JPS5980764A - Electroless plating bath for plating platinum or platinum-palladium alloy - Google Patents
Electroless plating bath for plating platinum or platinum-palladium alloyInfo
- Publication number
- JPS5980764A JPS5980764A JP19058782A JP19058782A JPS5980764A JP S5980764 A JPS5980764 A JP S5980764A JP 19058782 A JP19058782 A JP 19058782A JP 19058782 A JP19058782 A JP 19058782A JP S5980764 A JPS5980764 A JP S5980764A
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- plating
- bath
- salt
- 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.)
- Granted
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
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
Description
【発明の詳細な説明】
本発明は、金属又は非金属表面に白金又は白金−パラジ
ウム合金を無電解メッキするためのヒドラジン型メッキ
浴に関し、特に浴液の安定性が優れ１、白金又は白金−
パラジウム合金の利用率が高く且つ操作温度が低い新規
なメッキ浴に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrazine type plating bath for electroless plating of platinum or platinum-palladium alloy onto metal or non-metallic surfaces, and in particular has excellent bath liquid stability.
This invention relates to a new plating bath that has a high palladium alloy utilization rate and a low operating temperature.
白金の無電解メッキに関する公知文献は少ない。There are few known documents regarding electroless plating of platinum.
一般に行われる無電解メッキ法から類推するならば、白
金塩類とヒドラジン、水素化ホウ素塩、アルキルアミン
ボラン、次亜リン酸塩、ホルマリン等から選択される還
元剤とからなる浴液が考えられる。By analogy with commonly used electroless plating methods, a bath solution consisting of platinum salts and a reducing agent selected from hydrazine, borohydride salts, alkylamine borane, hypophosphite, formalin, etc. can be considered.
しかし、白金イオンの還元は他金属の場合に比べて比較
的速かに進むために浴液の安定性が悪い。However, since the reduction of platinum ions proceeds relatively quickly compared to the case of other metals, the stability of the bath solution is poor.
このため、上記のいずれの組み合わせにおいても、被メ
ツキ体表面に選択的にメッキ層を成長させることが困難
であると思われる。For this reason, in any of the above combinations, it seems difficult to selectively grow a plating layer on the surface of the object to be plated.
例えば、上記の還元剤の内で、水素化ホウ素塩は還元力
が強過ぎるため白金の還元が進み過ぎて浴中に析出（即
ち自己分解）してしまうので、反応抑制のための安定化
剤を加える必要があるが、この場合の適当な安定化剤は
見当らない。また、アルキルアミンボラン型の浴液は確
かに安定であり自己分解が少ないが、還元温度が高＜７
０〜８０℃で遂行される。このため、適用可能なプラス
チツクスの範囲が狭く、また高温によるアンモニアの蒸
発量が多くて操業面からも好ましくないという欠点があ
る。また、次亜リン酸塩及びホルマリンについては、還
元力が弱いため高温で行なう必要があるが、高温にした
場合は自己分解が激しく、この自己分解を抑える安定化
剤も見当らない。しかしながら、還元剤としてヒドラジ
ンを用いる場合については、従来他の金属のメッキに用
いられている浴液をそのまま白金に適用することは、浴
液の安定性が極めて悪いため不可能であるが、白金イオ
ンの形態、安定化剤等を選択することにより、浴液の安
定性を改善出来る可能性があると思われる。For example, among the above-mentioned reducing agents, boron hydride has too strong a reducing power, so the reduction of platinum progresses too much and precipitates in the bath (i.e., self-decomposes). However, no suitable stabilizer has been found in this case. In addition, alkylaminoborane type bath liquids are certainly stable and have little self-decomposition, but the reduction temperature is high <7
It is carried out at 0-80°C. For this reason, the range of applicable plastics is narrow, and the amount of ammonia evaporated due to high temperatures is large, which is unfavorable from an operational standpoint. Furthermore, hypophosphite and formalin have weak reducing power, so it is necessary to carry out the process at high temperature, but when the temperature is high, self-decomposition is severe, and no stabilizer has been found to suppress this self-decomposition. However, when using hydrazine as a reducing agent, it is impossible to directly apply the bath solution conventionally used for plating other metals to platinum because the stability of the bath solution is extremely poor. It seems possible to improve the stability of the bath solution by selecting the ion form, stabilizer, etc.
本発明者は、白金のヒドラジン型浴肢の安定性を改善す
るため、種々の白金イオン細体及び共存安定化剤につい
て蜆意研究した結果、特に白金をニトロ錯塩又はニトロ
アンミン錯塩として用い且つ安定化剤としてヒドロキシ
ルアミン塩を使用した場合には、浴液の安定性が著しく
向上すること、この場合選択析出性が著しく高められ、
白金の利用率が９５％以上であり極めて高く且つメッキ
温度は６０℃以下の低温で出来ること及びホウ素塩を含
まないためメッキ層が硬化することなく接着強度が大き
いこと、更に上起白金的塩と、パラジウムのニトロ錯塩
又はニトロアンミン錯塩とを同時に用いた場合には白金
−パラジウム合金が同様にメッキ出来ることを見出し、
本発明を完成するに至った。In order to improve the stability of platinum hydrazine-type baths, the present inventor conducted research on various platinum ion particles and coexisting stabilizers. When a hydroxylamine salt is used as a curing agent, the stability of the bath solution is significantly improved, and in this case, the selective precipitation property is significantly improved.
The platinum utilization rate is over 95%, which is extremely high, and plating can be done at a low temperature of 60°C or less, and since it does not contain boron salt, the plating layer does not harden and has high adhesive strength. It was discovered that a platinum-palladium alloy can be plated in the same way when a nitro complex salt or a nitroammine complex salt of palladium is used at the same time.
The present invention has now been completed.
即ち本発明は、（ａ）白金のニトロ錯塩若しくは（及び
）ニトロアンミン錯塩又はこれ（これら）とパラジウム
のニトロ錯塩若しくは（及び）ニトロアンミン錯塩、（
ｂ）ヒドロキシルアミン塩、並びに（Ｃ）ヒドラジンを
含有し、ｐＨ１０〜１Ｂであることを特徴とする白金又
は白金−パラジウム合金の無電解メッキ浴に係る。That is, the present invention provides (a) a nitro complex salt of platinum or (and) a nitro ammine complex salt, or a nitro complex salt or (and) a nitro ammine complex salt of platinum and (these), (
The present invention relates to an electroless plating bath for platinum or platinum-palladium alloy, which contains b) a hydroxylamine salt and (C) hydrazine, and has a pH of 10 to 1B.
本発明にかける白金ニトロ錯塩又は白金ニトロアンミン
錯塩としては、例えばに２ （Ｐｔ（ＮＯ２） ４）、
Ｎａ２ 〔ＰｔｒＮＯ２）４〕、（ＮＨｓ）２Ｐｔ（Ｎ
Ｏ２）ｚ等の結晶をアンモニア水に溶解して使用するか
、又は白金のアンミン錯塩若しくはクロロアンミン錯塩
の溶液に亜硝酸のアルカリ金属塩等の塩をアンモニア水
中で反応させて得たものを使用する。しかし、浴液中の
共存イオンがメッキ条件番と影響を与えることが多いの
で、メッキの品質管理の面から考えると、できるだけ純
結晶を用いるのが好ましい。Examples of platinum nitro complex salts or platinum nitroamine complex salts used in the present invention include 2 (Pt(NO2) 4),
Na2 [PtrNO2)4], (NHs)2Pt(N
Use crystals such as O2)z dissolved in ammonia water, or use a solution obtained by reacting a solution of platinum ammine complex salt or chloroammine complex salt with a salt such as an alkali metal salt of nitrous acid in ammonia water. do. However, coexisting ions in the bath solution often affect the plating conditions, so from the viewpoint of quality control of plating, it is preferable to use as pure a crystal as possible.
結晶を用いる場合は、通常１種を用いるが、２種以上を
用いても差し支えない。When using crystals, one type is usually used, but two or more types may be used.
白金−パラジウム合金をメッキする場合には、上記白金
錯塩とパラジウムニトロ錯塩又は（及び）パラジウムニ
トロアンミン錯塩の結晶とをアンモニア水に溶解して用
いるか、又は白金のアンミン錯塩若しくはクロロアンミ
ン錯塩とパラジウムのアンミン錯塩若しくはクロロアン
ミン錯塩の溶液に亜硝酸塩をアンモニア水中で反応させ
て得たものを用いる。上記パラジウム錯塩としては、例
えばに２ ［Ｐｄ（ＮＯ２’４〕、Ｎａ２１ＴＰｄ（Ｎ
Ｏ２）４ ］、（ＮＨ３）２Ｐｄ（ＮＯｚ）ｚ等の結晶
を挙げることが出来る。結晶を用いる場合は、これらの
少くとも１種を用いる１、白金−パラジウム合金をメッ
キする際の白金とパラジウムとの金属としてのモル比は
、通常白金１モルに対してパラジウム０．１〜１．５モ
ル程度である。When plating a platinum-palladium alloy, the above-mentioned platinum complex salt and palladium nitro complex salt or (and) crystals of palladium nitroammine complex salt are dissolved in aqueous ammonia, or the platinum ammine complex salt or chloroammine complex salt and palladium are used. A solution obtained by reacting a solution of ammine complex salt or chloroammine complex salt with nitrite in aqueous ammonia is used. Examples of the palladium complex salts include 2[Pd(NO2'4], Na21TPd(N
Examples include crystals such as O2)4], (NH3)2Pd(NOz)z, and the like. When using crystals, use at least one of these 1. When plating a platinum-palladium alloy, the molar ratio of platinum and palladium as metals is usually 0.1 to 1 mole of palladium to 1 mole of platinum. It is about .5 mol.
本発明において使用するヒドロキシルアミン塩としては
、水溶性の塩例えば塩酸塩、硫酸塩、硝酸塩等が好まし
い。As the hydroxylamine salt used in the present invention, water-soluble salts such as hydrochloride, sulfate, nitrate, etc. are preferable.
本発明におけるヒドラジンとしては、水溶液の状態でヒ
ドラジンとなるもの、例えばヒドラジンの水和物、塩酸
塩、硫酸塩等が好適に使用できる。As the hydrazine in the present invention, hydrazine that becomes hydrazine in an aqueous solution state, such as hydrazine hydrate, hydrochloride, sulfate, etc., can be suitably used.
本発明の浴液組成としては、白金又は白金−パラジウＡ
（７）濃度力５ Ｘ １０−’−５Ｘ １０−２Ｍ／１
（白Ｍ（７）場合、０．１〜Ｉ Ｏ？／ｅ＞好ｉ）：
ｔ、 ＜ ハ２．５Ｘ１０−３〜２．５ｘｌＯＭ／ｌ
（白金の場合、ｏ、５〜６ｙ／ｌ）、ヒドロキシルアミ
ンか０．００１４〜０．７ Ｍ／ｌ （堝酸塩の場合、
０．１〜５０ ｆ’／ｌ ）好ましくは０．００１４〜
０．０１４Ｍ＃ （塩酸塩の場合、０．１・−１ｆ／ｌ
ｌ及びヒドラジンをｏ、ｏ ｏ ａ〜１．５ Ｍ／ｌ
（−水和物の場合、０．１５〜７６ｙ／ｌ）好ましく
は０．００８ ＝ ０．８ ｈ、Ｖｌ（−水和物の場合
、０．１５へ−１５ｙ／ｌ ）である。本発明において
は上記組成の浴液を、アンモニア水又はアルカリ性 Ｈ
緩衝液により、ｐＨ１０〜１８好ましくは１１・〜１２
の範囲に調製して使用する。The bath liquid composition of the present invention includes platinum or platinum-palladium A.
(7) Concentration force 5 X 10-'-5X 10-2M/1
(For white M(7), 0.1~I O?/e>favorable i):
t, < Ha2.5X10-3~2.5xlOM/l
(for platinum, o, 5-6y/l), hydroxylamine or 0.0014-0.7 M/l (for borate,
0.1-50 f'/l) Preferably 0.0014-
0.014M# (for hydrochloride, 0.1・-1f/l
l and hydrazine at o, o o a~1.5 M/l
(-0.15 to 76 y/l in case of hydrate) Preferably 0.008 = 0.8 h, Vl (-0.15 to -15 y/l in case of hydrate). In the present invention, the bath solution having the above composition is aqueous ammonia or alkaline H
Depending on the buffer, pH 10-18 preferably 11-12
Prepare and use within the following range.
ｐＨが１８以上になると還元速度が速くなり自己分解し
易くなる。またｐＨが１０より低いと還元速度が小さく
なりメッキ時間が長くなる。ヒドロキシルアミンが０．
００１５Ｍ／ｌ 未満になると浴液の安定性が悪くなり
、また０、７ Ｍ／Ａ’ を越えるとメッキ層の成長
を極端に抑えるので好ましくない０
斯くして作成された本発明メッキ浴に、予め活性化処理
を経た被メッキ体を浸漬すると、室温〜６０℃程度好ま
しくは８０〜６０℃の温度で、接触的に還元反応が進行
し、良質の白金又は白金−パラジウム合金メッキ層が成
長する。メッキ温度が室温より低いとメッキが進行しに
くくなる。）また、メッキ温度が６０℃を越えると自己
分解が起こり始める。上記温度範囲内ではメッキは良好
に進行し、その際の浴液中の白金又は白金−パラジウム
の反応率は９５〜９８％に達し、浴液中での自己分解あ
るいは反応容器壁への析出は全く起らない。メッキ時間
は被メッキ体の形状にもよるので一定ではないが、例え
ば約２μｍの白金メッキ層を得る場合の例を述べれば１
．６〜２時間という短時間である。When the pH is 18 or higher, the reduction rate becomes faster and self-decomposition becomes easier. Furthermore, if the pH is lower than 10, the reduction rate will be low and the plating time will be long. Hydroxylamine is 0.
If it is less than 0.015 M/l, the stability of the bath solution will deteriorate, and if it exceeds 0.7 M/A', the growth of the plating layer will be extremely suppressed, which is undesirable. When the object to be plated that has been previously activated is immersed, a reduction reaction proceeds catalytically at a temperature of room temperature to 60°C, preferably 80 to 60°C, and a high-quality platinum or platinum-palladium alloy plating layer grows. . If the plating temperature is lower than room temperature, plating will be difficult to proceed. ) Furthermore, when the plating temperature exceeds 60°C, self-decomposition begins to occur. Within the above temperature range, plating progresses well, and the reaction rate of platinum or platinum-palladium in the bath solution reaches 95-98%, and there is no self-decomposition in the bath solution or precipitation on the walls of the reaction vessel. It doesn't happen at all. The plating time is not constant as it depends on the shape of the object to be plated, but to give an example of obtaining a platinum plating layer of approximately 2 μm, it is 1
．． It is a short time of 6 to 2 hours.
本発明のメッキ浴においては、前記白金錯塩自体が著し
く安定であり（前記パラジウム錯塩も同様）、ヒドロキ
シルアミン塩が加わるとさらに安定な錯体を形成し自己
分解はほとんど抑えられる。In the plating bath of the present invention, the platinum complex salt itself is extremely stable (the same goes for the palladium complex salt), and when a hydroxylamine salt is added, an even more stable complex is formed, and self-decomposition is almost suppressed.
このため本発明メッキ浴は、被メッキ体が浸漬されない
場合には長時間にわたって自己分解することなく極めて
優れた安定性を有する。Therefore, the plating bath of the present invention has extremely excellent stability without self-decomposition over a long period of time when the object to be plated is not immersed.
本発明メッキ浴が適用できる対象としては、金属、例え
ば銅、ニッケル、鉄、それらの合金、チタン、タンタル
等の電子部品あるいは電極材料等の工業材料等が挙げら
れる。また、アクリロニトリル−ブタジェン−スチレン
共電合体（ＡＢＳ）樹脂、ポリアミド樹脂、カーボネー
ト樹脂等の合成樹脂、ガラス、セラミックス等、通゛ｌ
ドの無電解メッキが可能な材質に対して適用できる。Examples of objects to which the plating bath of the present invention can be applied include metals such as copper, nickel, iron, alloys thereof, electronic parts such as titanium and tantalum, and industrial materials such as electrode materials. In addition, synthetic resins such as acrylonitrile-butadiene-styrene coelectrolyte (ABS) resin, polyamide resin, carbonate resin, glass, ceramics, etc.
It can be applied to materials that can be electrolessly plated.
また、カチオン交換膜に白金を接合して使用される水素
あるいは酸素製造水電解槽のユニットセルの製造に応用
できる。本発明メッキ浴はこの種の接合体の製造におい
て、従来のアルキルアミンボラン型のメッキ浴に比べて
腺の汚染が少ない点でより優れている。It can also be applied to the production of unit cells for hydrogen or oxygen producing water electrolyzers, which are used by bonding platinum to a cation exchange membrane. The plating bath of the present invention is superior to conventional alkylamine borane type plating baths in producing less gland contamination in the production of this type of bonded body.
いずれの場合も、被メッキ体については予め活性化処理
を行っておくのが好ましい。In either case, it is preferable that the object to be plated be subjected to an activation treatment in advance.
金属の場合は、表面清浄後、パラジウム、白金、ロジウ
ム等の塩類水溶故に浸漬し、必要ならば引続き水素化ホ
ウ素塩水溶液等に浸漬還元処理して活性化した後、本発
明メッキ浴に浸漬する。In the case of metal, after surface cleaning, it is immersed in an aqueous salt solution such as palladium, platinum, rhodium, etc., and if necessary, it is subsequently immersed in an aqueous boron hydride salt solution, etc. for reduction treatment and activated, and then immersed in the plating bath of the present invention. .
高分子材料、ガラス、セラミックスの場合にも、通常、
これらの表面に銅、ニッケル等の化学メッキを行なう場
合に利用されている表面親水化、増感処理、活性化処理
を行った後、本発明メッキ浴に浸漬する。Also in the case of polymeric materials, glasses, and ceramics, usually
These surfaces are subjected to surface hydrophilic treatment, sensitization treatment, and activation treatment that are used when chemically plating copper, nickel, etc., and then immersed in the plating bath of the present invention.
また、イオン交換膜の場合は、表面粗化、清浄処理をし
た後、膜の極性に応じてアニオン性又はカチオン性の白
金錨イオンを吸着させ、ついで水素化ホウ素ナトリウム
溶液等で還元して０．５〜２μｍ程度の第一層を接合し
た後、本発明メッキ浴素塩、ジメチルアミンボラン等を
用いて析出させた白金又は白金−パラジウム合金に比べ
て、ホウ素を含まないため暴と硬度が低く柔軟性に富み
接合強度が大きい。このため電極材料等のメッキに適し
ている。また、膜−電極接合体の場合のような柔軟性基
体へのメッキにも適している。In addition, in the case of ion exchange membranes, after surface roughening and cleaning treatment, anionic or cationic platinum anchor ions are adsorbed depending on the polarity of the membrane, and then reduced to zero with sodium borohydride solution, etc. After bonding the first layer with a thickness of approximately 5 to 2 μm, the hardness is significantly lower because it does not contain boron, compared to platinum or platinum-palladium alloy deposited using the plating bath salt of the present invention, dimethylamine borane, etc. It is low, highly flexible, and has high bonding strength. Therefore, it is suitable for plating electrode materials, etc. It is also suitable for plating flexible substrates such as membrane-electrode assemblies.
本発明メッキ浴は、白金又は白金−パラジウム合金のメ
ッキの他に、白金やパラジウムと同様に安定なニトロ６
１又はニトロアンミン鉛塩を作るイリジウム、ロジウム
等の金属単独又は白金との合金のメッキにも応用するこ
とが出来る。The plating bath of the present invention can be used for plating platinum or platinum-palladium alloy as well as nitro-6, which is stable like platinum and palladium.
It can also be applied to plating metals such as iridium, rhodium, etc. alone or alloys with platinum, which produce 1 or nitroammine lead salts.
以下、実施例を挙げて本発明を更に具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
過フルオロカーボンスルホン酸型のカチオン交換膜〔デ
ュポン社製、［ナフィオン１１７Ｊ、ｌ１ｆｉ厚７ミル
（約０．１７５ ｍｍ）：）を用い、直径約３９ ｍｍ
円形部分に白金を接合した。Example 1 A perfluorocarbon sulfonic acid type cation exchange membrane [manufactured by DuPont, [Nafion 117J, 11fi thickness 7 mil (about 0.175 mm)] was used, and the diameter was about 39 mm.
Platinum was bonded to the circular part.
膜の前処理には、まず、サンドブラスト粗化を行い、続
いて４Ｎ−ＨＣノで煮沸して清浄化後、熱水洗滌した。For pretreatment of the membrane, first, it was roughened by sandblasting, then boiled with 4N-HC to clean it, and then washed with hot water.
処理膜をメッキ用セルに挾み、膜の両側にアンモニア水
中で四塩化白金を煮沸して得た白金アンミン錯塩溶液（
白金５０ Ｉｎｙ／ ｌ ＯＯｍ、ｄ）を入れ、室温２
時間浸漬した。水洗後、同セルにｐＨ１２の水素化ホウ
素すｌラム０．０５％溶液を加え、４０〜６０℃で２時
間還元して約１μｍ厚の白金層を膜の両表面に析出させ
た。The treated membrane was placed in a plating cell, and a platinum ammine complex salt solution (obtained by boiling platinum tetrachloride in aqueous ammonia) was placed on both sides of the membrane.
Add platinum 50 Iny/l OOm, d) and leave at room temperature 2
Soaked for an hour. After washing with water, a 0.05% sulfur borohydride solution with a pH of 12 was added to the cell, and reduction was carried out at 40 to 60° C. for 2 hours to deposit a platinum layer with a thickness of about 1 μm on both surfaces of the membrane.
この活性化膜を下記組成の化学メッキ浴に浸漬した。This activated film was immersed in a chemical plating bath having the following composition.
（ｌ ジニトロジアンミン白金 ０．５ｙ（
２） アンモニア水（２８％） ５０ｎ＋
６！（３）水 ２５ Ｑ ｍｌ（４）
ヒドロキシルアミンｔＭ！ｉ２ＬＭ５０％水溶液
ＩＱｎｌｌ（５） ヒドラジン−水和
物（ヒド
ラジンとして８０％） ５ ｍｅ（６）
水 全社４００ｍ１（７
） ｐＨ１１，７
浴液はｆｌ） （２１＋３１を加温溶解して溶液とし、
ついで＋４） （５） ｔｅｌを加えて調製した。(l dinitrodiammine platinum 0.5y(
2) Ammonia water (28%) 50n+
6! (3) Water 25 Q ml (4)
Hydroxylamine tM! i2LM50% aqueous solution
IQnll (5) Hydrazine-hydrate (80% as hydrazine) 5 me (6)
Water Company-wide 400m1 (7
) pH 11.7 Bath solution is fl) (Dissolve 21+31 by heating to make a solution,
Then +4) (5) tel was added to prepare.
メッキは４０〜５０℃、２時間行い、白金析出量は９１
ＱＩ／Ｃ１ｎ２メツキ厚は約８μｍ であった。Plating was carried out at 40 to 50°C for 2 hours, and the amount of platinum deposited was 91.
The QI/C1n2 plating thickness was approximately 8 μm.
この同浴液中に析出は起らず、原液中の白金の利用率は
約９８％であった。No precipitation occurred in this bath solution, and the utilization rate of platinum in the stock solution was about 98%.
実施例２
スルホン酸型及びカルボン酸型膜の複合膜（デュポン社
製、［ナフィオン９０１ ｊ ）を用いそのカルボン酸
膜側に白金を接合した。Example 2 A composite membrane of sulfonic acid type and carboxylic acid type membranes (manufactured by DuPont, [Nafion 901 j]) was used, and platinum was bonded to the carboxylic acid membrane side.
実施例１と同様に、セルに挾み、白金アンミン錯塩溶液
に浸漬した後、ｐＨ１２の水素化ホウ素ナトリウム溶液
で還元して第一還元層を作成した後、下記組成の化学メ
ッキ浴に浸漬（、た。In the same manner as in Example 1, the cell was sandwiched and immersed in a platinum ammine complex salt solution, and then reduced with a sodium borohydride solution of pH 12 to create a first reduction layer, and then immersed in a chemical plating bath with the following composition ( ,Ta.
（１） テトラニトロ白金酸カリウム ０．６ｙ
（２）アンモニア水（２８％） ２０ｍ１（
３） 水１００ｍ１
（４） ヒドロキシルアミン塩酸塩 ０゜２２
（５） ヒドラジン−水和物（ヒド
ラジンとして８０％） ９ ｍｌ（６）
水 全社２
００ｍ１（７）ｐＨ１１，８
浴液はｆｌ） （２＋ ＋３１を加温溶解して水溶液を
得た後、（４）（５）（６）を加えて調製した。(1) Potassium tetranitroplatinate 0.6y
(2) Ammonia water (28%) 20ml (
3) Water 100ml (4) Hydroxylamine hydrochloride 0°22
(5) Hydrazine-hydrate (80% as hydrazine) 9 ml (6)
Water Companywide 2
00ml (7) pH 11.8 Bath solution was fl) (2+ After heating and dissolving +31 to obtain an aqueous solution, it was prepared by adding (4), (5), and (6).
メッキは４０〜４５℃、２時間行い、白金析出量３ｍｙ
／ｃｍ２、メッキ厚約２．５μｍであった。Plating was carried out at 40-45℃ for 2 hours, and the amount of platinum deposited was 3my.
/cm2, and the plating thickness was about 2.5 μm.
この間、浴液中での析出は起らず、原液中の白金の利用
率は９８％であった。During this time, no precipitation occurred in the bath solution, and the utilization rate of platinum in the stock solution was 98%.
実施例３
銅板試料（２Ｘ ４０ｍ）をシアン化ナトリウム溶液で
脱脂清浄化処理した後、５％塩化パラジウム、２Ｎ−塩
酸溶液に室温８０秒間浸漬して活性化した。水洗後下記
メッキ浴液（実施例２と同様にして調製した）に４０℃
、２時間浸漬して約２μｍ（？）白金−パラジウム合金
メッキを得た。Example 3 A copper plate sample (2×40 m) was degreased and cleaned with a sodium cyanide solution, and then activated by immersing it in a 5% palladium chloride, 2N hydrochloric acid solution at room temperature for 80 seconds. After washing with water, add the following plating bath solution (prepared in the same manner as Example 2) to 40°C.
After soaking for 2 hours, a platinum-palladium alloy plating of approximately 2 μm (?) was obtained.
浴液中の分解はなく、金属の利用率はいずれも９６％で
あった。There was no decomposition in the bath liquid, and the metal utilization rate was 96% in all cases.
（１） テトラニトロ白金酸カリウム ０．０５ｙ
（２） テトラニトロパラジウム酸
カリウム ０．０５ｙ（３）
アンモニア氷 ５ ｍ１（４）
水 ８０１Ｍ’
（５） ヒドロキシルアミン塩酸塩 ０．１ｙ
（６） ヒドラジン−水和物（ヒド
ラジンとして８０％） １．５１ｎｌ（７
）水 全量４０ｎｌｄ（ｓ）
ｐＨ１１・８
実施例４
ニッケル試料片１’２Ｘ４Ｃｍ）をアルカリ脱脂し、塩
化ロジウＡ２ｙ、塩酸１０ｍ１．水１００ｍｄの溶液魯
こ８０秒浸漬して活性化した後、水洗し、下記組成の浴
液を用いて４０〜５０℃で２時間、メッキ処理を行った
。(1) Potassium tetranitroplatinate 0.05y
(2) Potassium tetranitropalladate 0.05y (3)
Ammonia ice 5 m1 (4)
Water 801M' (5) Hydroxylamine hydrochloride 0.1y
(6) Hydrazine-hydrate (80% as hydrazine) 1.51 nl (7
)Water total amount 40nld(s)
pH 11.8 Example 4 A nickel sample piece (1'2X4Cm) was degreased with alkali and treated with rhodium chloride A2y and hydrochloric acid 10ml. After activation by immersion in a solution of 100 md of water for 80 seconds, it was washed with water and plated at 40 to 50°C for 2 hours using a bath solution having the following composition.
（１） ジニトロジアンミン白金 ｏ、ｏｓｙ
（２） ７ ：／ モニア水（２８％）
５１１１ｅ（３）水 ２０ｒｒ＋１
（４１ヒＩ”口＋シルｙ ｉ ７１Ｍ酸ｔｊｉ、
０．１ｐ（６） ヒドラジン−水和物（ヒド
ラジンとして８０％） １．５ｍｅ（６）
水 ４０１ｎノ
（７１ｐｌｌ
１１．５ニッケル表面に約２μｍ厚の白金メッキ層が得
られ、白金の利用率は９８％であった。(1) Dinitrodiammine platinum o, osy
(2) 7:/ Monia water (28%)
5111e (3) Water 20rr+1 (41hi I"mouth+sil y i 71M acid tji,
0.1p(6) Hydrazine-hydrate (80% as hydrazine) 1.5me(6)
Water 401n (71pll)
A platinum plating layer with a thickness of approximately 2 μm was obtained on the surface of the 11.5 nickel, and the utilization rate of platinum was 98%.
実施例５
ＡＢＳ樹脂（日本合成ゴム（株）製）の厚さ２ ｍ１１
１の板状試料（８Ｘ４ｃｍ）に白金メッキを行った。Example 5 Thickness of ABS resin (manufactured by Japan Synthetic Rubber Co., Ltd.) 2 m11
A plate-shaped sample (8×4 cm) of No. 1 was plated with platinum.
試料の前処理は、公知のクロム酸エツチングとキャタリ
スト俗諺よび活性化浴により活性化を施した。The pretreatment of the sample included activation using known chromic acid etching and catalyst activation bath.
白金メッキ浴は実施例１の組成のものを用い、４０〜５
０℃、２時間浸漬して約２μ■１のメッキを得た。この
間浴液の分解は見られず、利用率は９７％であった０
（以上）The platinum plating bath used had the composition of Example 1.
After immersion at 0°C for 2 hours, a plating thickness of about 2 μl was obtained. During this period, no decomposition of the bath liquid was observed, and the utilization rate was 97%.
Claims (1)
ンミン錯塩、又はこれ（これら）とパラジウムのニトロ
錯塩若しくは（及び）ニトロアンミン錯塩、（１））ヒ
ドロキシルアミン塩、並びに（Ｃ）ヒドラジンを含有し
１．ＨＩＯ〜１Ｂであることを特徴とする白金又は白金
−パラジウム合金の無電解メッキ浴。■ Contains (a) a nitro complex salt or (and) a nitroammine complex salt of platinum, or a nitro complex salt or (and) a nitroammine complex salt of palladium, (1)) a hydroxylamine salt, and (C) hydrazine. 1. An electroless plating bath for platinum or platinum-palladium alloy, characterized in that the bath is HIO~1B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19058782A JPS5933667B2 (en) | 1982-10-28 | 1982-10-28 | Electroless plating bath for platinum or platinum-palladium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19058782A JPS5933667B2 (en) | 1982-10-28 | 1982-10-28 | Electroless plating bath for platinum or platinum-palladium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5980764A true JPS5980764A (en) | 1984-05-10 |
| JPS5933667B2 JPS5933667B2 (en) | 1984-08-17 |
Family
ID=16260541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19058782A Expired JPS5933667B2 (en) | 1982-10-28 | 1982-10-28 | Electroless plating bath for platinum or platinum-palladium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5933667B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6363610B1 (en) | 1999-10-21 | 2002-04-02 | Allied Signal, Inc. | Gas turbine rotor bimetallic ring seal and method therefor |
| EP1308541A1 (en) * | 2001-10-04 | 2003-05-07 | Shipley Company LLC | Plating bath and method for depositing a metal layer on a substrate |
| US6706420B1 (en) | 2000-07-06 | 2004-03-16 | Honeywell International Inc. | Electroless platinum-rhodium alloy plating |
| WO2007047374A2 (en) | 2005-10-13 | 2007-04-26 | Velocys, Inc. | Electroless plating in microchannels |
| JP2007314876A (en) * | 2006-04-28 | 2007-12-06 | Nippon Kanizen Kk | Electroless nickel plating liquid |
| US20100055422A1 (en) * | 2008-08-28 | 2010-03-04 | Bob Kong | Electroless Deposition of Platinum on Copper |
| CN102071413A (en) * | 2010-12-22 | 2011-05-25 | 东北大学 | Method for chemically plating platinum on surface of conductive carbon substrate |
| JP2012247322A (en) * | 2011-05-30 | 2012-12-13 | Hitachi-Ge Nuclear Energy Ltd | Method for forming platinum film on plant component |
| WO2014162935A1 (en) * | 2013-04-05 | 2014-10-09 | メタローテクノロジーズジャパン株式会社 | Electroless platinum plating solution and electroless platinum plating method using said plating solution |
-
1982
- 1982-10-28 JP JP19058782A patent/JPS5933667B2/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6363610B1 (en) | 1999-10-21 | 2002-04-02 | Allied Signal, Inc. | Gas turbine rotor bimetallic ring seal and method therefor |
| US6706420B1 (en) | 2000-07-06 | 2004-03-16 | Honeywell International Inc. | Electroless platinum-rhodium alloy plating |
| EP1308541A1 (en) * | 2001-10-04 | 2003-05-07 | Shipley Company LLC | Plating bath and method for depositing a metal layer on a substrate |
| WO2007047374A2 (en) | 2005-10-13 | 2007-04-26 | Velocys, Inc. | Electroless plating in microchannels |
| JP2007314876A (en) * | 2006-04-28 | 2007-12-06 | Nippon Kanizen Kk | Electroless nickel plating liquid |
| US20100055422A1 (en) * | 2008-08-28 | 2010-03-04 | Bob Kong | Electroless Deposition of Platinum on Copper |
| CN102071413A (en) * | 2010-12-22 | 2011-05-25 | 东北大学 | Method for chemically plating platinum on surface of conductive carbon substrate |
| JP2012247322A (en) * | 2011-05-30 | 2012-12-13 | Hitachi-Ge Nuclear Energy Ltd | Method for forming platinum film on plant component |
| WO2014162935A1 (en) * | 2013-04-05 | 2014-10-09 | メタローテクノロジーズジャパン株式会社 | Electroless platinum plating solution and electroless platinum plating method using said plating solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5933667B2 (en) | 1984-08-17 |
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