JPH0124231B2 - - Google Patents
Info
- Publication number
- JPH0124231B2 JPH0124231B2 JP10493783A JP10493783A JPH0124231B2 JP H0124231 B2 JPH0124231 B2 JP H0124231B2 JP 10493783 A JP10493783 A JP 10493783A JP 10493783 A JP10493783 A JP 10493783A JP H0124231 B2 JPH0124231 B2 JP H0124231B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- speed
- plating
- plating solution
- group
- 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
Links
- 238000007747 plating Methods 0.000 claims description 97
- 229910052709 silver Inorganic materials 0.000 claims description 91
- 239000004332 silver Substances 0.000 claims description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 90
- 238000001556 precipitation Methods 0.000 claims description 34
- 238000006073 displacement reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 11
- 150000001923 cyclic compounds Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- -1 iron Chemical compound 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 4
- 229940098221 silver cyanide Drugs 0.000 claims description 4
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 241001061127 Thione Species 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000003139 buffering effect Effects 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 39
- 229910000906 Bronze Inorganic materials 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 239000010974 bronze Substances 0.000 description 15
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 7
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical class 0.000 description 3
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- LUZZASVJWGRCFO-UHFFFAOYSA-N [Na].[Ag]C#N Chemical compound [Na].[Ag]C#N LUZZASVJWGRCFO-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000337 buffer salt Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- HKSGQTYSSZOJOA-UHFFFAOYSA-N potassium argentocyanide Chemical compound [K+].[Ag+].N#[C-].N#[C-] HKSGQTYSSZOJOA-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
本発明は、高速銀めつき液に関するものであ
り、特に、銅、銅合金、鉄、鉄合金、ニツケル、
ニツケル合金などの銀よりも卑な金属から成る基
材を浸漬しても、銀の置換析出が生じないよう
に、
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を環内に含む環状化合物を
含有せしめた高速銀めつき液に関するものであ
る。
最近では、電子部品材料に銀めつきを施すとき
経済的観点から、高速度めつき法が広く採用され
ている。この方法は、銀のめつき速度を大きくす
るため、めつき液を高温にし、めつき液中の銀濃
度を高め、めつき液の流速を大きくして行なわれ
る。この方法に用いられる高速銀めつき液は、フ
リーのシアン化物の濃度を十分低く保たれねばな
らない。これは、フリーのシアン化物の濃度が高
いとこのフリーのシアン化物が高温で激しく分解
し、多量のシアンガスが発生して危険となるため
である。そこで、高速銀めつき液には、銀塩をシ
アン化銀アルカリの形で導入し、さらに電解時に
陰極から生成するフリーのシアン化物を徐々に分
解させて除去し、蓄積せしめないようにするた
め、液のPHを7.5〜9.0程度に保つためのPH緩衝系
を形成することが特徴である。
また、現在では、高価格である銀をさらに有効
に利用するため高速で、めつき必要部分のみにめ
つきを行う高速部分めつき法が行われている。
この高速部分めつき法は、めつき不要部分にマ
スクを施し、被めつき部分に銀めつき液をポンプ
により高速で噴出させ、被めつき基材と不溶性陽
極の間に電流を流すことにより、めつきを施すと
いうジエツトめつき法が主体である。このような
高速度部分銀めつきにおいての従来の最大の問題
点は、銀めつきを施したい銀より卑なる金属基材
上に、銀めつき液に浸漬しただけで銀が置換析出
してしまうことである。この銀の置換析出は金属
基材として、銅、銅合金、鉄、鉄合金、ニツケル
合金を用いた時に顕著である。この置換析出した
銀は、通常基材との密着性が悪く、この上に電解
で銀めつきを施した場合、めつき皮膜のはがれや
加熱時にふくれや変色が生じ、めつき不良の原因
となる。このめつき不良は、電子部品の銀めつき
に関しては特に致命的である。また、これのみな
らず、部分めつきの場合はめつき不要部分にも析
出することになるため、高価格の銀が損失されて
しまう。従来のめつき方法では、このような密着
性の悪い銀の置換析出を防ぐためには、銀濃度の
低いめつき液から、ストライクめつきとよばれる
薄い銀めつきを施し、その後、通常のめつきをそ
の上へ施している。しかし、部分めつきに関して
はストライクめつきを行うことは、めつきの密着
性を向上させることはできるが、めつき不要部分
にもストライクめつきを行わねばならないため銀
の損失となる。このような高速部分めつきにおけ
る銀の置換析出を防止する目的で、メルカプト化
合物を含有せしめた銀めつき液も提案されてい
る。（特開昭55−34699号）しかし、ここで推奨さ
れているチオ乳酸やチオリンゴ酸は悪臭を有する
うえに、銅イオンの存在下では、銀の置換析出を
防止する効果が消失し易いという欠点を有してい
る。
従つて、例えば、銅基材上へ銀めつきを行う場
合に、銀の置換析出が少しずつおこつて銅イオン
が液中に蓄積したり、また外部から銅イオンが混
入するなどにより、液中の銅イオンの濃度が高ま
ると、この後は、同じメルカプタン化合物を添加
して置換析出を防止しようとしても置換析出を防
止する効果はすぐ消失してしまう。このことは、
液の管理を困難にするものである。
また、他にも、銀の置換析出を防止する目的
で、「環状核に直接結合したメルカプト基を有す
る芳香族または複素環化合物を含む銀めつき液」
（特開昭57−43995号）や「ジチオカルバミン酸も
しくはその塩および／又はチオセミカルバジツド
もしくはその塩を添加して成る銀めつき液（特開
昭57−131382号）も提案されている。しかし、こ
れらで提案されている化合物は、フリーのシアン
化物の濃度が高い銀めつき液中に添加すれば銀よ
り卑な金属の浸漬による銀の置換析出を防止する
ことができるが、高速度めつきで用いられるフリ
ーのシアン化物が十分低くなつている銀めつき液
中では沈殿物を生じせしめ、置換析出を防止する
効果は有しない。
以上のように、現在までの既存技術では高速度
部分めつきにおいて、銀の置換析出を防止して密
着性の良好な銀めつき皮膜を得、銀の損失を防ぐ
ことは必ずしも十分ではないのである。
本発明は、上述のような既存技術の欠点を解決
するために、
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を環内に含む環状化合物を
用い、フリーのシアン化物濃度が十分低い高速銀
めつき液において銀の置換析出を防止し、銀スト
ライクめつきなしで該基材上へ密着性の良好な銀
めつきを施すことを目的としたものである。この
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を環内に含む環状化合物の
銀の置換析出を防止する効果はきわめて高く、し
かも、悪臭を有さず、Cuイオンの存在下におい
ても効果を消失しにくい。また、フリーのシアン
化物濃度が十分低い高速銀めつき液中に添加して
も沈殿を生じない。
これらの化合物は、通常のフリーのシアン化物
濃度が十分低い高速度銀めつき液に、0.05ｇ／ｌ
含有せしめれば完全に置換析出を防止することが
でき、条件によつては0.02ｇ／ｌでも十分な効果
が得られる。
本発明に用いられる
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を環内に含む環状化合物
は、チオン基の両側にＮ原子が付いていること、
さらに環状となつていることで、高速めつきを行
う場合の高温，高流速，高電流密度という厳しい
条件下でも分解されにくく、安定化されている。
これに対し、
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を有していても環状でない
化合物や、環状であつてもチオン基の両側共にＮ
原子が付いていない化合物では、高速めつきが行
われる条件下では分解し易い。このような分解反
応に対しては、
The present invention relates to a high-speed silver plating solution, particularly for copper, copper alloys, iron, iron alloys, nickel,
Even if a base material made of a metal less base than silver, such as a nickel alloy, is immersed, silver substitution precipitation will not occur. (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) The present invention relates to a high-speed silver plating solution containing a cyclic compound containing a thioureylene group in the ring. Recently, high-speed plating methods have been widely adopted from an economic standpoint when silver plating electronic component materials. In this method, in order to increase the silver plating speed, the plating solution is heated to a high temperature, the silver concentration in the plating solution is increased, and the flow rate of the plating solution is increased. The high speed silver plating solution used in this process must have a sufficiently low concentration of free cyanide. This is because when the concentration of free cyanide is high, the free cyanide decomposes violently at high temperatures and generates a large amount of cyanide gas, which is dangerous. Therefore, silver salt is introduced into the high-speed silver plating solution in the form of alkali silver cyanide, and the free cyanide generated from the cathode during electrolysis is gradually decomposed and removed to prevent it from accumulating. It is characterized by forming a PH buffer system to maintain the pH of the liquid at around 7.5 to 9.0. Furthermore, in order to make more effective use of silver, which is expensive, a high-speed partial plating method is currently being used in which only the areas that require plating are plated at high speed. This high-speed partial plating method involves applying a mask to areas that do not require plating, spraying silver plating liquid onto the plating area at high speed using a pump, and passing an electric current between the plating base material and the insoluble anode. The main method is the jet plating method, in which plating is applied. The biggest conventional problem with such high-speed selective silver plating is that silver is precipitated by substitution on the metal base material baser than silver simply by immersing it in a silver plating solution. It's about putting it away. This displacement precipitation of silver is remarkable when copper, copper alloy, iron, iron alloy, or nickel alloy is used as the metal base material. This displacement-precipitated silver usually has poor adhesion to the base material, and when silver plating is applied electrolytically on it, the plating film may peel off or blister or discolor when heated, causing poor plating. Become. This plating defect is especially fatal when it comes to silver plating of electronic parts. Moreover, in addition to this, in the case of partial plating, silver is deposited in areas where plating is not required, resulting in a loss of high-priced silver. In conventional plating methods, in order to prevent such substitutional precipitation of silver with poor adhesion, thin silver plating called strike plating is applied using a plating solution with a low silver concentration, and then regular plating is applied. Tsuki is applied on top of it. However, with regard to partial plating, strike plating can improve the adhesion of plating, but it results in a loss of silver because strike plating must be performed on areas that do not need plating. Silver plating solutions containing mercapto compounds have also been proposed for the purpose of preventing substitutional precipitation of silver during such high-speed partial plating. (Japanese Unexamined Patent Publication No. 55-34699) However, the thiolactic acid and thiomalic acid recommended here have the disadvantage that they have a bad odor and their effectiveness in preventing silver displacement precipitation is easily lost in the presence of copper ions. have. Therefore, when silver plating is performed on a copper substrate, for example, substitutional precipitation of silver occurs little by little and copper ions accumulate in the solution, or copper ions enter the solution from the outside. When the concentration of copper ions increases, even if the same mercaptan compound is added to prevent displacement precipitation, the effect of preventing displacement precipitation immediately disappears. This means that
This makes liquid management difficult. In addition, for the purpose of preventing substitutional precipitation of silver, "a silver plating solution containing an aromatic or heterocyclic compound having a mercapto group directly bonded to a cyclic nucleus" is used.
(Japanese Unexamined Patent Publication No. 57-43995) and "A silver plating solution containing dithiocarbamic acid or its salt and/or thiosemicarbazide or its salt (Japanese Unexamined Patent Publication No. 57-131382) have also been proposed. However, when these proposed compounds are added to a silver plating solution with a high concentration of free cyanide, they can prevent the displacement precipitation of silver due to immersion in metals less base than silver; In the silver plating solution where the free cyanide content used in speed plating is sufficiently low, it will form a precipitate and will not be effective in preventing displacement precipitation. In speed partial plating, it is not always sufficient to prevent silver displacement precipitation, obtain a silver plating film with good adhesion, and prevent silver loss. In order to solve the shortcomings of (R 1 , R 2 are hydrogen, alkyl group, or aryl group) A cyclic compound containing a thioureylene group in the ring is used to prevent substitutional precipitation of silver in a high-speed silver plating solution with a sufficiently low free cyanide concentration, The purpose of this method is to provide silver plating with good adhesion onto the substrate without silver strike plating. this (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) The cyclic compound containing a thioureylene group in the ring has an extremely high effect of preventing silver substitution precipitation, and has no bad odor and the presence of Cu ions. The effect does not easily disappear even at the bottom. Furthermore, no precipitation occurs even when added to a high-speed silver plating solution with a sufficiently low free cyanide concentration. These compounds can be added at 0.05 g/l to a high speed silver plating solution with a sufficiently low free cyanide concentration.
If it is included, displacement precipitation can be completely prevented, and depending on the conditions, a sufficient effect can be obtained even at 0.02 g/l. used in the present invention (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) A cyclic compound containing a thioureylene group in the ring has N atoms on both sides of the thione group,
Furthermore, its annular shape makes it difficult to decompose and stabilized even under the harsh conditions of high temperature, high flow rate, and high current density when performing high-speed plating.
On the other hand, (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) Even if it has a thioureylene group, it is not cyclic, or even if it is cyclic, both sides of the thione group are N
Compounds without atoms are easily decomposed under high-speed plating conditions. For such decomposition reactions,
【式】なるチオウレイレ
ン基を含む環状化合物で、しかも環が５員環また
は６員環であり、そして、環の他の構成原子がＣ
またはＮである化合物が特に安定である。
本発明に用いられる
（R1，R2は水素またはアルキル基またはアリ
ール基）
なるチオウレイレン基を環内に含む環状化合物と
しては、２−チオバルビツル酸、２−イミダゾリ
ジンチオン、１−フエニル−２−テトラゾリン−
５−チオンまたはこれらの誘導体が拳げられる。
これら環状化合物の添加量は、銀の置換析出を防
止するのに必要かつ十分な量添加すれば良いが、
一般に浴に対し10〜300mg／ｌの添加量が好適で
ある。
本発明の高速銀めつき液は、銀塩としてシアン
化銀アルカリを含有する。シアン化銀アルカリと
しては、シアン化銀ナトリウムも用い得るが、一
般にシアン化銀カリウムが最良である。また、液
のPH緩衝性と、電気伝導性を付与するためリン
酸、ピロリン酸、クエン酸のアルカリ金属塩を含
有する。また、ホウ酸などのPH緩衝塩をさらに加
えてもよい。
本発明の高速銀めつき液は通常の装置を用い、
通常の高速めつきを行うときの条件で使用され得
る。例えば、銀塩の濃度は、銀として50〜80ｇ／
ｌ、液温は40〜80℃、電流密度は20〜200A／ｄ
m2PHは7.5〜9.0の間で使用され得る。このような
条件で適当な流速で高速めつきを行うと、得られ
る銀めつき皮膜は密着性がよく、均一、平滑で、
硬度も低く、電子部品用の銀めつきとしては最適
のものである。ただ、光沢は低いが、もし、光沢
の高いめつき皮膜を得たい場合は、セレン化合物
を添加すればよい。また使用者の目的に応じてア
ンチモン化合物、EDTA、その他の界面活性剤
など当業者に公知の成分を添加し、めつき皮膜の
性質やめつき条件を改めることを拒むものではな
い。
以上のように、本発明の高速銀めつき液は、
銅、銅合金、鉄、鉄合金、ニツケル、ニツケル合
金などの銀よりも卑な金属基材に対して高速めつ
きを施すときに、銀の置換析出を防止するため、
めつき皮膜の密着性が高められ、銀の損失をなく
すことができる。しかも、銅イオンなどの不純物
によりこの効果が失われず、きわめて液の管理が
容易であり、消耗成分を随時補充し、定期的に活
性炭過を行えば半恒久的な使用が可能である。
以下に本発明の実施例について説明する。
実施例 １
次の組成の高速銀めつき液を作製した。
KAg（CN）2 120ｇ／ｌ
K2HPO4 90ｇ／ｌ
２−チオバルビツル酸 50mg／ｌ
これをPH8.3に調整し、通常の方法でアルカリ
脱脂、酸洗を施したリン青銅板を浸漬したとこ
ろ、リン青銅板上への銀の置換析出は全く生じな
かつた。さらにこの液を用い同じ処理を施したリ
ン青銅板にジエツトめつき法で高速部分めつきを
行つた。電流密度は100A／ｄm2液温は65℃とし
た。得られた銀めつき皮膜は均一、平滑で硬度も
低いものであつた。密着性は良好であり、これを
350℃で２分間加熱したところ、ふくれなどの外
観変化は生じなかつた。
実施例 ２
実施例１の２−チオバルビツル酸のかわりに２
−イミダゾリジンチオンを30mg／ｌ添加し、同様
の実験を行つたところ、ほとんど同じ結果を得
た。
実施例 ３
次の組成の高速銀めつき液を作製した。
KAg（CN）2 120ｇ／ｌ
K4P2O7 70ｇ／ｌ
H3BO3 30ｇ／ｌ
１−フエニル−２−テトラゾリン
−５−チオン 30mg／ｌ
この溶液をPH8.3に調整し、通常の方法でアル
カリ脱脂、酸洗を施したリン青銅板を浸漬したと
ころ、リン青銅板上への銀の置換析出は全く生じ
なかつた。
次にこの組成の高速銀めつき液を用い、同じ前
処理をしたリン青銅板に100A／ｄm2の電流密度
で65℃でジエツトめつき法により高速部分めつき
を行つた。得られた銀めつき皮膜は、均一、平滑
で密着性は良好であり、これを350℃で２分間加
熱してもふくれなどの外観変化は生じなかつた。
なお、実施例１〜３において、それぞれ２−チ
オバルビツル酸、２−イミダゾリジンチオン、１
−フエニル−２−テトラゾリン−５−チオンを含
まない溶液で同様の実験を行うと、いずれも密着
性の悪い銀の置換析出がおこつた。
比較実験結果 １
次の組成の高速銀めつき液を作製した。
KAg（CN）2 120ｇ／ｌ
K2HPO4 90ｇ／ｌ
これをPH8.3に調整し、表１の化合物をそれぞ
れ濃度が100mg／ｌとなるように添加し、ジエツ
トめつき法で高速部分めつきを行うこととした。[Formula] A cyclic compound containing a thioureylene group, the ring is a 5-membered ring or a 6-membered ring, and other constituent atoms of the ring are C
or N compounds are particularly stable. used in the present invention (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) Examples of cyclic compounds containing a thioureylene group in the ring include 2-thiobarbituric acid, 2-imidazolidinethione, 1-phenyl-2-tetrazoline-
5-thione or a derivative thereof is used.
These cyclic compounds may be added in an amount necessary and sufficient to prevent substitutional precipitation of silver.
In general, an amount of 10 to 300 mg/l added to the bath is suitable. The high-speed silver plating solution of the present invention contains alkali silver cyanide as a silver salt. Although sodium silver cyanide can also be used as the alkali silver cyanide, potassium silver cyanide is generally best. It also contains alkali metal salts of phosphoric acid, pyrophosphoric acid, and citric acid to impart pH buffering properties and electrical conductivity to the liquid. Additionally, a PH buffer salt such as boric acid may be further added. The high-speed silver plating solution of the present invention uses ordinary equipment,
It can be used under normal high-speed plating conditions. For example, the concentration of silver salt is 50 to 80 g of silver/
l, liquid temperature is 40~80℃, current density is 20~200A/d
m2PH can be used between 7.5 and 9.0. When high-speed plating is performed at an appropriate flow rate under these conditions, the resulting silver-plated film has good adhesion, is uniform, smooth, and
It has low hardness and is ideal for silver plating for electronic parts. However, the gloss is low, but if you want to obtain a highly glossy plating film, you can add a selenium compound. Furthermore, depending on the purpose of the user, components known to those skilled in the art such as antimony compounds, EDTA, and other surfactants may be added to modify the properties of the plating film and the plating conditions. As described above, the high-speed silver plating solution of the present invention is
To prevent substitutional precipitation of silver when performing high-speed plating on metal substrates baser than silver, such as copper, copper alloys, iron, iron alloys, nickel, and nickel alloys,
The adhesion of the plating film is improved and silver loss can be eliminated. Moreover, this effect is not lost due to impurities such as copper ions, and the liquid is extremely easy to manage, and semi-permanent use is possible by replenishing consumable components as needed and periodically filtering with activated carbon. Examples of the present invention will be described below. Example 1 A high-speed silver plating solution having the following composition was prepared. KAg (CN) 2 120g/l K 2 HPO 4 90g/l 2-thiobarbituric acid 50mg/l This was adjusted to pH 8.3, and a phosphor bronze plate that had been alkaline degreased and pickled in the usual way was immersed. , no substitutional precipitation of silver occurred on the phosphor bronze plate. Furthermore, using this solution, high-speed partial plating was carried out using the jet plating method on a phosphor bronze plate that had been subjected to the same treatment. The current density was 100 A/dm 2 and the liquid temperature was 65°C. The silver-plated film obtained was uniform, smooth, and had low hardness. The adhesion is good and this
When heated at 350°C for 2 minutes, no change in appearance such as blistering occurred. Example 2 2 in place of 2-thiobarbituric acid in Example 1
- When a similar experiment was carried out by adding 30 mg/l of imidazolidinethione, almost the same results were obtained. Example 3 A high-speed silver plating solution having the following composition was prepared. KAg (CN) 2 120g/l K 4 P 2 O 7 70g/l H 3 BO 3 30g/l 1-phenyl-2-tetrazoline-5-thione 30mg/l This solution was adjusted to pH 8.3, and When a phosphor bronze plate that had been subjected to alkaline degreasing and pickling was immersed in the method, no substitutional precipitation of silver occurred on the phosphor bronze plate. Next, using the high speed silver plating solution having this composition, high speed partial plating was performed on a phosphor bronze plate which had undergone the same pretreatment at a current density of 100 A/dm 2 at 65° C. by jet plating method. The silver-plated film obtained was uniform, smooth, and had good adhesion, and no change in appearance such as blistering occurred even when it was heated at 350° C. for 2 minutes. In Examples 1 to 3, 2-thiobarbituric acid, 2-imidazolidinethione, and 1
When similar experiments were conducted using solutions that did not contain -phenyl-2-tetrazoline-5-thione, displacement precipitation of silver with poor adhesion occurred in all cases. Comparative Experiment Results 1 A high-speed silver plating solution with the following composition was prepared. KAg (CN) 2 120g/l K 2 HPO 4 90g/l Adjust the pH to 8.3, add the compounds in Table 1 to a concentration of 100mg/l, and high-speed partial plating using the jet plating method. We decided to conduct a test.
【表】【table】
【表】
置換析出防止効果の欄の印は、次のことを示す。
〇；銀の置換析出が全く生じず、リン青銅板の
色の変化がない。
△；銀の置換析出が部分的におこり、リン青銅
板が部分的に白色化する。
×；銀の置換析出が全面でおこり、リン青銅板
が完全に白色化する。
表１に示すように、本発明の添加剤である２−
チオバルビツル酸、２−イミダゾリジンチオン、
１−フエニル−２−テトラゾリン−５−チオンは
沈殿を生じしめなかつた。しかし、比較例として
挙げたもののいくつかは沈殿を生じた。これらの
高速銀めつき液に通常の方法でアルカリ脱脂、酸
洗を施したリン青銅板を30秒間浸漬したところ、
各添加剤による銀の置換析出の防止効果は表１に
示すようになつた。
このような置換析出を生じしめる高速銀めつき
液を用い、前処理をしたリン青銅板に実施例１と
同じ条件で高速銀めつきを行うと、めつき不要部
分に多量の銀が析出したのみならず、得られた銀
めつき皮膜は、外観上むらが大きく、密着性が悪
く、350℃で２分間加熱を行うと変色、ふくれを
生じた。
比較実験結果 ２
比較実験結果１と同じ組成の高速銀めつき液を
作製し、リン青銅板を浸漬して銅イオンを溶出さ
せた。この液に次の化合物
Γ チオ乳酸
Γ チオリンゴ酸
Γ ２−チオバルビツル酸
Γ ２−イミダゾリジンチオン
Γ １−フエニル−２−テトラゾリン−５−チオ
ン
を50mg／ｌずつ添加した。
この溶液を用い、通常の方法でアルカリ脱脂、
酸洗を施したリン青銅板を浸漬すると全て置換析
出は生じなかつた。さらに、これらの銀めつき液
を用い、実施例１と同様の条件で高速度部分めつ
きを行つたところ、いずれも良好な銀めつき皮膜
が得られた。
この銀めつき液をこの後72時間放置した。同じ
様に前処理を施したリン青銅板を浸漬したとこ
ろ、チオ乳酸、チオリンゴ酸を添加した溶液で
は、密着性の悪い銀の置換析出が生じた。さらに
高速度めつきを行うと、得られた銀めつき液皮膜
は密着性が悪く、外観上むらが多いものであつ
た。
一方、本発明の添加剤である２−チオバルビツ
ル酸、２−イミダゾリジンチオン、１−フエニル
−２−テトラゾリン−５−チオンを添加した溶液
では、72時間の放置の後も前処理したリン青銅板
上への銀の置換析出は完全に防止されていた。高
速めつきを行うと、得られた銀めつき皮膜は以前
と変わらず、良好なものであつた。また、240時
間以上の放置の後も同様の結果が得られた。[Table] The mark in the column of substitution precipitation prevention effect indicates the following. ○: No substitutional precipitation of silver occurred, and there was no change in the color of the phosphor bronze plate. Δ: Substitutional precipitation of silver occurs partially, and the phosphor bronze plate becomes partially white. ×: Substitutional precipitation of silver occurs over the entire surface, and the phosphor bronze plate becomes completely white. As shown in Table 1, 2-
Thiobarbituric acid, 2-imidazolidinethione,
1-Phenyl-2-tetrazoline-5-thione did not form a precipitate. However, some of the comparative examples produced precipitation. When a phosphor bronze plate that had been alkaline degreased and pickled in the usual way was immersed in these high-speed silver plating solutions for 30 seconds,
Table 1 shows the effect of each additive on preventing silver displacement precipitation. When high-speed silver plating was performed on a pretreated phosphor bronze plate under the same conditions as in Example 1 using a high-speed silver plating solution that causes such substitutional precipitation, a large amount of silver was deposited in areas where plating was not required. In addition, the resulting silver-plated film had a highly uneven appearance, poor adhesion, and discolored and blistered when heated at 350° C. for 2 minutes. Comparative Experiment Results 2 A high-speed silver plating solution having the same composition as Comparative Experiment Results 1 was prepared, and a phosphor bronze plate was immersed in it to elute copper ions. To this solution, the following compounds Γ thiolactic acid Γ thiomalic acid Γ 2-thiobarbituric acid Γ 2-imidazolidinethione Γ 1-phenyl-2-tetrazoline-5-thione were added at 50 mg/l each. Using this solution, perform alkaline degreasing in the usual way.
When the pickled phosphor bronze plate was immersed, no displacement precipitation occurred. Furthermore, when high-speed partial plating was performed using these silver plating solutions under the same conditions as in Example 1, good silver plating films were obtained in all cases. This silver plating solution was then allowed to stand for 72 hours. When a phosphor bronze plate pretreated in the same manner was immersed in a solution containing thiolactic acid and thiomalic acid, substitutional precipitation of silver with poor adhesion occurred. When high-speed plating was further performed, the resulting silver plating liquid film had poor adhesion and was highly uneven in appearance. On the other hand, in a solution containing 2-thiobarbituric acid, 2-imidazolidinethione, and 1-phenyl-2-tetrazoline-5-thione, which are the additives of the present invention, even after standing for 72 hours, the solution did not remain on the pretreated phosphor bronze plate. The displacement precipitation of silver was completely prevented. When high-speed plating was performed, the silver-plated film obtained was as good as before. Similar results were also obtained after being left for more than 240 hours.
Claims (1)
金、ニツケル、ニツケル合金などの銀より卑な金
属のいずれかから成る基材上へ銀を電気めつきす
るための銀めつき液において、 （R1，R2は水素またはアルキル基またはアリ
ール基） なるチオウレイレン基を環内に含む環状化合物を
銀の置換析出を防止するに十分な量添加し、浸漬
による該基材上への銀の置換析出を防止すること
を特徴とする高速銀めつき液。 ２ （R1，R2は水素またはアルキル基またはアリ
ール基） なるチオウレイレン基を環内に含む環状化合物
は、環が５員環または６員環であり、そして、環
の他の構成原子がＣまたはＮである特許請求の範
囲第１項に記載の高速銀めつき液。 ３ （R1，R2は水素またはアルキル基またはアリ
ール基） なるチオウレイレン基を環内に含む環状化合物
は、２−チオバルビツル酸、２−イミダゾリジン
チオン、１−フエニル−２−テトラゾリン−５−
チオンまたはこれらの誘導体である特許請求の範
囲第２項に記載の高速銀めつき液。 ４ 高速銀めつき液は、銀塩としてシアン化銀ア
ルカリを含有し、かつ、 （R1，R2は水素またはアルキル基またはアリ
ール基） なるチオウレイレン基を環内に含む環状化合物の
存在下で、浸漬による銀の置換析出が防止できる
ように、フリーのシアン化物の量が十分低くなつ
ている特許請求の範囲第１項に記載の高速銀めつ
き液。 ５ 高速銀めつき液は、リン酸、ピロリン酸、ク
エン酸のアルカリ金属塩の中から選ばれる塩を電
気伝導性及びPH緩衝性を付与するために含有し、
PHが7.5〜9.0の範囲内に調整された特許請求の範
囲第１項に記載の高速銀めつき液。[Claims] 1. A method for electroplating silver onto a substrate made of copper, a copper alloy, a copper plating base, or a metal less base than silver such as iron, an iron alloy, nickel, or a nickel alloy. In silver plating liquid, (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) A cyclic compound containing a thioureylene group in the ring is added in an amount sufficient to prevent substitutional precipitation of silver, and silver is deposited on the substrate by immersion. A high-speed silver plating solution that prevents displacement precipitation. 2 (R 1 and R 2 are hydrogen, an alkyl group, or an aryl group) A cyclic compound containing a thioureylene group in the ring is a 5- or 6-membered ring, and the other constituent atoms of the ring are C or The high-speed silver plating solution according to claim 1, which is N. 3 (R 1 , R 2 are hydrogen, an alkyl group, or an aryl group) Cyclic compounds containing a thioureylene group in the ring include 2-thiobarbituric acid, 2-imidazolidinethione, 1-phenyl-2-tetrazoline-5-
The high-speed silver plating solution according to claim 2, which is thione or a derivative thereof. 4. The high-speed silver plating solution contains alkali silver cyanide as a silver salt, and (R 1 and R 2 are hydrogen, alkyl groups, or aryl groups) In the presence of a cyclic compound containing a thioureylene group in the ring, the amount of free cyanide is sufficient to prevent displacement precipitation of silver due to immersion. A high-speed silver plating solution according to claim 1, in which the claims are extended. 5. The high-speed silver plating solution contains a salt selected from alkali metal salts of phosphoric acid, pyrophosphoric acid, and citric acid to impart electrical conductivity and PH buffering properties,
The high-speed silver plating solution according to claim 1, wherein the pH is adjusted within the range of 7.5 to 9.0.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10493783A JPS59232288A (en) | 1983-06-14 | 1983-06-14 | High speed silver plating liquid |
| US06/617,215 US4614568A (en) | 1983-06-14 | 1984-06-04 | High-speed silver plating and baths therefor |
| KR1019840003181A KR890001106B1 (en) | 1983-06-14 | 1984-06-07 | High-speed silver plating |
| GB08414641A GB2141441B (en) | 1983-06-14 | 1984-06-08 | High-speed silver plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10493783A JPS59232288A (en) | 1983-06-14 | 1983-06-14 | High speed silver plating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59232288A JPS59232288A (en) | 1984-12-27 |
| JPH0124231B2 true JPH0124231B2 (en) | 1989-05-10 |
Family
ID=14394003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10493783A Granted JPS59232288A (en) | 1983-06-14 | 1983-06-14 | High speed silver plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59232288A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014112430A1 (en) * | 2013-01-15 | 2014-07-24 | 三菱瓦斯化学株式会社 | Silicon etching liquid, silicon etching method, and microelectromechanical element |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4604167A (en) * | 1984-01-26 | 1986-08-05 | Shinko Electric Industries Co., Ltd. | Silver plating solution and silver plating process and pretreatment solution therefor |
| JPS6223996A (en) * | 1985-07-23 | 1987-01-31 | Nippon Mining Co Ltd | Silver plating method |
| JP6230778B2 (en) * | 2012-05-31 | 2017-11-15 | 日亜化学工業株式会社 | Electrolytic silver plating solution for optical semiconductor devices |
-
1983
- 1983-06-14 JP JP10493783A patent/JPS59232288A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014112430A1 (en) * | 2013-01-15 | 2014-07-24 | 三菱瓦斯化学株式会社 | Silicon etching liquid, silicon etching method, and microelectromechanical element |
| JPWO2014112430A1 (en) * | 2013-01-15 | 2017-01-19 | 三菱瓦斯化学株式会社 | Silicon etching solution, etching method, and microelectromechanical element |
| US9875904B2 (en) | 2013-01-15 | 2018-01-23 | Mitsubishi Gas Chemical Company, Inc. | Silicon etching liquid, silicon etching method, and microelectromechanical element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59232288A (en) | 1984-12-27 |
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