887A Granted JPS6468478A (en) | 1987-09-07 | 1987-09-07 | Metal plating method using silver hydrosol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6468478A (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI95816C (en) * | 1989-05-04 | 1996-03-25 | Ad Tech Holdings Ltd | Antimicrobial article and method of making the same |
JPH0757907B2 (en) * | 1989-09-18 | 1995-06-21 | 静岡県 | Electroless plating method for electrical insulators |
US6780467B2 (en) | 2000-04-25 | 2004-08-24 | Nikko Materials Co., Ltd. | Plating pretreatment agent and metal plating method using the same |
US7767009B2 (en) | 2005-09-14 | 2010-08-03 | OMG Electronic Chemicals, Inc. | Solution and process for improving the solderability of a metal surface |
WO2014045972A1 (en) | 2012-09-20 | 2014-03-27 | Dic株式会社 | Electrically conductive material and method for producing same |
JP5648232B1 (en) | 2013-06-21 | 2015-01-07 | Dic株式会社 | Electroless plating catalyst, metal film using the same, and method for producing the same |
JP6129001B2 (en) * | 2013-07-17 | 2017-05-17 | 名古屋メッキ工業株式会社 | Electroless metal plating method for organic fiber materials |
CN109440453A (en) * | 2018-10-22 | 2019-03-08 | 复旦大学 | A kind of preparation method of Cu-Ni-Gd-B-P electronic fabric |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59120249A (en) * | 1982-12-27 | 1984-07-11 | Agency Of Ind Science & Technol | Preparation of noble metal catalyst |
JPS6263676A (en) * | 1985-09-14 | 1987-03-20 | Agency Of Ind Science & Technol | Method for plating polyethylene terephthalate film with ferromagnetic metal |
-
1987
- 1987-09-07 JP JP22370887A patent/JPS6468478A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59120249A (en) * | 1982-12-27 | 1984-07-11 | Agency Of Ind Science & Technol | Preparation of noble metal catalyst |
JPS6263676A (en) * | 1985-09-14 | 1987-03-20 | Agency Of Ind Science & Technol | Method for plating polyethylene terephthalate film with ferromagnetic metal |
Also Published As
Publication number | Publication date |
---|---|
JPS6468478A (en) | 1989-03-14 |
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