JPH01319683A - Platinum colloidal solution and electroless platinum plating method using the same solution and production of platinum carrier - Google Patents
Platinum colloidal solution and electroless platinum plating method using the same solution and production of platinum carrierInfo
- Publication number
- JPH01319683A JPH01319683A JP14997488A JP14997488A JPH01319683A JP H01319683 A JPH01319683 A JP H01319683A JP 14997488 A JP14997488 A JP 14997488A JP 14997488 A JP14997488 A JP 14997488A JP H01319683 A JPH01319683 A JP H01319683A
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- solution
- plated
- electroless
- colloidal
- 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.)
- Pending
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 222
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 111
- 238000007747 plating Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 230000001681 protective effect Effects 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 150000003057 platinum Chemical class 0.000 claims abstract description 10
- 150000004676 glycans Chemical class 0.000 claims abstract description 7
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 7
- 239000005017 polysaccharide Substances 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims description 30
- 235000000346 sugar Nutrition 0.000 claims description 8
- 150000008163 sugars Chemical class 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000001814 pectin Substances 0.000 abstract description 6
- 229920001277 pectin Polymers 0.000 abstract description 6
- 235000010987 pectin Nutrition 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 229920001817 Agar Polymers 0.000 abstract description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 abstract description 2
- 239000008272 agar Substances 0.000 abstract description 2
- 239000008103 glucose Substances 0.000 abstract description 2
- 150000001720 carbohydrates Chemical class 0.000 abstract 3
- 229930091371 Fructose Natural products 0.000 abstract 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 abstract 1
- 239000005715 Fructose Substances 0.000 abstract 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 abstract 1
- 229910020437 K2PtCl6 Inorganic materials 0.000 abstract 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 230000009965 odorless effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 239000000919 ceramic Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 239000003014 ion exchange membrane Substances 0.000 description 3
- 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 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BIDAISPAUFXVCX-UHFFFAOYSA-N B1[C-]=CC=C1 Chemical compound B1[C-]=CC=C1 BIDAISPAUFXVCX-UHFFFAOYSA-N 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000057 Mannan Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
この発明は白金コロイド溶液及びそれを用いた無電解白
金メッキ方法ならびに白金担持体の製法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a platinum colloidal solution, an electroless platinum plating method using the same, and a method for producing a platinum carrier.
〈従来の技術〉
一般的にガラスやセラミック等の非金属物製の被メッキ
物に無電解メッキを行う場合には、その前処理として被
メッキ物表面の活性・触媒化処理が必要である。この活
性・触媒化処理方法としては、触媒能を有する金属イオ
ンと還元剤とを組合わせたもの、或いは金属のコロイド
溶液などに浸漬して被メッキ物の表面を活性・触媒化さ
せる方法が知られている（特開昭５６−１３９６７０号
、特開昭５６−１６０７７１号公報参照）。そして、触
媒能を有する金属としてはパラジウムが広く使用されて
おり、還元剤としては塩化第一錫が使用されていた。<Prior Art> Generally, when performing electroless plating on a non-metallic object such as glass or ceramic, it is necessary to activate and catalyze the surface of the object to be plated as a pretreatment. As this activation/catalytic treatment method, there are known methods of activating and catalyzing the surface of the plated object by immersing it in a combination of metal ions with catalytic ability and a reducing agent, or in a colloidal solution of metal. (Refer to Japanese Patent Application Laid-open Nos. 139670/1982 and 160771/1983). Palladium has been widely used as a metal with catalytic ability, and stannous chloride has been used as a reducing agent.
〈発明が解決しようとする課題〉
しかしながら、無電解メッキの中でも白金の無電解メッ
キを行う場合などは、その無電解白金メッキの主な用途
がセンザー用電極のメッキであることから、白金の高純
度析出が要求されるものであるが、従来のようにパラジ
ウムにより被メッキ物を活性・触媒化したものでは、そ
の上に析出する白金の純度があまり１−がらず実用性に
乏しかった。更に、還元剤として用いた塩化第一・錫も
、白金と一緒に析出し易く、前述の如（高純度の析出が
要求される無電解白金メッキには好ましくなかった。<Problem to be solved by the invention> However, when performing electroless plating of platinum among electroless plating, since the main use of electroless platinum plating is plating of sensor electrodes, the high Purity precipitation is required, but in the conventional method in which the plated object is activated and catalyzed with palladium, the purity of the platinum deposited thereon is not so high as to be of practical use. Furthermore, stannous chloride used as a reducing agent is also likely to precipitate together with platinum, which is not preferred for electroless platinum plating, which requires high-purity precipitation (as described above).
また、このような点に鑑ので白金により被メッキ物上面
の活性・触媒化をする例もある。それは、塩化白金酸水
溶液を用い、還元剤として硼素化水素すトリウムを用い
たものである。しかし、このような例にしても、白金粒
子の被メッキ物に対する付着性が十分であるとはいえず
、付着する白金の量のわりには使用する白金の量が多く
、白金のロスによる不経済性が指摘されていた。しかも
、還元剤である硼素化水素すＩ〜リウノ、の寿命が短命
であることから、実用土十分なものとはいえなかった。In addition, in view of this point, there are examples in which the upper surface of the object to be plated is activated and catalyzed using platinum. It uses an aqueous solution of chloroplatinic acid and sodium borohydride as a reducing agent. However, even in such an example, the adhesion of the platinum particles to the object to be plated is not sufficient, and the amount of platinum used is large compared to the amount of platinum that adheres, resulting in uneconomical losses due to platinum loss. Gender was pointed out. Moreover, since the life of the reducing agent, hydrogen borolide, is short-lived, it could not be said to be a sufficient material for practical use.
この発明はこのような従来の技術に着目して為されたも
のであり、活性・触媒化するだめの白金が被メッキ物に
均−且つ確実にイ」着する白金コロイド溶液及びそれを
用いた無電解白金メッキ方法を提供せんとするものであ
る。The present invention has been made by focusing on such conventional technology, and it provides a platinum colloid solution and a platinum colloid solution that uniformly and reliably deposits platinum to be activated and catalyzed on the object to be plated, and a platinum colloid solution using the same. It is an object of the present invention to provide an electroless platinum plating method.
また、この発明の別の目的として、白金を担持体に付着
させることにより、化学合成反応用の触媒や電極として
広（利用できる白金担持体の製法も提供せんとするもの
である。Another object of the present invention is to provide a method for producing a platinum support that can be widely used as a catalyst or electrode for chemical synthesis reactions by attaching platinum to the support.
〈課題を解決するための手段〉
この発明は上記の目的を達成するために、多糖類を保護
コロイド剤として０．１〜１００ｇ、＃、還元性糖類を
還元剤として０．１〜１００ ｇ／ｆｆ、および白金塩
を０．０１〜３０ ｇ／ｆｆ含有してなる白金皿１０イ
ド溶液を開発したものである。<Means for Solving the Problems> In order to achieve the above object, the present invention uses polysaccharide as a protective colloid agent in an amount of 0.1 to 100 g/#, and reducing sugar as a reducing agent in an amount of 0.1 to 100 g/ A platinum plate solution containing 0.01 to 30 g/ff of platinum salt and platinum salt was developed.
また、前記白金コロイド溶液を被メッキ物に施し、該白
金コロイド溶液中に析出した白金粒子を被メッキ物上に
何着させた後、保護コロイド剤及び還元剤を除去し、次
いで無電解白金メッキ液を被メッキ物に施して無電解白
金メッキする無電解白金メッキ方法を開発したものであ
る。Further, the platinum colloid solution is applied to the object to be plated, and after the platinum particles precipitated in the platinum colloid solution are deposited on the object to be plated, the protective colloid agent and reducing agent are removed, and then electroless platinum plating is performed. An electroless platinum plating method has been developed in which electroless platinum plating is performed by applying a solution to the object to be plated.
更に、前記白金コロイド溶液を担持体に施し、該白金コ
ロイド溶液中に析出した白金粒子を被メッキ物上に付着
させた後、保護コロイド剤及び還元剤を除去する白金担
持体の製法を開発したものである。Furthermore, we have developed a method for manufacturing a platinum support in which the platinum colloid solution is applied to the support, the platinum particles precipitated in the platinum colloid solution are deposited on the object to be plated, and then the protective colloid agent and reducing agent are removed. It is something.
〈作 用〉
この発明に係る白金コロイド溶液は、まず多糖類を保護
コロイド剤として０．１〜］、ＯＯｇ／ρ含んでいる。<Function> The platinum colloid solution according to the present invention first contains a polysaccharide as a protective colloid agent in an amount of 0.1 to OOg/ρ.
この保護コロイド剤に用いられる多糖類の例としてはペ
クチン、寒天、デンプン、マンナン、グルコマンナンな
どを挙げることができる。Examples of polysaccharides used in this protective colloid include pectin, agar, starch, mannan, and glucomannan.
また、還元性糖類を還元剤として０．１〜１００ｇ／Ｉ
！、含んでいる。この還元剤に用いられる還元性糖類の
例としてはグルコース、ペクチン、フルクＩ・−スなど
を挙げることができる。更に、白金塩を０．０１〜３０
ｇ／ｐ、含んでいる。白金塩としては、１ＩｚＰｔ、ｃ
］６、ＫｚＰｔＣＩ６、ＮａｚＰｔＣ１６などの塩化白
金酸塩が好適である。尚、必要により水酸化ナトリウｌ
、や水酸化カリウムなどのｐＨ調整剤を添加しても良い
。Also, using reducing sugars as a reducing agent, 0.1 to 100 g/I
! , contains. Examples of reducing sugars used in this reducing agent include glucose, pectin, and fruc I.-su. Furthermore, platinum salt is added at 0.01 to 30
g/p, including. As platinum salt, 1IzPt,c
]6, KzPtCI6, NazPtC16 and other chloroplatinates are preferred. In addition, if necessary, sodium hydroxide
, or potassium hydroxide may be added.
このような組成をした本願発明に係る白金コロイド溶液
は安定性が非常に良く、白金粒子の凝集などが一切起こ
らないものである。また、従来はホルマリンを還元剤と
して使用していたので、残留ホルマリンによる不快臭な
どの問題もあったが、本発明に係る白金コロイド溶液の
場合は、還元剤として還元性糖類を採用しているので、
臭いの問題などは一切ない。更に「ペクチン」は、保護
コロイド剤としての機能、還元剤としての機能の両方を
備えているので、実用上非常に便利である。The platinum colloidal solution according to the present invention having such a composition has very good stability and does not cause any aggregation of platinum particles. Furthermore, since formalin was conventionally used as a reducing agent, there were problems such as unpleasant odor due to residual formalin, but in the case of the platinum colloid solution according to the present invention, reducing sugars are used as the reducing agent. So,
There are no odor issues at all. Furthermore, "pectin" has both the function of a protective colloid agent and the function of a reducing agent, so it is very convenient in practice.
そして、ガラスやセラミックなどの被メッキ物をこの白
金コロイド溶液中に浸漬したりして、被メッキ物の表面
に白金コロイド溶液を施せば、表面上に白金粒子が析出
して均一に吸着する。その後被メッキ物を白金コロイド
溶液中から取出し、塩酸その他の酸に浸漬したりして、
保護コロイド剤や還元剤の糖類を加水分解反応により除
去する。When an object to be plated, such as glass or ceramic, is immersed in this colloidal platinum solution and the colloidal platinum solution is applied to the surface of the object to be plated, platinum particles are precipitated on the surface and uniformly adsorbed. After that, the object to be plated is taken out of the platinum colloid solution and immersed in hydrochloric acid or other acid.
Protective colloid agents and reducing agent sugars are removed by hydrolysis reaction.
すると、高純度の白金粒子だけが被メッキ物の表面上に
密着状態で吸着する。つまり、被メッキ物の表面に白金
による薄層が形成された状態となり表面か活性・触媒化
される。従って、この活性・触媒化された被メッキ物の
表面に、無電解白金メッキ液による白金メッキを行えば
、パラジウムにより前処理していた従来と比べ、析出す
る白金の純度が商い。従って、高純度が要求されるセン
サーなどの用途に利用することができるようになる。Then, only high-purity platinum particles are adsorbed in close contact with the surface of the object to be plated. In other words, a thin layer of platinum is formed on the surface of the object to be plated, and the surface is activated and catalyzed. Therefore, if the surface of the activated and catalyzed object to be plated is plated with platinum using an electroless platinum plating solution, the purity of the precipitated platinum will be higher than in the conventional method in which the plated surface is pretreated with palladium. Therefore, it can be used in applications such as sensors that require high purity.
更に、ごの白金コロイド溶液を担持体に施し、前記と同
様の要領で、白金コロイド溶液中の白金を担持体−」二
に付着させたものは、化学合成反応用の触媒や電極とし
て利用することができ、或いはイオン交換膜に付着させ
て電解用接合体として利用することもできる。Furthermore, a colloidal platinum solution is applied to the support, and the platinum in the colloidal platinum solution is adhered to the support in the same manner as described above.The resulting product can be used as a catalyst or electrode for chemical synthesis reactions. Alternatively, it can be attached to an ion exchange membrane and used as a bond for electrolysis.
〈実 施 例〉 以下、この発明の好適な実施例を説明する。<Example> Hereinafter, preferred embodiments of this invention will be described.
まず最初に白金コロイド溶液の製造方法について述べる
。以下の第１表のような、白金塩、保護コロイド剤、還
元剤、ｐ Ｈ１１整剤を含んだ水溶液をつくる。First, a method for producing a platinum colloid solution will be described. Prepare an aqueous solution containing a platinum salt, a protective colloid, a reducing agent, and a pH 11 adjuster as shown in Table 1 below.
第１表 そしてこの水溶液を１００°Ｃの温度で加熱する。Table 1 This aqueous solution is then heated at a temperature of 100°C.
すると、水溶液が黒色に変色して求める白金コロイド溶
液ができる。得られた白金コロイド溶液は分散性が良く
、白金粒子が凝集したりすることはない。また、実施例
５に示すように、「ペクチン」の場合は１種類で保護コ
ロイド剤及び還元剤を兼用することができるので有利で
ある。尚、参考例１〜３ば、溶液がコロイド状にならな
かったり、或いはポルマリン臭を発生したりするのでコ
ロイド熔？夜としては好ましくなかった。Then, the aqueous solution turns black and the desired platinum colloid solution is created. The obtained platinum colloidal solution has good dispersibility, and the platinum particles do not aggregate. Furthermore, as shown in Example 5, "pectin" is advantageous because one type of pectin can serve as both a protective colloid agent and a reducing agent. In addition, in Reference Examples 1 to 3, the solutions did not become colloidal or emitted a polymeric odor. It wasn't a good night.
そして、前記実施例１の白金コしフィト溶液を用いて、
セラミック片の無電解白金メッキを行うことにした。ま
ず、セラミック片を白金コロイド溶液中に浸漬した。す
ると、白金コロイド溶液中の白金粒子がセラミック片の
表面に析出して均一に吸着される。次いて、白金粒子の
吸着が終了したら、セラミック片を白金コロイド？容液
中から取出し、今度は濃度１０％の塩酸に浸漬する。す
ると、セラミック片に付着している白金粒子以外の成分
、すなわち保護コ１コイＦ剤及び還元剤としての糖類が
加水分解反応により分解されて除去される。そして、Ｉ
Ｊ［を取り除いたセラミック片を水洗・乾燥すれば、表
面が白金の薄層で活性・触媒化されたセラミック片を得
ることができる。そして、このセラミンク片の表面に吸
着された白金粒子の純度を調べたところ１００％の高い
純度で、且つ密着性も十分であった。Then, using the platinum powder solution of Example 1,
We decided to perform electroless platinum plating on ceramic pieces. First, a ceramic piece was immersed in a platinum colloid solution. Then, the platinum particles in the platinum colloid solution are deposited on the surface of the ceramic piece and uniformly adsorbed. Next, after the platinum particles have been adsorbed, the ceramic piece is mixed with a platinum colloid. Take it out of the solution and immerse it in 10% hydrochloric acid. Then, the components other than the platinum particles adhering to the ceramic piece, that is, the protective coating F agent and sugars as a reducing agent are decomposed and removed by a hydrolysis reaction. And I
By washing and drying the ceramic piece from which J[ has been removed, it is possible to obtain a ceramic piece whose surface is activated and catalyzed by a thin layer of platinum. When the purity of the platinum particles adsorbed on the surface of this ceramic piece was examined, the purity was as high as 100%, and the adhesion was also sufficient.
次いで、このようにして活性・触媒化されたセラミンク
片を、今度は以下の如き無電解白金メッキ液にて無電解
白金メッキを行った。Next, the thus activated and catalyzed ceramic piece was electrolessly platinized using the following electroless platinum plating solution.
・白金（Ｐｔ（ＮＯ７）ｚ（ＮＨ３）ｚの形で）
２ｇ／ｊ２・アンモニア水 ５
０ｍ！・ヒドラジンＣＮＩ［２ＮＨ２・ｔｈｆ））
２ ｍ ｆｆ温 度
６０″ＣｐＨ１２
メッキ時間 ３０分得られた析
出物は外観及び密着性も良好で、しかも純度の高いもの
であった。このことは、被メッキ物の表面を活性・触媒
化している純度の高い白金粒子での前処理に因るもので
あり、従来の如き純度の低い白金粒子或いはパラジウム
による前処理では無電解白金メノギによる白金析出物の
純度向上は無理であった。つまり、この発明に係る無電
解白金メッキは、前処理として被メッキ物を密着性及び
純度の良い白金粒子にて予め活性・触媒化しておくこと
から、その上に行・う無電解白金メッキも密着性が高く
なると共に純度も良くなるものである。- Platinum (in the form of Pt(NO7)z(NH3)z)
2g/j2・Ammonia water 5
0m!・Hydrazine CNI [2NH2・thf))
2 m ff temperature
60"C pH12 Plating time: 30 minutes The obtained precipitate had good appearance and adhesion, and was highly pure. This indicates that the platinum of high purity activates and catalyzes the surface of the plated object. This is due to pretreatment with particles, and it has been impossible to improve the purity of platinum precipitates using electroless platinum agate with conventional pretreatment with platinum particles or palladium of low purity. In electrolytic platinum plating, the object to be plated is activated and catalyzed using platinum particles with good adhesion and purity as a pre-treatment, so the electroless platinum plating performed on top of that also has high adhesion and purity. It will also get better.
更に、この白金コロイド溶液を担持体に施し、前記と同
様の要領で、白金：１０イド溶液中の白金を電極やイオ
ン交換膜の担持体上に付着させれば、化学合成反応用の
高品質の触媒や電極、或いは電解用接合体を得ることか
できる。Furthermore, if this platinum colloid solution is applied to a carrier and the platinum in the platinum:10ide solution is deposited on the carrier of an electrode or ion exchange membrane in the same manner as described above, a high quality product for chemical synthesis reactions can be obtained. It is possible to obtain catalysts, electrodes, or electrolytic assemblies.
〈発明の効果〉
この発明に係る白金コロイド溶液は、白金粒子−の凝集
などが一切起こらない安定したものであり、また、還元
剤として還元性糖類を採用しているので、臭いの問題な
ども一切ない。しかも、白金粒子が高純度で且つ均一に
吸着するので、高純度が要求される無電解白金メッキの
前処理を行うのに最適である。加えて、密着性も良いの
で、使用する白金コロイド溶液のロスか少なく経済的に
もイ］利である。<Effects of the Invention> The colloidal platinum solution according to the present invention is stable, with no aggregation of platinum particles, and since reducing sugars are used as the reducing agent, there are no problems with odor. Not at all. Moreover, since the platinum particles are highly pure and uniformly adsorbed, it is ideal for pre-treatment of electroless platinum plating, which requires high purity. In addition, since it has good adhesion, there is less loss of platinum colloid solution, which is economically advantageous.
また、この発明に係る無電解白金メッキ方法は、被メッ
キ物に白金コ【コイド溶液を施し、高純度の白金粒子だ
けを被メッキ物の表面上に密着状態で吸着させるので、
被メッキ物の表面が白金粒子により活性・触媒化される
。従ってこの活性・触媒化された被メッキ物の表面に無
電解白金メッキ液による白金メッキを行えば、パラジウ
ムなどにより前処理をしていた従来と比べ、析出する白
金粒子の純度が高い。従って、高純度が要求されるセン
ーリ°−などの用途に利用することかできる。Further, in the electroless platinum plating method according to the present invention, a platinum coid solution is applied to the object to be plated, and only high-purity platinum particles are adsorbed in close contact with the surface of the object to be plated.
The surface of the object to be plated is activated and catalyzed by the platinum particles. Therefore, if the surface of the activated and catalyzed object to be plated is plated with platinum using an electroless platinum plating solution, the purity of the precipitated platinum particles will be higher than in the conventional method in which pretreatment with palladium or the like is performed. Therefore, it can be used in applications such as sensors that require high purity.
更に、この発明に係る白金担持体の製法は、白金コロイ
ド溶液を担持体に施し、白金コロイド溶液中に析出した
白金粒子を電極やイオン交換膜の担持体上に高純度で何
着させることができるので、化学合成反応用の高品質の
触媒や電極、或いは電解用接合体を容易に得ることがで
きる。Furthermore, the method for producing a platinum support according to the present invention involves applying a colloidal platinum solution to the support, and depositing the platinum particles precipitated in the colloidal platinum solution onto the support of an electrode or ion exchange membrane in high purity. Therefore, high-quality catalysts and electrodes for chemical synthesis reactions, or assemblies for electrolysis can be easily obtained.
Claims (3)
／ｌ、還元性糖類を還元剤として０．１〜１００ｇ／ｌ
、および白金塩を０．０１〜３０ｇ／ｌ含有してなる白
金コロイド溶液。(1) 0.1-100g of polysaccharide as a protective colloid agent
/l, 0.1-100g/l using reducing sugars as reducing agent
, and a platinum colloid solution containing 0.01 to 30 g/l of platinum salt.
ッキ物に施し、該白金コロイド溶液中に析出した白金粒
子を被メッキ物上に付着させた後、保護コロイド剤及び
還元剤を除去し、次いで無電解白金メッキ液を被メッキ
物に施して無電解白金メッキする無電解白金メッキ方法
。(2) After applying the colloidal platinum solution according to claim 1 to the object to be plated and depositing the platinum particles precipitated in the colloidal platinum solution onto the object to be plated, the protective colloid agent and the reducing agent are removed. , an electroless platinum plating method in which electroless platinum plating is performed by applying an electroless platinum plating solution to the object to be plated.
体に施し、白金コロイド溶液中に析出した白金粒子を被
メッキ物上に付着させた後、保護コロイド剤及び還元剤
を除去する白金担持体の製法(3) Platinum support in which the platinum colloidal solution according to claim 1 is applied to a carrier, the platinum particles precipitated in the platinum colloidal solution are deposited on the object to be plated, and then the protective colloid agent and reducing agent are removed. body manufacturing method
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14997488A JPH01319683A (en) | 1988-06-20 | 1988-06-20 | Platinum colloidal solution and electroless platinum plating method using the same solution and production of platinum carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14997488A JPH01319683A (en) | 1988-06-20 | 1988-06-20 | Platinum colloidal solution and electroless platinum plating method using the same solution and production of platinum carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01319683A true JPH01319683A (en) | 1989-12-25 |
Family
ID=15486697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14997488A Pending JPH01319683A (en) | 1988-06-20 | 1988-06-20 | Platinum colloidal solution and electroless platinum plating method using the same solution and production of platinum carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01319683A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5250490A (en) * | 1991-12-24 | 1993-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Noble metal supported on a base metal catalyst |
| JP2008121106A (en) * | 2006-07-07 | 2008-05-29 | Rohm & Haas Electronic Materials Llc | Improved electroless copper composition |
| KR100886794B1 (en) * | 2000-07-29 | 2009-03-05 | 우미코레 아게 운트 코 카게 | Noble metal nanoparticles, a process for preparing these and their use |
| CN105612272A (en) * | 2014-07-17 | 2016-05-25 | 日本电镀工程股份有限公司 | Pretreatment solution for electroless plating and electroless plating method |
| WO2017064874A1 (en) * | 2015-10-15 | 2017-04-20 | 小島化学薬品株式会社 | Electroless platinum plating solution |
| US20170171982A1 (en) * | 2015-12-14 | 2017-06-15 | Rohm And Haas Electronic Materials Llc | Environmentally friendly stable catalysts for electroless metallization of printed circuit boards and through-holes |
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| JPS57134586A (en) * | 1981-02-13 | 1982-08-19 | Agency Of Ind Science & Technol | Production of joined body for electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JPS57134586A (en) * | 1981-02-13 | 1982-08-19 | Agency Of Ind Science & Technol | Production of joined body for electrolysis |
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|---|---|---|---|---|
| US5250490A (en) * | 1991-12-24 | 1993-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Noble metal supported on a base metal catalyst |
| USRE36330E (en) * | 1991-12-24 | 1999-10-05 | Witco Corporation | Noble metal supported on a base metal catalyst |
| KR100886794B1 (en) * | 2000-07-29 | 2009-03-05 | 우미코레 아게 운트 코 카게 | Noble metal nanoparticles, a process for preparing these and their use |
| JP2008121106A (en) * | 2006-07-07 | 2008-05-29 | Rohm & Haas Electronic Materials Llc | Improved electroless copper composition |
| EP1876260A3 (en) * | 2006-07-07 | 2010-03-17 | Rohm and Haas Electronic Materials LLC | Improved electroless copper compositions |
| CN105612272A (en) * | 2014-07-17 | 2016-05-25 | 日本电镀工程股份有限公司 | Pretreatment solution for electroless plating and electroless plating method |
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| WO2017064874A1 (en) * | 2015-10-15 | 2017-04-20 | 小島化学薬品株式会社 | Electroless platinum plating solution |
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| JP2017110297A (en) * | 2015-12-14 | 2017-06-22 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Environmentally friendly stable catalyst for electroless metalization of printed circuit board and through-hole |
| JP2017110298A (en) * | 2015-12-14 | 2017-06-22 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ | Environmentally friendly stable catalyst for electroless metalization of printed circuit board and through-hole |
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