JPH0613753B2 - Method for producing solution containing fine metal body used for electroless plating - Google Patents
Method for producing solution containing fine metal body used for electroless platingInfo
- Publication number
- JPH0613753B2 JPH0613753B2 JP63246772A JP24677288A JPH0613753B2 JP H0613753 B2 JPH0613753 B2 JP H0613753B2 JP 63246772 A JP63246772 A JP 63246772A JP 24677288 A JP24677288 A JP 24677288A JP H0613753 B2 JPH0613753 B2 JP H0613753B2
- Authority
- JP
- Japan
- Prior art keywords
- fine metal
- solution containing
- metal body
- solution
- electroless plating
- 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
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
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、ニッケル，コバルト，銅イオン等を利用し
て、無電解メッキに利用される微細な金属体を含む溶液
の製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a solution containing a fine metal body used for electroless plating, using nickel, cobalt, copper ions, or the like. is there.
従来、非導電性物質及び無電解メッキの析出反応が容易
に起こらない被メッキ物に対して、広く用いられている
無電解メッキを行う方法としては被メッキ物を塩化第一
錫の塩酸溶液に浸漬させ、還元力の強い第一錫イオン結
合させ水洗いを行った後に塩化パラジウムの塩酸溶液に
浸漬させ、レドックス反応により被メッキ物表面にパラ
ジウム核を沈着させ、パラジウム核を触媒として、無電
解メッキを行い、メッキ被膜を得る方法はよく知られて
いる。外にもパラジウムやスズコロイドを利用するいく
つかの方法が知られている。Conventionally, as a method for performing electroless plating that has been widely used for a non-conductive substance and an electroless plating deposition reaction that does not easily occur, the stannous chloride hydrochloric acid solution is used as the plating object. Immersion, stannous ion binding with strong reducing power, washing with water, then immersion in hydrochloric acid solution of palladium chloride, redox reaction to deposit palladium nuclei on the surface of the object to be plated, using palladium nuclei as a catalyst for electroless plating It is well known to carry out the above to obtain a plating film. There are also some known methods using palladium or tin colloid.
（公開特許公報昭６１−２０７６６７号，昭６１−１８
６４８０号） しかしながら、これらの方法は貴金属を核として使用す
るために、無電解メッキ液中に被メッキ物から離れた貴
金属触媒が無電解メッキ液の自己分解の大きな要因にな
るという欠点があり、また触媒が貴金属であるために生
産コストに占める、触媒を付与する作業工程上に掛かる
コストの割合が大きい欠点がある。そしてまた、塩化第
一錫塩酸溶液を使用する方法は、酸性や塩酸に弱い被メ
ッキ物に対しては、表面を損傷するという欠点があっ
た。(Japanese Patent Laid-Open Publication Nos. 61-207667 and 61-18
However, since these methods use a noble metal as a nucleus, there is a drawback that the noble metal catalyst separated from the object to be plated in the electroless plating solution becomes a major factor of self-decomposition of the electroless plating solution. In addition, since the catalyst is a noble metal, there is a drawback that the cost of the working process of applying the catalyst is large in the production cost. Further, the method using the stannous chloride solution has a drawback that the surface of the object to be plated, which is weak against acidity or hydrochloric acid, is damaged.
従来における無電解メッキの触媒は、貴金属触媒を利用
するものであるため貴金属触媒の混入による無電解メッ
キ液の自己分解，貴金属触媒の使用による生産コストの
増加及び被メッキ物表面が貴金属触媒を含む酸性水溶液
によって、損傷するという欠点があったが、この発明は
それらの問題を克服し貴金属触媒の代替え品を簡単な操
作で、しかも大量に安価で生産し得て工業的に実施する
のに有利な無電解メッキに利用される触媒の代替え品と
なる微細な金属体を含む溶液の製造を提供しようとする
ものである。Since the conventional electroless plating catalyst utilizes a noble metal catalyst, the electroless plating solution is self-decomposed by the mixture of the noble metal catalyst, the production cost is increased by using the noble metal catalyst, and the surface of the object to be plated contains the noble metal catalyst. Although it has a drawback of being damaged by an acidic aqueous solution, the present invention overcomes those problems and is advantageous in that it can be used as a substitute for a noble metal catalyst in a simple operation and can be mass-produced at low cost, and industrially implemented. An object of the present invention is to provide a solution containing a fine metal body, which is a substitute for a catalyst used for various electroless plating.
上記の目的を達成するために、本発明は無電解メッキに
ついて鋭意研究を重ねた結果、初めて貴金属の触媒を使
用せずに上記の問題点を解決した。In order to achieve the above object, the present invention has conducted intensive studies on electroless plating, and as a result, solved the above problems for the first time without using a precious metal catalyst.
すなわちニッケル，コバルト，銅イオンを還元処理する
ことにより、無電解メッキの触媒代替え品にし得ること
を発見し、この知見を基に本発明をなすに到ったもので
ある。本発明では、ニッケル，コバルト，銅イオンを含
む水溶液を還元剤により還元処理を行い微細な金属体を
生成させた後、これを無電解メッキ触媒の代替え品とし
て使用する。That is, it has been discovered that reduction of nickel, cobalt, and copper ions can be used as a catalyst substitute for electroless plating, and the present invention has been completed based on this finding. In the present invention, an aqueous solution containing nickel, cobalt, and copper ions is subjected to a reduction treatment with a reducing agent to form a fine metal body, which is then used as a substitute for the electroless plating catalyst.
本発明において金属塩水溶液を得るには、水を触媒とし
て水に可溶な金属塩化合物である。In order to obtain an aqueous metal salt solution in the present invention, a metal salt compound that is soluble in water using water as a catalyst is used.
代表的な例として、酢酸ニッケル（II）・４水和物、硫
酸ニッケル（II）アンモニウム・６水和物、炭酸ニッケ
ル（II）・４水和物、塩化ニッケル（II）・６水和物、
硫酸ニッケル（II）・６水和物、酢酸コバルト（II）・
４水和物、コバルト（II）アンモニウム・６水和物、塩
化コバルト（II）・６水和物、硫酸二アンモニウムコバ
ルト（II）・６水和物、りん酸コバルト・８水和物、硫
酸コバルト（II）・７水和物、酢酸銅（II）・１水和
物、塩酸銅（II）・２水和物、塩化二アンモニウム銅
（II）・２水和物、りん酸銅（II）・３水和物、塩化カ
リウム銅（II）・２水和物、硫酸銅（II）・５水和物、
及び塩化ニッケル（II）、硫酸ニッケル（II）、塩化銅
（II）、硫酸銅（II）、塩化コバルト（II）、硫酸コバ
ルト（II）等である。Representative examples are nickel (II) acetate tetrahydrate, nickel (II) sulfate ammonium hexahydrate, nickel (II) carbonate tetrahydrate, nickel (II) chloride hexahydrate. ,
Nickel (II) sulfate hexahydrate, cobalt (II) acetate
Tetrahydrate, Cobalt (II) Ammonium Hexahydrate, Cobalt (II) Chloride Hexahydrate, Diammonium Cobalt (II) Hexahydrate, Cobalt Phosphate Octahydrate, Sulfuric Acid Cobalt (II) heptahydrate, copper (II) acetate monohydrate, copper (II) hydrochloride dihydrate, diammonium copper (II) chloride dihydrate, copper phosphate (II ) ・ Trihydrate, potassium chloride (II) chloride ・ dihydrate, copper (II) sulfate ・ pentahydrate,
And nickel (II) chloride, nickel (II) sulfate, copper (II) chloride, copper (II) sulfate, cobalt (II) chloride, cobalt (II) sulfate and the like.
還元剤として使用される薬品は、水素化ホウ素ナトリウ
ム、水素化ホウ素カリウム、ジメチルアミンボランなど
の使用により還元処理を行う。溶液中の微細な金属体を
分散させるために、還元処理を行う前に金属イオンを含
む水溶液中に分散剤を予め混入し撹拌して置く必要があ
る。The chemical used as the reducing agent is subjected to reduction treatment by using sodium borohydride, potassium borohydride, dimethylamine borane, or the like. In order to disperse the fine metal body in the solution, it is necessary to mix the dispersant in an aqueous solution containing metal ions in advance and to stir it before carrying out the reduction treatment.
分散剤としてはゼラチンを使用し、被メッキ物に応じて
界面活性剤を入れる。ゼラチンを使用する目的は、溶液
中の金属体を均一な分散状態で使用するためである。界
面活性剤の場合は、ゼラチンと同様な均一な分散状態に
する目的の他に、被メッキ物表面の表面張力を低下さ
せ、被メッキ物表面に溶液中の金属体の付着量を増加さ
せる目的を持っている。微細な金属体を含む溶液中に分
散させ被メッキ物に付着が容易に起こるように、分散剤
により水溶液の調整を行う。Gelatin is used as a dispersant, and a surfactant is added depending on the object to be plated. The purpose of using gelatin is to use the metal body in the solution in a uniformly dispersed state. In the case of a surfactant, in addition to the purpose of achieving a uniform dispersed state similar to gelatin, it also lowers the surface tension of the surface of the object to be plated and increases the amount of metal bodies attached to the surface of the object to be plated in the solution. have. The aqueous solution is adjusted with a dispersant so that the fine metal body is dispersed in a solution and easily adheres to the object to be plated.
溶液中に添加される安定剤とは、微細な金属体の溶液を
安定化させる目的で添加される。The stabilizer added to the solution is added for the purpose of stabilizing the solution of the fine metal body.
液中の微細な金属体の溶液を緩やかな還元反応が起こる
状態の雰囲気を与えることで、微細な金属体がイオンに
戻ることを防止する働きを目的として添加される。安定
剤はジメチルアミンボラン、または次亜リン酸ナトリウ
ムを使用し、３〜４０ｇ／の範囲で加えて微細な金属
体の溶液を安定化させる。It is added for the purpose of preventing the fine metal body from returning to ions by providing the atmosphere of the solution of the fine metal body in the liquid in a state where a gradual reduction reaction occurs. Dimethylamine borane or sodium hypophosphite is used as a stabilizer, and is added in a range of 3 to 40 g / to stabilize a solution of fine metal bodies.
微細な金属体を含む溶液を被メッキ物の表面状態によ
り、溶液のpHは＝１〜10の範囲内で変更することも可能
で、例えばプラスチックの種類により、アルカリ性の溶
液に浸漬された場合にプラスチック表面がオーバーエッ
チングされ、このまま用いるとメッキに不適当な表面状
態になり、この場合はpHを変更する必要がある。pHを変
更する場合には、錯化剤を入れた後に、硫酸，塩酸等の
酸性を示す水溶液や水酸化ナトリウム等のアルカリ性を
示す物質を入れて被メッキ物の表面状態を損傷しないよ
うなpHの値に変更して使用する。pHを調整する場合は錯
化剤を入れ水酸化物が出来るのを防止する。Depending on the surface condition of the object to be plated, the solution containing fine metal bodies can be changed to a pH within the range of 1 to 10. For example, when the solution is immersed in an alkaline solution depending on the type of plastic. The plastic surface is over-etched, and if it is used as it is, it will have an unsuitable surface condition for plating. In this case, it is necessary to change the pH. When changing the pH, after adding a complexing agent, add an acidic aqueous solution such as sulfuric acid or hydrochloric acid or an alkaline substance such as sodium hydroxide so that the surface condition of the plated object is not damaged. Change to the value of and use. When adjusting the pH, add a complexing agent to prevent hydroxide formation.
錯化剤は、モノカルボン酸、ジカルボン酸、オキシカル
ボン酸、及びカルボン酸塩類を使用する。代表的な例と
して安息香酸、コハク酸、乳酸、酢酸ナトリウムなどを
10〜50ｇ／入れて水酸化物の生成を錯化剤により生成
しないようにした後にpHの調整を行い使用する。Complexing agents use monocarboxylic acids, dicarboxylic acids, oxycarboxylic acids, and carboxylates. Benzoic acid, succinic acid, lactic acid, sodium acetate, etc. are typical examples.
The amount is adjusted to 10 to 50 g / percent so as to prevent the formation of hydroxide by the complexing agent, and then the pH is adjusted before use.
溶媒としてはイオン交換水または蒸留水を使用する。Ion-exchanged water or distilled water is used as the solvent.
このようにして上記の諸試薬を使用して無電解メッキの
触媒代替え品となる微細な金属体を含む溶液を製造する
ものである。Thus, the above-mentioned reagents are used to produce a solution containing a fine metal body which is a catalyst substitute for electroless plating.
金属塩は５〜50ｇ／の範囲で溶媒中に溶かし、分散剤
は１〜10ｇ／の濃度範囲で溶かし、撹拌しながら金属
イオンを還元処理する。The metal salt is dissolved in the solvent in the range of 5 to 50 g /, the dispersant is dissolved in the concentration range of 1 to 10 g /, and the metal ion is reduced while stirring.
還元剤の濃度は金属イオン濃度、金属塩の種類により多
少異なるが、通常は１〜40ｇ／の範囲内で使用され
る。The concentration of the reducing agent varies somewhat depending on the metal ion concentration and the type of metal salt, but it is usually used within the range of 1 to 40 g /.
上記の手順で製造された、微細な金属体を含む溶液を使
用して非電導性物質及び無電解メッキ被膜の析出が容易
に起こらない被メッキ物に対しては、微細な金属体を含
む溶液中に被メッキ物を浸漬させ、微細な金属体を付着
した後に、被メッキ物表面に付着が十分でない微細な金
属体を水で洗い流して、無電解メッキ液中に浸漬して被
メッキ物表面にメッキ被膜の析出を行うものである。For the object to be plated produced by the above procedure, which does not easily cause the deposition of the non-conductive substance and the electroless plating film using the solution containing the fine metal body, the solution containing the fine metal body After immersing the object to be plated in it and depositing a fine metal body on it, rinse the fine metal body that does not adhere sufficiently to the surface of the object to be plated with water and immerse it in the electroless plating solution to surface the object to be plated. The plating film is deposited on.
本発明の微細な金属体の特徴の一つである、微細な物体
ほど質量当たりの表面積の割合が増加することはよく知
られている事柄である。It is well known that one of the features of the fine metal body of the present invention is that the proportion of the surface area per mass increases as the body becomes finer.
この質量と表面積との関係を利用して、被メッキ物に微
細な金属体を付着させることで、実質はプラスチックな
がらプラスチックの表面は微細な金属体によって覆わ
れ、被メッキ物の表面は一種の金属と同様になり、メッ
キ浴の自己触媒性を利用してメッキの析出反応を起こす
ことにより、通常のパラジウムを使用した触媒効果とは
根本的に異なる作用で被メッキ物に金属メッキ被膜を得
ることが可能である。By utilizing this relationship between the mass and the surface area, by attaching a fine metal body to the object to be plated, the surface of the plastic is covered with a fine metal body, even though it is actually plastic, and the surface of the object to be plated is a kind of It becomes similar to a metal, and by using the autocatalytic property of the plating bath to cause a plating deposition reaction, a metal plating film is obtained on the object to be plated with an action that is fundamentally different from the catalytic effect using ordinary palladium. It is possible.
〔実施例：１〕 硫酸ニッケル・６水和物を30ｇとゼラチン３ｇを蒸留水
１に溶かし、よく撹拌を行いながら水素化ホウ素ナト
リウム25ｇ／を溶かした溶液200mlを前記撹拌してい
る水溶液中に徐々に加えて金属塩の還元処理を行い、還
元処理された微細な金属体を含む溶液中に、次亜リン酸
ナトリウム30ｇを安定剤として入れた後に、硫酸を入れ
てpH＝１に調整した後に、エッチングされたＡＢＳ樹脂
を微細な金属体を含む溶液中に浸漬し、付着させて水洗
いを行い、一般的によく知られている、硫酸ニッケル26
ｇ／，酢酸ナトリウム26ｇ／，クエン酸ナトリウム
15ｇ／，次亜リン酸ナトリウム16ｇ／，チオ尿素３
ppm、温度90℃・pH＝5.0の組成条件で無電解ニッケルメ
ッキ液中に浸漬し、ＡＢＳ樹脂表面にニッケルメッキ被
膜の析出を行う。１時間無電解ニッケルメッキ液中に浸
漬したところ、約17μのニッケルメッキ被膜を得ること
ができた。[Example 1] 30 g of nickel sulfate hexahydrate and 3 g of gelatin are dissolved in distilled water 1, and 200 ml of a solution in which 25 g / sodium borohydride is dissolved while stirring well is added to the stirring aqueous solution. The metal salt was gradually added to carry out a reduction treatment, and 30 g of sodium hypophosphite was added as a stabilizer to a solution containing fine metal bodies subjected to the reduction treatment, and then sulfuric acid was added to adjust the pH to 1. After that, the etched ABS resin is dipped in a solution containing a fine metal body, adhered and washed with water, and nickel sulfate 26, which is generally well known, is used.
g /, sodium acetate 26g /, sodium citrate
15g /, sodium hypophosphite 16g /, thiourea 3
It is immersed in an electroless nickel plating solution under the composition conditions of ppm, temperature 90 ° C. and pH = 5.0 to deposit a nickel plating film on the ABS resin surface. When immersed in an electroless nickel plating solution for 1 hour, a nickel plating film of about 17 μm could be obtained.
〔実施例：２〕 塩化ニッケル・６水和物10ｇとゼラチン１ｇを蒸留水１
に溶かし、十分に撹拌を行いながら、水素化ホウ素ナ
トリウム30ｇ／を溶かした液100mlを、撹拌されてい
る前記水溶液中へ徐々に加えて還元処理を行い、微細な
金属体を含む溶液を製造した後に安定剤を加えて、前記
の実施例１と同様にエッチングされたＡＢＳ樹脂を用い
てニッケルメッキを行った。[Example: 2] 10 g of nickel chloride hexahydrate and 1 g of gelatin were added to distilled water 1
100 g of a solution of sodium borohydride (30 g / mol) was gradually added to the stirred aqueous solution to carry out a reduction treatment to prepare a solution containing fine metal bodies. After that, a stabilizer was added, and nickel plating was performed using the ABS resin etched as in Example 1 above.
〔実施例：３〕 硫酸コバルト（II）・７水和物20ｇとゼラチン５ｇを、
蒸留水１に溶かし、よく撹拌を行いながら水素化ホウ
素ナトリウム40ｇ／をとかした液100mlを撹拌されて
いる前記の水溶液中へ徐々に加えて還元処理を行い、微
細な金属体を含む溶液を製造した後に、次亜リン酸ナト
リウム30ｇ、錯化剤として酢酸ナトリウムを20ｇを溶か
し、微細な金属体を含む溶液に入れた後、水酸化ナトリ
ウムによりpH＝10.に調整する。[Example: 3] 20 g of cobalt (II) sulfate heptahydrate and 5 g of gelatin,
Dissolve in distilled water 1 and add 100 ml of a solution containing 40 g / sodium borohydride while stirring well to the above stirred aqueous solution to carry out a reduction treatment to produce a solution containing fine metal bodies. After that, 30 g of sodium hypophosphite and 20 g of sodium acetate as a complexing agent are dissolved and put in a solution containing fine metal bodies, and then adjusted to pH = 10 with sodium hydroxide.
エッチングされたＡＢＳ樹脂を微細な金属体を含む溶液
中に浸漬して、ＡＢＳ樹脂表面に付着させ水洗いした後
に無電解コバルトメッキ浴中にてコバルトメッキ被膜を
得ることができる。The etched ABS resin can be immersed in a solution containing a fine metal body, adhered to the surface of the ABS resin and washed with water, and then a cobalt plating film can be obtained in an electroless cobalt plating bath.
コバルトメッキ浴の組成は硫酸コバルト・７水和物20ｇ
／、次亜リン酸ナトリウム21ｇ／、酒石酸ナトリウ
ム115ｇ／、ほう酸30ｇ／、pH＝9.0温度90℃の浴組
成でメッキを行った。１時間の無電解コバルトメッキ液
に浸漬したところ、13μのコバルトメッキ被膜を得るこ
とができた。The composition of the cobalt plating bath is 20 g of cobalt sulfate heptahydrate.
/, Sodium hypophosphite 21 g /, sodium tartrate 115 g /, boric acid 30 g /, pH = 9.0. When immersed in an electroless cobalt plating solution for 1 hour, a 13 μ cobalt plating film could be obtained.
〔実施例：４〕 硫酸銅（II）・２水和物を15ｇとゼラチン１ｇを蒸留水
１に溶かし撹拌しながら、水素化ホウ素ナトリウム10
ｇ／を溶かした400mlの水溶液を、前記撹拌されてい
る水溶液へ徐々に加えて還元処理を行い、微細な金属体
を製造する。製造された微細な金属体を含む溶液の安定
剤として次亜リン酸ナトリウム30ｇを入れて、エッチン
グされたＡＢＳ樹脂を微細な金属体溶液中に浸漬して水
洗いを行い、ＡＢＳ樹脂表面に付着させて無電解銅メッ
キ液中にて銅メッキ被膜を得た。[Example 4] 15 g of copper (II) sulfate dihydrate and 1 g of gelatin were dissolved in 1 of distilled water and stirred while stirring with sodium borohydride 10
A 400 ml aqueous solution in which g / is dissolved is gradually added to the stirred aqueous solution to carry out a reduction treatment to produce a fine metal body. 30 g of sodium hypophosphite was added as a stabilizer for the solution containing the produced fine metal body, and the etched ABS resin was immersed in the fine metal body solution and washed with water to adhere to the ABS resin surface. To obtain a copper plating film in an electroless copper plating solution.
無電解銅メッキ液の組成は、硫酸銅10ｇ／、エチレン
ジアミン４酢酸２ナトリウム30ｇ／、ホルムアルデヒ
ド（37％）、３ml／、ビピリジル若干、ポリエチレン
グリコール若干、pH＝12.2、温度70℃の浴組成を使用し
た。The composition of the electroless copper plating solution is a bath composition of copper sulfate 10 g /, ethylenediamine tetraacetic acid disodium 30 g /, formaldehyde (37%), 3 ml /, bipyridyl, a little polyethylene glycol, pH = 12.2, and a temperature of 70 ° C. did.
１時間にわたり無電解銅メッキ液に浸漬したところ、2.
2μの銅メッキ被膜を得ることができた。When immersed in electroless copper plating solution for 1 hour, 2.
It was possible to obtain a copper plating film of 2μ.
本発明は、以上説明したように構成されているので、以
下記述のような幾多の効果を奏する。Since the present invention is configured as described above, it has various effects as described below.
本発明方法に従うと、非導電性物質及び無電解メッキの
析出反応が容易に起こらない被メッキ物に対し無電解メ
ッキ浴の種類と同じ金属の微細な金属体を含む溶液を用
いることができ、無電解メッキ浴中に不要な異種金属の
混入を防ぐことができて無電解メッキ液の自己分解の危
険性を少なくすることができる。また従来の錫・パラジ
ウム触媒を使用するのに比べて約30％近く安い費用で製
造することができる。さらに実用上最大な問題であった
溶液中における微細な金属体の安定化の条件も、次亜リ
ン酸ナトリウムやジメチルアミンボランを調整しながら
添加することによって、微細な金属体を含む溶液が安定
な状態で利用できる。なお通常行われる貴金属触媒の回
収や錫を含む塩酸水溶液の使用がないため、作業工程の
簡略化などにより、製品価格を低減する効果は大きく、
貴金属触媒を使用しないため生産コストを抑えて、容易
に金属塩濃度を増加させ、被メッキ物表面に付着する微
細な金属体を増加させることにより、析出速度を早める
ことが可能で析出されたメッキ被膜の密着力においても
従来の触媒と比較して勝るとも劣ることはない。According to the method of the present invention, a solution containing a fine metal body of the same metal as the type of the electroless plating bath can be used for the non-conductive substance and the object to be plated in which the deposition reaction of the electroless plating does not easily occur, Unwanted dissimilar metals can be prevented from mixing in the electroless plating bath, and the risk of self-decomposition of the electroless plating solution can be reduced. It can also be manufactured at a cost that is about 30% cheaper than using conventional tin-palladium catalysts. Furthermore, regarding the conditions for stabilizing the fine metal body in the solution, which was the biggest problem in practical use, the solution containing the fine metal body was stabilized by adding sodium hypophosphite and dimethylamine borane while adjusting. It can be used in any condition. In addition, since there is no recovery of precious metal catalysts or the use of aqueous hydrochloric acid containing tin, which is usually done, the effect of reducing the product price by simplifying the work process is great,
Since no precious metal catalyst is used, the production cost can be suppressed, the metal salt concentration can be easily increased, and the fine metal particles that adhere to the surface of the object to be plated can be increased to speed up the deposition rate. The coating adhesion is not inferior to conventional catalysts.
実施例中の無電解メッキ浴の組成と微細な金属体を含む
溶液を得る組成はほぼ同じであるから、メッキ作業工程
上で生ずる各種メッキ廃液の利用において、同様の触媒
を得ることは困難でない。Since the composition of the electroless plating bath and the composition for obtaining a solution containing a fine metal body in the examples are almost the same, it is not difficult to obtain a similar catalyst in the use of various plating waste liquids generated in the plating operation process. .
資源の有効利用からも効果が期待できる。Effects can be expected from the effective use of resources.
Claims (6)
り還元処理した後に安定剤を入れるとともに、pHをアル
カリ側に調整する場合は錯化剤を入れることを特徴とす
る、無電解メッキに使用する微細な金属体を含む溶液の
製造方法。1. A complexing agent when a dispersant is put in an aqueous solution containing nickel ions, cobalt ions, or copper ions, reduced by a reducing agent, and then a stabilizer is added, and the pH is adjusted to an alkaline side. A method for producing a solution containing a fine metal body used in electroless plating, which comprises:
る特許請求の範囲第１項記載の方法。2. The method according to claim 1, wherein the dispersant is gelatin or a surfactant.
酸、オキシカルボン酸またはカルボン酸塩類である特許
請求の範囲第１項記載の方法。3. The method according to claim 1, wherein the complexing agent is a monocarboxylic acid, a dicarboxylic acid, an oxycarboxylic acid or a carboxylic acid salt.
化ホウ素カリウムまたはジメチルアミンボランである特
許請求の範囲第１項記載の方法。4. The method according to claim 1, wherein the reducing agent is sodium borohydride, potassium borohydride or dimethylamine borane.
メチルアミンボランである特許請求の範囲第１項記載の
方法。5. The method according to claim 1, wherein the stabilizer is sodium hypophosphite or dimethylamine borane.
面状態により、pH＝１〜１０に調整する特許請求の範囲
第１項記載の方法。6. The method according to claim 1, wherein the pH of the solution containing the fine metal body is adjusted to 1 to 10 depending on the surface condition of the object to be plated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63246772A JPH0613753B2 (en) | 1988-09-29 | 1988-09-29 | Method for producing solution containing fine metal body used for electroless plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63246772A JPH0613753B2 (en) | 1988-09-29 | 1988-09-29 | Method for producing solution containing fine metal body used for electroless plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0293076A JPH0293076A (en) | 1990-04-03 |
| JPH0613753B2 true JPH0613753B2 (en) | 1994-02-23 |
Family
ID=17153437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63246772A Expired - Lifetime JPH0613753B2 (en) | 1988-09-29 | 1988-09-29 | Method for producing solution containing fine metal body used for electroless plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613753B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827753A (en) * | 1994-07-20 | 1996-01-30 | East Japan Railway Co | Removal and collection device of chewing gum attached to floor surface |
| JP2975860B2 (en) * | 1995-02-03 | 1999-11-10 | 株式会社スイデン | Chewing gum peeler in chewing gum suction vacuum cleaner |
| WO2013118600A1 (en) * | 2012-02-08 | 2013-08-15 | 石原薬品株式会社 | Pretreatment solution for electroless nickel plating or electroless nickel alloy plating, and plating method |
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|---|---|---|---|---|
| JP3361717B2 (en) * | 1997-04-17 | 2003-01-07 | 株式会社日立製作所 | Method for forming electrode of semiconductor device |
| PT878235E (en) * | 1997-05-05 | 2007-01-31 | Akzo Nobel Nv | Method of producing a catalyst by electroless deposition of the active metal on the support |
| JP3393190B2 (en) * | 1999-02-22 | 2003-04-07 | 有限会社関東学院大学表面工学研究所 | Method for selectively activating copper pattern and activator used therefor |
| JP6201153B2 (en) * | 2014-09-11 | 2017-09-27 | 石原ケミカル株式会社 | Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method |
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| JP6268379B2 (en) * | 2016-07-08 | 2018-01-31 | 石原ケミカル株式会社 | Nickel colloidal catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method |
| JP6343787B1 (en) | 2017-06-01 | 2018-06-20 | 石原ケミカル株式会社 | Copper colloid catalyst solution for electroless copper plating and electroless copper plating method |
| JP6943050B2 (en) * | 2017-07-18 | 2021-09-29 | Dic株式会社 | Metal nanoparticle water dispersion |
| JP6858425B1 (en) * | 2020-06-24 | 2021-04-14 | 石原ケミカル株式会社 | Nickel colloid catalyst solution for electroless nickel or nickel alloy plating and electroless nickel or nickel alloy plating method |
| JP6950051B1 (en) * | 2020-07-22 | 2021-10-13 | 上村工業株式会社 | An electroless Ni-P plating catalyst solution and a method for forming an electroless Ni-P plating film using the catalyst solution. |
| KR20230101816A (en) * | 2020-11-05 | 2023-07-06 | 디아이씨 가부시끼가이샤 | Method of forming metal film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0639714B2 (en) * | 1985-12-23 | 1994-05-25 | 太陽誘電株式会社 | Chemical copper plating solution |
| JPS6333577A (en) * | 1986-07-28 | 1988-02-13 | Hitachi Condenser Co Ltd | Electroless plating solution |
-
1988
- 1988-09-29 JP JP63246772A patent/JPH0613753B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0827753A (en) * | 1994-07-20 | 1996-01-30 | East Japan Railway Co | Removal and collection device of chewing gum attached to floor surface |
| JP2975860B2 (en) * | 1995-02-03 | 1999-11-10 | 株式会社スイデン | Chewing gum peeler in chewing gum suction vacuum cleaner |
| WO2013118600A1 (en) * | 2012-02-08 | 2013-08-15 | 石原薬品株式会社 | Pretreatment solution for electroless nickel plating or electroless nickel alloy plating, and plating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0293076A (en) | 1990-04-03 |
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