JPH0250975A - Method for stabilizing palladium hydrosol - Google Patents
Method for stabilizing palladium hydrosolInfo
- Publication number
- JPH0250975A JPH0250975A JP20213888A JP20213888A JPH0250975A JP H0250975 A JPH0250975 A JP H0250975A JP 20213888 A JP20213888 A JP 20213888A JP 20213888 A JP20213888 A JP 20213888A JP H0250975 A JPH0250975 A JP H0250975A
- Authority
- JP
- Japan
- Prior art keywords
- hydrosol
- palladium
- exchange resin
- cation exchange
- palladium hydrosol
- 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.)
- Granted
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims description 187
- 229910052763 palladium Inorganic materials 0.000 title claims description 95
- 238000000034 method Methods 0.000 title claims description 8
- 230000000087 stabilizing effect Effects 0.000 title claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000005345 coagulation Methods 0.000 abstract description 10
- 230000015271 coagulation Effects 0.000 abstract description 10
- 238000007747 plating Methods 0.000 abstract description 10
- 238000001556 precipitation Methods 0.000 abstract description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000012279 sodium borohydride Substances 0.000 abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 239000002612 dispersion medium Substances 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000000084 colloidal system Substances 0.000 description 22
- 239000003456 ion exchange resin Substances 0.000 description 11
- 229920003303 ion-exchange polymer Polymers 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 5
- 229910002113 barium titanate Inorganic materials 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229940023913 cation exchange resins Drugs 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 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
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 102100031151 C-C chemokine receptor type 2 Human genes 0.000 description 2
- 101710149815 C-C chemokine receptor type 2 Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、無電解金属めっきを施す際の触媒付与のため
に使用されるパラジウムヒドロゾルの安定化方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for stabilizing palladium hydrosol used for providing a catalyst during electroless metal plating.
紙や不織布などの繊維成形物、ガラス、セラミックス及
び高分子材料等は本来絶縁体であるが、これらを基材と
して無電解金属めっきによって各種金属を付与すること
により、磁気的性質や導電性等の電気的性質を持たせる
ことが行われている。Fiber molded products such as paper and nonwoven fabrics, glass, ceramics, and polymeric materials are originally insulators, but by applying various metals to these base materials through electroless metal plating, they can be made to have magnetic properties, conductivity, etc. Efforts are being made to impart the same electrical properties.
また、金属や金属酸化物の場合にも、これらを基材とし
て無電解金属めっきによって他の各種金属を付与するこ
とにより、磁気的性質や電気的性質を改良したり、本来
有する特性とは全く別の新しい磁気的性質や電気的性質
を持たせることが行われている。In addition, in the case of metals and metal oxides, by applying various other metals to these base materials through electroless metal plating, it is possible to improve their magnetic and electrical properties, or to improve their magnetic and electrical properties. Efforts are being made to impart new magnetic and electrical properties.
本発明者は、無電解金属めっきを施すに当たって、基材
（被めっき物）を水を分散媒とするパラジウムヒドロゾ
ル中に浸漬後、水洗を行うことで被めっき物表面にパラ
ジウムコロイドを付与し、次いで、無電解金属めっきす
る方法（例えば、特開昭６１−２０７６６６号公報）を
提案している。When performing electroless metal plating, the present inventor applied palladium colloid to the surface of the object to be plated by immersing the base material (the object to be plated) in palladium hydrosol using water as a dispersion medium and then washing with water. Then, a method of electroless metal plating (for example, JP-A-61-207666) has been proposed.
上記の無電解金属めっきに用いられているパラジウムヒ
ドロゾルは、塩化パラジウム（ＩＩＩ塩などのパラジウ
ム塩水溶液を、界面活性剤の存在下で、水素化ホウ素ナ
トリウム、ヒドラジン等の水溶性還元剤で還元して得ら
れる粒径２０〜５０人のパラジウムコロイドを含む分散
液である。The palladium hydrosol used in the above electroless metal plating is produced by reducing an aqueous palladium salt solution such as palladium chloride (III salt) with a water-soluble reducing agent such as sodium borohydride or hydrazine in the presence of a surfactant. This is a dispersion containing a palladium colloid with a particle size of 20 to 50 particles.
〔発明が解決しようとする課題］
前述のパラジウムヒドロゾルを使用して被めっき物の表
面にパラジウムコロイドを均−且つ強固に付与させるた
めには、パラジウムヒドロゾルが長期に亘り安定に保た
れることが望ましい。しかし、パラジウムヒドロゾルを
連続或いは長期にわたり繰り返して使用すると、パラジ
ウムヒドロゾル中のパラジウムコロイドが凝集沈澱して
使用できなくなるという状態が生じてくる。[Problem to be solved by the invention] In order to uniformly and firmly apply palladium colloid to the surface of the object to be plated using the above-mentioned palladium hydrosol, the palladium hydrosol must be kept stable for a long period of time. This is desirable. However, when palladium hydrosol is used continuously or repeatedly over a long period of time, a situation arises in which the palladium colloid in the palladium hydrosol aggregates and precipitates, making it unusable.
パラジウムコロイドが凝集沈澱してくるのは、パラジウ
ムヒドロゾル中に被めっき物を浸漬処理した時に、被め
っき物の一部成分が溶出したり、また、被めっき物の前
処理（エンチング等）時の酸やアルカリ等が混入したり
し、これらの不純物（電解質）特に２価以上の陽イオン
がその原因と考えられ、このことがパラジウムヒドロゾ
ルを連続或いは長期にわたり繰り返し使用する際の難点
となっていた。゛
従って、無電解金属めっきを施す際の触媒付与のために
使用されるパラジウムヒドロゾルは、通常、その使用に
当たっては、使用するたびに被めっき物の表面に付着さ
せるパラジウムコロイドの必要量よりも過剰のパラジウ
ムコロイドを存在させたものを調製し、使用後は過剰分
のパラジウムコロイドが残留しているにもかかわらず廃
棄しているのが現状である。Palladium colloid coagulates and precipitates because some components of the plating object are eluted when the object is immersed in palladium hydrosol, or during pretreatment (etching, etc.) of the object to be plated. These impurities (electrolytes), especially divalent or higher cations, are considered to be the cause, and this poses a problem when using palladium hydrosol continuously or repeatedly over a long period of time. was. Therefore, when using palladium hydrosol, which is used to provide a catalyst during electroless metal plating, the amount of palladium colloid that is deposited on the surface of the object to be plated is usually lower than the amount required each time it is used. Currently, products containing an excess of palladium colloid are prepared and discarded after use, even though the excess palladium colloid remains.
本発明は、パラジウムヒドロゾルの使用に際しての上記
問題点を解決することを技術的課題とするものである。The technical object of the present invention is to solve the above-mentioned problems when using palladium hydrosol.
本発明者らは、前記技術的課題を解決するために長期に
亘り鋭意検討を重ねた結果、パラジウムヒドロゾル中の
パラジウムコロイドを凝集沈澱させる原因と考えられる
不純物（電解質）着目し、パラジウムコロイド粒子を含
むパラジウムヒドロゾル中に陽イオン交換樹脂を存在さ
せ、これに被めっき物をパラジウムヒドロゾル中に浸漬
する際に混入する不純物を捕捉させれば、パラジウムコ
ロイドの凝集沈澱を防止できることを見出し、本発明を
完成するに至ったのである。As a result of extensive research over a long period of time in order to solve the above technical problem, the present inventors focused on the impurity (electrolyte) that is thought to be the cause of coagulation and precipitation of palladium colloid in palladium hydrosol, and developed palladium colloid particles. It has been discovered that coagulation and precipitation of palladium colloid can be prevented by allowing a cation exchange resin to exist in a palladium hydrosol containing palladium hydrosol and trapping impurities mixed in when the object to be plated is immersed in the palladium hydrosol. This led to the completion of the present invention.
即ち、本発明は、負電荷を有したパラジウムコロイド粒
子を含むパラジウムヒドロゾル中に陽イオン交換樹脂を
存在させることを特徴とするパラジウムヒドロゾルの安
定化方法である。That is, the present invention is a method for stabilizing palladium hydrosol, which is characterized in that a cation exchange resin is present in palladium hydrosol containing negatively charged palladium colloidal particles.
先ず、本発明において最も重要な点は、負電荷を有した
パラジウムコロイド粒子を含むパラジウムヒドロゾル中
に陽イオン交換樹脂を存在させた点にある。陽イオン交
換樹脂を、負電荷を有したパラジウムコロイド粒子を含
むパラジウムヒドロゾル中に存在させた場合には、被め
っき物をパラジウムヒドロゾル中に浸漬する際に混入す
る不純物特に２価以上の陽イオンを効率よく捕捉させる
ことができるので、パラジウムヒドロゾル中のパラジウ
ムコロイドの凝集沈澱が惹起せず、その結果、安定な状
態を維持しつつ連続或いは長期にわたり繰り返し使用す
ることができるのである。First, the most important point in the present invention is that a cation exchange resin is present in a palladium hydrosol containing negatively charged palladium colloidal particles. When a cation exchange resin is present in a palladium hydrosol containing negatively charged palladium colloidal particles, impurities, especially divalent or more valent cations, mixed in when the object to be plated is immersed in the palladium hydrosol can be removed. Since ions can be efficiently captured, the palladium colloid in the palladium hydrosol does not coagulate and precipitate, and as a result, it can be used continuously or repeatedly over long periods of time while maintaining a stable state.
次に、本発明実施にあたっての諸条件について述べる。Next, various conditions for implementing the present invention will be described.
本発明における負電荷を有したパラジウムコロイド粒子
を含むパラジウムヒドロゾルは、次の方法により調製す
ることができる。The palladium hydrosol containing negatively charged palladium colloidal particles in the present invention can be prepared by the following method.
パラジウムｆｌ［ｌ塩の水溶液を水溶性高分子、陰イオ
ン性界面活性剤及び非イオン性界面活性剤のいずれか一
種又は二種との存在下で、水素化ホウ素ナトリウム、ヒ
ドラジン等の還元剤で還元処理すれば、負電荷を有した
パラジウムコロイド粒子を含むパラジウムヒドロゾルが
得られる。An aqueous solution of palladium fl[l salt is treated with a reducing agent such as sodium borohydride or hydrazine in the presence of one or two of a water-soluble polymer, an anionic surfactant, and a nonionic surfactant. The reduction treatment yields a palladium hydrosol containing negatively charged palladium colloidal particles.
尚、水溶性高分子としては、ヒドロキシプロピルセルロ
ース、ポリ酢酸ビニル、ポリビニルアルコール、ポリビ
ニルピロリドン等が使用できる。Note that, as the water-soluble polymer, hydroxypropylcellulose, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, etc. can be used.
また、界面活性剤としては、ドデシルベンゼンスルホン
酸ナトリウム等の陰イオン性界面活性剤、ポリエチレン
グリコール−Ｐ−ノニルフェニルエーテル等の非イオン
性界面活性剤を使用することができる。Further, as the surfactant, anionic surfactants such as sodium dodecylbenzenesulfonate and nonionic surfactants such as polyethylene glycol-P-nonylphenyl ether can be used.
本発明における陽イオン交換樹脂としては、スルホン酸
型陽イオン交換樹脂、カルボン酸型陽イオン交換樹脂等
であり、好ましくはこれらをＮａ、Ｋ 、 ＮＨ４等の
１価の陽イオンに再生したものを使用することができる
。The cation exchange resins used in the present invention include sulfonic acid type cation exchange resins, carboxylic acid type cation exchange resins, etc., and preferably those regenerated into monovalent cations such as Na, K, NH4, etc. can be used.
負電荷を有したパラジウムコロイド粒子を含むパラジウ
ムヒドロゾル中に存在させる陽イオン交換樹脂の量は、
パラジウムヒドロゾル１尼に対して０．１ｇ以上が好ま
しい。０，１ｇより少ない場合は、パラジウムヒドロゾ
ル中に陽イオン交換樹脂を存在させる効果が充分でない
。The amount of cation exchange resin present in the palladium hydrosol containing negatively charged palladium colloidal particles is:
The amount is preferably 0.1 g or more per 1 portion of palladium hydrosol. If it is less than 0.1 g, the effect of the presence of the cation exchange resin in the palladium hydrosol will not be sufficient.
パラジウムヒドロゾル中に陽イオン交換樹脂を存在させ
るに当たっては、直接粒状で混合させてもよいが、不織
布等で陽イオン交換樹脂をパックし、この不織布パック
をパラジウムヒドロゾル中に存在させておくという状態
がより好ましい。When making the cation exchange resin exist in the palladium hydrosol, it is possible to mix it directly in the form of granules, but it is also possible to pack the cation exchange resin with a nonwoven fabric, etc., and make this nonwoven fabric pack exist in the palladium hydrosol. The condition is more favorable.
〔実施例］ 次に、実施例及び比較例により本発明を説明する。〔Example] Next, the present invention will be explained with reference to Examples and Comparative Examples.
〈パラジウムヒドロゾルの調製〉試料Ａ−Ｄ。<Preparation of palladium hydrosol> Samples A-D.
試料：Ａ
塩化パラジウム（Ｉ［＋ ２５０μｍｏｌを塩化ナトリ
ウム１．２５ ｍ ｍｏｌを含む水溶液２．５ｍｌに溶
解し、次いで、純水で９４蔵に希釈した。この溶液を激
しく攪拌しながら、ポリビニルアルコール２５■を含む
水溶液１ ｍｌを加え、次いで、水素化ホウ素ナトリウ
ム１ｍ ｍｏｌを含む水溶液５滅を滴下すると、溶液の
色が急、変し、負電荷を有したパラジウムコロイド粒子
を含むｐＨ９，０のパラジウムヒドロゾルを得た。Sample: A 250 μmol of palladium chloride (I [+) was dissolved in 2.5 ml of an aqueous solution containing 1.25 mmol of sodium chloride, and then diluted to 94 μmol with pure water. While vigorously stirring this solution, 25 μmol of polyvinyl alcohol When 1 ml of an aqueous solution containing (1) was added and then 5 ml of an aqueous solution containing 1 m mol of sodium borohydride was added dropwise, the color of the solution suddenly changed and palladium at pH 9.0 containing negatively charged palladium colloidal particles was added. A hydrosol was obtained.
試料：Ｂ
塩化パラジウム（ＩＯ５０μｍｏｌを塩化ナトリウム２
５０μｍｏｌを含む水溶液２ 、５ ｍｆｌに溶解し、
次いで、純水で９４戒に希釈した。この溶液を激しく攪
拌しながら、ドデシルベンゼンスルホン酸ナトリウム１
０ｍｇを含む水溶液１ ｍｌを加え、次いで、水素化ホ
ウ素ナトリウム２００μｍｏｌを含む水溶液５成を滴下
すると、溶液の色が象、変し、負電荷を有したパラジウ
ムコロイド粒子を含むｐＨ８，７のパラジウムヒドロゾ
ルを得た。Sample: B Palladium chloride (50 μmol of IO was mixed with 2 sodium chloride)
Dissolved in 2.5 mfl of an aqueous solution containing 50 μmol,
Then, it was diluted to 94 precepts with pure water. While stirring this solution vigorously, add 1 portion of sodium dodecylbenzenesulfonate.
When 1 ml of an aqueous solution containing 0 mg of sodium borohydride was added, and then 5 aqueous solutions containing 200 μmol of sodium borohydride were added dropwise, the color of the solution changed, indicating that palladium hydride with a pH of 8.7 containing negatively charged palladium colloidal particles was added. Got Sol.
試料：Ｃ
水溶性高分子としてポリビニルアルコール１５ｍｇと界
面活性剤としてドデシルベンゼンスルホン酸ナトリウム
２５ｍｇとを使用した以外は、試料Ａと同様にして負電
荷を有したパラジウムコロイド粒子を含むｐｕ ８．８
のパラジウムヒドロゾルを得た。Sample: C Pu 8.8 containing negatively charged palladium colloid particles in the same manner as Sample A except that 15 mg of polyvinyl alcohol was used as the water-soluble polymer and 25 mg of sodium dodecylbenzenesulfonate was used as the surfactant.
A palladium hydrosol was obtained.
試料：Ｄ
水溶性高分子としてポリ酢酸ビニル２５■と界面活性剤
としてポリエチレングリコール−Ｐ−ノニルフェニルエ
ーテル２５ｍｇとを使用した以外は、試料Ｂと同様にし
て負電荷を有したパラジウムコロイド粒子を含むｐＨ８
，７のパラジウムヒドロゾルを得た。Sample: D Contains negatively charged palladium colloidal particles in the same manner as Sample B, except that 25 mg of polyvinyl acetate was used as the water-soluble polymer and 25 mg of polyethylene glycol-P-nonylphenyl ether was used as the surfactant. pH8
, 7 was obtained.
実施例１
試料Ａのパラジウムヒドロゾル５０成中に、カルボン酸
系弱酸性イオン交換樹脂（ダウエックスＣＣト２室町化
学工業■製）をＮａ型に再生した０、３ｇのＮａ型カル
ボン酸系弱酸性イオン交換樹脂を不織布にパックした状
態で存在させ、次いで、４０゛Ｃに昇温した。このパラ
ジウムヒドロゾル中へ表面に正電荷を有したチタン酸バ
リウム系成形体（円筒型φ６肛×φ２．３祁×７．５肛
）２５個を１５分間浸漬した後、炉別し、パラジウムヒ
ドロゾルだけを別容器に移した。Example 1 During the formation of the palladium hydrosol 50 of Sample A, 0.3 g of Na-type weakly acidic carboxylic acid ion exchange resin (manufactured by DOWEX CCTO 2 Muromachi Chemical Industry Co., Ltd.) was regenerated into Na-type. An acidic ion exchange resin was present in a packed state in a nonwoven fabric, and then the temperature was raised to 40°C. After immersing 25 pieces of barium titanate-based molded bodies (cylindrical shape φ6 holes x φ2.3 holes x 7.5 holes) with positive charges on the surface into this palladium hydrosol for 15 minutes, they were separated into a furnace and palladium Only the sol was transferred to a separate container.
続いて、炉別後の前記パラジウムヒドロゾルを用いて、
前記一連の操作を２０回連続繰り返して合計５００個の
チタン酸バリウム系成形体に触媒付与を施した。２０回
連続繰り返した後のパラジウムヒドロゾルは、パラジウ
ムコロイドの凝集沈澱が惹起しておらず安定な状態を維
持していた。Subsequently, using the palladium hydrosol after furnace separation,
The above series of operations was repeated 20 times to apply a catalyst to a total of 500 barium titanate molded bodies. The palladium hydrosol after 20 consecutive repetitions maintained a stable state without causing coagulation and precipitation of palladium colloid.
実施例２
陽イオン交換樹脂として、Ｎａ型カルボン酸系弱酸性イ
オン交換樹脂の代わりに、スルホン酸系強酸性イオン交
換樹脂（ダウエックス５０Ｗ−×８室町化学工業■製）
のＮａ型に再生したＮａ型スルホン酸系強酸性イオン交
換樹脂２．５ｇを使用し、１５回の操作を連続繰り返し
た以外は、実施例１と同様にして合計３７５個のチタン
酸バリウム系成形体に触媒付与を施した。１５回連続繰
り返した後のパラジウムヒドロゾルは、パラジウムコロ
イドの凝集沈澱が惹起しておらず安定な状態を維持して
いた。Example 2 As a cation exchange resin, a sulfonic acid type strong acid ion exchange resin (manufactured by DOWEX 50W-×8 Muromachi Chemical Industry ■) was used instead of a Na type carboxylic acid type weak acid ion exchange resin.
A total of 375 barium titanate moldings were made in the same manner as in Example 1, except that 2.5 g of the Na-type sulfonic acid-based strongly acidic ion exchange resin regenerated to the Na-type was used and the operation was repeated 15 times. The body was catalyzed. The palladium hydrosol after 15 consecutive repetitions maintained a stable state without causing coagulation and precipitation of palladium colloid.
実施例３
試料Ｂのパラジウムヒドロゾル１００ｄ中に、カルボン
酸系弱酸性イオン交換樹脂（ダウエックスＣＣＲ−２室
町化学工業■製）をに型に再生した０、３ｇのに型カル
ボン酸系弱酸性イオン交換樹脂を不織布にパンクした状
態で存在させ、次いで、４０°Ｃに昇温した。このパラ
ジウムヒドロゾル中へ表面に正電荷を有したチタン酸バ
リウム系成形体（φ２０ｍｍＸ２ｍｍ） ５個を１５分
間浸漬した後、炉別し、パラジウムヒドロゾルだけを別
容器に移した。Example 3 In 100 d of the palladium hydrosol of Sample B, 0.3 g of a weakly acidic carboxylic acid ion exchange resin (DOWEX CCR-2 manufactured by Muromachi Chemical Industry Co., Ltd.) was regenerated into a mold. The ion exchange resin was present in the nonwoven fabric in a punctured state, and then the temperature was raised to 40°C. Five pieces of barium titanate molded bodies (φ20 mm x 2 mm) each having a positive charge on the surface were immersed in this palladium hydrosol for 15 minutes, and then separated in a furnace, and only the palladium hydrosol was transferred to a separate container.
続いて、炉別後の前記パラジウムヒドロゾルを用いて、
前記一連の操作を４０回連続繰り返して合計２００個の
チタン酸バリウム系成形体に触媒付与を施した。４０回
連続繰り返した後のパラジウムヒドロゾルは、パラジウ
ムコロイドの凝集沈澱が惹起しておらず安定な状態を維
持していた。Subsequently, using the palladium hydrosol after furnace separation,
The above series of operations was repeated 40 times to apply a catalyst to a total of 200 barium titanate molded bodies. The palladium hydrosol after 40 consecutive cycles maintained a stable state without causing coagulation and precipitation of palladium colloid.
実施例４
試料Ｃのパラジウムヒドロゾル５０威中に、カルボン酸
系弱酸性イオン交換樹脂（ダウエックスＣＣＲ−２室町
化学工業■製）をＮＨ４型に再生した１、０ｇのＮＨ４
型カルボン酸系弱酸性イオン交換樹脂を不織布乙こバッ
クした状態で存在させ、次いで、４０°Ｃに昇温した。Example 4 1.0 g of NH4, which was obtained by regenerating carboxylic acid-based weakly acidic ion exchange resin (DOWEX CCR-2 manufactured by Muromachi Chemical Industry Co., Ltd.) into the NH4 form, was added to the palladium hydrosol 50 of Sample C.
A type carboxylic acid type weakly acidic ion exchange resin was made to exist in a state covered with a non-woven fabric, and then the temperature was raised to 40°C.
このパラジウムヒドロゾル中へ表面に正電荷を有したチ
タン酸ストロンチウム系成形体（φ６ ｍｍ Ｘ ０．
１８ｍｍ ） ２０個を１５分間浸漬した後、炉別し、
パラジウムヒドロゾルだけを別容器に移した。A strontium titanate-based molded body having a positive charge on the surface (φ6 mm
18mm) After immersing 20 pieces for 15 minutes, they were separated into furnaces,
Only the palladium hydrosol was transferred to a separate container.
続いて、ｒ別後の前記パラジウムヒドロゾルを用いて、
前記一連の操作を２０回連続繰り返して合計４００個の
チタン酸ストロンチウム系成形体に触媒付与を施した。Subsequently, using the palladium hydrosol after r separation,
The above series of operations was repeated 20 times to apply a catalyst to a total of 400 strontium titanate molded bodies.
２０回連続繰り返した後のパラジウムヒドロゾルは、パ
ラジウムコロイドの凝集沈澱が惹起しておらず安定な状
態を維持していた。The palladium hydrosol after 20 consecutive repetitions maintained a stable state without causing coagulation and precipitation of palladium colloid.
実施例５
試料りのパラジウムヒドロゾル５０ｍＱ中に、スルホン
酸系強酸性イオン交換樹脂（ダウエックス５０ｔ＃−Ｘ
８室町化学工業■製）をに型に再生した２、０ｇのに型
スルボン酸系強酸性イオン交換樹脂を不織布にパックし
た状態で存在させ、次いで、４０°Ｃに昇温した。この
パラジウムヒドロゾル中へ表面ニ正電荷を有したチタン
酸ジルコン酸鉛系成形体（４０ｍｍＸ ８ ｍｍＸ０．
２ ｍｍ） ５個を１５分間浸漬した後炉別し、パラジ
ウムヒドロゾルだけを別容器に移した。Example 5 A sulfonic acid-based strongly acidic ion exchange resin (Dowex 50t#-X) was added to a sample of palladium hydrosol 50mQ.
8 Muromachi Kagaku Kogyo ■) was regenerated into a mold and 2.0 g of a molded sulfonic acid-based strongly acidic ion exchange resin was placed in a packed state in a nonwoven fabric, and then the temperature was raised to 40°C. A lead zirconate titanate molded body (40 mm x 8 mm x 0.5 mm
After immersing 5 pieces (2 mm) for 15 minutes, they were separated from the furnace, and only the palladium hydrosol was transferred to a separate container.
続いて、炉別後の前記パラジウムヒドロゾルを用いて、
前記一連の操作を２０回連続繰り返して合計１００個の
チタン酸ジルコン酸鉛系成形体に触媒付与を施した。２
０回連続繰り返した後のパラジウムヒドロゾルは、パラ
ジウムコロイドの凝集沈澱が惹起しておらず安定な状態
を維持していた。Subsequently, using the palladium hydrosol after furnace separation,
The above series of operations was repeated 20 times to apply a catalyst to a total of 100 lead zirconate titanate molded bodies. 2
The palladium hydrosol after 0 consecutive repetitions maintained a stable state without causing coagulation and precipitation of palladium colloid.
比較例１
試料Ａのパラジウムヒドロゾル中に陽イオン交換樹脂を
存在させない以外は、実施例１と同様な操作を繰り返し
たが、３回連続繰り返した後のパラジウムヒドロゾル中
には、パラジウムコロイドの凝集沈澱が認められた。Comparative Example 1 The same operation as in Example 1 was repeated except that the cation exchange resin was not present in the palladium hydrosol of sample A, but the palladium colloid was present in the palladium hydrosol after three consecutive repetitions. Agglomerated precipitate was observed.
比較例２
試料Ｂのパラジウムヒドロゾル中に陽イオン交換樹脂を
存在させない以外は、実施例３と同様な操作を繰り返し
たが、５回連続繰り返した後のパラジウムヒドロゾル中
には、パラジウムコロイドの凝集沈澱が認められた。Comparative Example 2 The same operation as in Example 3 was repeated except that the cation exchange resin was not present in the palladium hydrosol of sample B, but the palladium colloid was present in the palladium hydrosol after 5 consecutive repetitions. Agglomerated precipitate was observed.
本発明に係るパラジウムヒドロゾルの安定化方法は、前
出実施例に示した通り、パラジウムヒト０ゾル中ムこ被
めっき物を浸漬処理する際に混入する不純物を、該パラ
ジウムヒドロゾル中に予め陽イオン交換樹脂を存在させ
ておくことによって効率良く捕捉させることができるこ
とに起因して、パラジウムコロイドの凝集沈澱が惹起せ
ず、その結果、安定な状態を維持することができる。As shown in the previous example, the method for stabilizing palladium hydrosol according to the present invention is to remove impurities that are mixed into the palladium hydrosol during immersion treatment of the muco-plated object in the palladium hydrosol. Since the presence of the cation exchange resin enables efficient capture, coagulation and precipitation of palladium colloid does not occur, and as a result, a stable state can be maintained.
従って、本発明方法によれば、無電解金属めっきを施す
際の触媒付与のために使用する負電荷を有したパラジウ
ムコロイド粒子を含むパラジウムヒドロゾルを連続或い
は長期にわたり繰り返し、効率的に使用することができ
る。Therefore, according to the method of the present invention, palladium hydrosol containing negatively charged palladium colloid particles used for providing a catalyst during electroless metal plating can be used continuously or repeatedly over a long period of time and efficiently. Can be done.
Claims (1)
ラジウムヒドロゾル中に陽イオン交換樹脂を存在させる
ことを特徴とするパラジウムヒドロゾルの安定化方法。(1) A method for stabilizing palladium hydrosol, which comprises making a cation exchange resin exist in palladium hydrosol containing negatively charged palladium colloidal particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20213888A JP2626907B2 (en) | 1988-08-12 | 1988-08-12 | Palladium hydrosol stabilization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20213888A JP2626907B2 (en) | 1988-08-12 | 1988-08-12 | Palladium hydrosol stabilization method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0250975A true JPH0250975A (en) | 1990-02-20 |
| JP2626907B2 JP2626907B2 (en) | 1997-07-02 |
Family
ID=16452588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20213888A Expired - Fee Related JP2626907B2 (en) | 1988-08-12 | 1988-08-12 | Palladium hydrosol stabilization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2626907B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0899288A2 (en) * | 1997-08-29 | 1999-03-03 | Taisei Chemical Industries Ltd | Process for producing dispersion of functional compound |
| US7220140B2 (en) | 2005-10-17 | 2007-05-22 | Hosiden Corporation | Board connector |
-
1988
- 1988-08-12 JP JP20213888A patent/JP2626907B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0899288A2 (en) * | 1997-08-29 | 1999-03-03 | Taisei Chemical Industries Ltd | Process for producing dispersion of functional compound |
| EP0899288A3 (en) * | 1997-08-29 | 2001-03-28 | Taisei Chemical Industries Ltd | Process for producing dispersion of functional compound |
| US7220140B2 (en) | 2005-10-17 | 2007-05-22 | Hosiden Corporation | Board connector |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2626907B2 (en) | 1997-07-02 |
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