JPS6352120B2 - - Google Patents
Info
- Publication number
- JPS6352120B2 JPS6352120B2 JP1886982A JP1886982A JPS6352120B2 JP S6352120 B2 JPS6352120 B2 JP S6352120B2 JP 1886982 A JP1886982 A JP 1886982A JP 1886982 A JP1886982 A JP 1886982A JP S6352120 B2 JPS6352120 B2 JP S6352120B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- present
- general formula
- plating solution
- copper 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
Links
- 238000007747 plating Methods 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000009499 grossing Methods 0.000 description 12
- 150000004985 diamines Chemical class 0.000 description 6
- 238000005282 brightening Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- -1 polyethylene oxydicarboxylic acid Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
本発明は銅めつきに使用する酸性めつき液に関
する。めつきに要求される重要な特性として表面
が平滑にめつきされること、広い電流密度でめつ
きができることが挙げられる。
硫酸銅と硫酸を主成分とするめつき液において
も、平滑化作用、光沢化作用を有する種々の物質
例えばスルフイド類、ポリエーテル類、チオ尿素
類、チオ燐酸エステル、チオカルバミン酸エステ
ルなどが添加剤として用いられてきた。
それらの光沢剤や平滑化剤は一定の効果を示し
ているが工業上の様々の要求はよりすぐれた添加
剤を常に求めている。特に、電極と被めつき面と
の間隔が異なることによつて電流密度に差が生ず
ることから来る問題即ち、場所によるめつきの不
均一性があり、作業能率、製品価値の両面から、
より広い範囲にわたつて平滑で均一なめつきを行
ない得る方法が望まれている。
本発明はこうした要求にこたえる新規な平滑化
剤を含有する酸性銅めつき液を提供する。
即ち本発明は、一般式（）
HOOC・CH2O−（CH2CH2O）o−CH2COOHによ
り表わされるジカルボン酸（但しｎ＝０〜1000）
および／又は、一般式（）
H2N−（CH2）3−Ｏ−（CH2CH2O）o−（CH2）3−
NH2により表わされるジアミン（但しｎ＝０〜
1000）を、硫酸銅および硫酸を主成分とする酸性
銅めつき液に含有することを特徴とする銅めつき
液である。本発明は、さらに、これにポリビニル
ピロリドン（PVP）および／又は、ビニルピロ
リドン（VP）と酢酸ビニル（VA）の共重合物
を添加した酸性銅めつき液を提供する。
硫酸銅と硫酸を主成分とする銅めつき液は広く
一般に使用されている。最も基本的な液の組成と
しては硫酸銅（５水和物）50〜350ｇ／、硫酸
30〜250ｇ／である。PHは通常１以下の強酸性
で遊離の硫酸が存在する。銅イオン源としては硫
酸銅の他の部分的には他の銅塩、例えば炭酸銅、
ピロリン酸銅、ホウフツ化銅等をも併用して使う
ことができる。硫酸も部分的には他の酸、例えば
リン酸、フルオロ硼酸などを併用してもよい。ま
たその他の成分として塩化ナトリウム、塩化アン
モニウム、塩化カリウム、塩酸などの塩化物を塩
素量換算10〜100mg／添加してめつき液を作つ
てもよい。
本発明のめつき液はこの酸性めつき液に新規な
平滑化剤として、前記一般式（）で表わされる
ジカルボン酸（ポリエチレンオキシジカルボン
酸）及び／又は前記一般式（）で表わされるジ
アミン（ポリエチレンオキシジアミン）である。
ポリエチレングリコール鎖の重合度が、めつき
効果に及ぼす影響は重合度1000以下の範囲ではさ
ほど極端な変化はなく、その重合度でも一応は効
果が認められるが、重合度３〜150（分子量300〜
7000）程度が扱いやすい。
このジカルボン酸又はジアミンの添加量は0.01
ｇ／で効果が認められるが、それ以下では平滑
化作用が不十分でめつき表面が粗くなる。添加量
0.5〜６ｇ／の範囲は最も実用性のある好まし
い範囲で効果も明確である。
さらに増量すれば30ｇ／程度までは増量の効
果が認められるが、それ以上ではほとんど効果に
差はなく、経済的に利点はない。
本発明のジカルボン酸とジアミンは平滑化作用
にすぐれており、めつき作業の能率向上や凹凸の
大きな被めつき体の処理、電流効率の向上などに
効力を発揮する。但し、これだけでは光沢のある
銅めつきは得られないが、下地用の銅めつき（例
えばニツケルめつきの下地としての銅めつき）あ
るいはプリント配線等の機能めつき用としては、
本発明のジカルボン酸及び／又は、ジアミンの使
用だけで満足できる製品が得られる。
一般に表面粗さは、下地用としては1μ以下、
機能めつき用としては1.5μ以下であれば十分とい
われており、本発明の平滑化剤を使用すれば、広
い電流密度範囲でこの基準をみたす緻密でめつき
ムラのない製品を得ることができる。
めつき製品に良い光沢が要求される時には、本
発明の平滑化剤、ジカルボン酸とジアミンに加え
て、ポリビニルピロリドン（PVP）又はビニル
ピロリドン（VP）と酢酸ビニル（VA）との共
重合体を光沢剤として使用する。
PVPは一般には化粧品、食品添加物、代用血
清などの用途に用いられているが、銅めつきの添
加剤として有効であることはこれまで知られてい
なかつた。
VPとVAとの共重合体は、例えばルビスコー
ル（商品名：三菱油化製）として販売されている
が、用途は調髪剤等の化粧品、増粘剤であり、こ
れもまためつき関係への応用は新規である。
VPとVAとのモノマー比は、VP／VA＝70／
30〜20／80（重量比）ぐらいが適切である。
本発明の光沢剤は、広い電流密度範囲でくもり
のない光沢をだす特徴があり、0.01ｇ／の添加
で一応の効果が認められる。それ以下の量でも効
果は認められるが、光沢が劣り、実用性はない。
また10ｇ／以上加えるとザラ、ピツト、めつき
ムラが多くなることがあり、実用的には0.01〜
0.1ｇ／の範囲が好ましい。なお、本発明の光
沢剤は本発明の平滑化剤と併用した場合において
有用性をもつものであり、平滑化剤なしで単独に
使用した場合には光沢化作用を十分には示さず、
ピツト生成等の異常析出が発生する可能性があ
る。また同一量の添加では、PVP、ホモポリマ
ーの方がVPとVAとのコーポリマーよりも効果
が大きい。
本発明の光沢剤には、前記PVP及びVPとVA
のコーポリマーを使用することが望ましいが、他
の公知の光沢剤のうちある種のものはPVP及び
VPとVAのコーポリマーの一部又は全部におき
かえて使用することも可能である。
特に有機チオ化合物類、例えば
ベンゾインチオ尿素、ジエチルジチオカルバミ
ン酸、チオグリコール酸などは好適である。この
場合、これらの公知の光沢剤を0.0005〜２ｇ／
、好ましくは0.001〜0.01ｇ／使用する。こ
れらの光沢剤もまた多すぎるとザラ、めつきムラ
等の異常析出をひきおこす。
本発明のめつきの他の条件は従来のめつき方法
に準じて行なわれる。めつき温度は通常20〜35℃
でよく、高温になるほど光沢度は低下し、また光
沢剤の消費が大きい。低温では、液の電導度が低
下し、ひどい場合にはヤケが発生する。
本発明の平滑化剤と光沢剤を使用した場合、光
沢範囲が広く、例えばポリエチレングリコールを
用いた液と比較した場合、従来は0.5〜8.0A／ｄ
m2の光沢範囲が本発明では０〜12A／ｄm2に大き
く広がつている。
電着面の平滑性も向上し、表面粗さは比較例の
2.2μに比べて本発明では0.9〜1.3μである。めつき
時間は電流密度により異なるが、例えば電流密度
4.5A／ｄm2では１分間で1μの厚さとなりめつき
時間と電流密度を適切に調整することにより通常
使われる５〜30μ厚のめつきが効率よく大量に行
ない得る。
また従来問題が多かつた複雑な形状の被めつき
体の処理も容易となる。
〔実施例〕
基本液組成
硫酸銅（５水和物） 100，200ｇ／
硫酸 50，200ｇ／
塩化ナトリウム 100 mg／
にて、下記の平滑化剤、光沢剤を使用して、ハル
セル試験を行なつた結果を第１表に示す。
ハルセル試験条件は総電流2A、めつき時間10
分間、液温25℃、空気吹込み撹拌である。
光沢範囲は光沢を示す電流密度範囲で示し、表
面粗さは小坂研究所製表面粗さ計SE−３型で電
流密度2A／ｄm2の部分を測定した。
〔平滑化剤、光沢剤〕
本発明ジアミン 分子量6000
本発明ジカルボン酸 〃 6000
ポリエチレングリコール 〃 6000
PVP 〃 40000
VPとVAのコーポリマー
（ルビスコール、三菱油化製） モノマー比VP
／VA＝70／30
ベンゾインチオ尿素
ジエチルジチオカルバミン酸
The present invention relates to an acid plating solution used for copper plating. Important properties required for plating include the ability to plate a smooth surface and the ability to plate with a wide range of current densities. Even in plating solutions whose main components are copper sulfate and sulfuric acid, various substances with smoothing and brightening effects, such as sulfides, polyethers, thioureas, thiophosphates, thiocarbamates, etc., are used as additives. It has been used as. Although these brighteners and smoothing agents have shown certain effectiveness, various industrial demands are constantly calling for better additives. In particular, there are problems caused by differences in current density due to differences in the distance between the electrode and the surface to be plated, i.e., non-uniformity of plating depending on the location, which is a problem from both work efficiency and product value.
There is a need for a method that can provide smooth and uniform plating over a wider area. The present invention provides an acidic copper plating solution containing a novel smoothing agent that meets these demands. That is, the present invention provides a dicarboxylic acid represented by the general formula () HOOC・CH 2 O-(CH 2 CH 2 O) o -CH 2 COOH (where n = 0 to 1000) and/or the general formula () H 2 N-( CH2 ) 3 -O-( CH2CH2O )o- ( CH2 ) 3-
Diamine represented by NH 2 (however, n = 0 ~
1000) in an acidic copper plating solution containing copper sulfate and sulfuric acid as main components. The present invention further provides an acidic copper plating solution to which polyvinylpyrrolidone (PVP) and/or a copolymer of vinylpyrrolidone (VP) and vinyl acetate (VA) is added. Copper plating solutions containing copper sulfate and sulfuric acid as main components are widely used. The most basic liquid composition is 50 to 350 g of copper sulfate (pentahydrate), sulfuric acid
It is 30-250g/. The pH is usually 1 or less, a strong acidity, and free sulfuric acid is present. Copper ion sources other than copper sulfate include other copper salts, such as copper carbonate,
Copper pyrophosphate, copper borofluoride, etc. can also be used in combination. Sulfuric acid may also be used in combination with other acids such as phosphoric acid and fluoroboric acid. The plating solution may also be prepared by adding chlorides such as sodium chloride, ammonium chloride, potassium chloride, and hydrochloric acid as other components in an amount of 10 to 100 mg in terms of chlorine amount. The plating solution of the present invention uses a dicarboxylic acid (polyethylene oxydicarboxylic acid) represented by the above general formula () and/or a diamine (polyethylene oxydicarboxylic acid) represented by the above general formula ( oxydiamine). The influence of the degree of polymerization of polyethylene glycol chains on the plating effect does not change so drastically in the range of polymerization degree of 1000 or less, and an effect can be seen even at that degree of polymerization, but if the degree of polymerization is 3 to 150 (molecular weight 300 to
7000) is easy to handle. The amount of this dicarboxylic acid or diamine added is 0.01
An effect can be seen at g/g, but below that the smoothing effect is insufficient and the plated surface becomes rough. Addition amount
The range of 0.5 to 6 g/ is the most practical and preferred range, and the effect is clear. If the amount is increased further, the effect of increasing the amount up to about 30 g/g is recognized, but beyond that there is almost no difference in the effect and there is no economic advantage. The dicarboxylic acid and diamine of the present invention have an excellent smoothing effect, and are effective in improving the efficiency of plating work, treating plated objects with large irregularities, and improving current efficiency. However, this alone does not produce shiny copper plating, but it can be used for base copper plating (for example, copper plating as a base for nickel plating) or for functional plating such as printed wiring.
Satisfactory products can be obtained simply by using the dicarboxylic acids and/or diamines of the invention. Generally, the surface roughness is less than 1μ for the base material.
It is said that 1.5μ or less is sufficient for functional plating, and by using the smoothing agent of the present invention, it is possible to obtain products that are dense and have even plating that meet this standard over a wide current density range. can. When good gloss is required for a plated product, polyvinylpyrrolidone (PVP) or a copolymer of vinylpyrrolidone (VP) and vinyl acetate (VA) can be used in addition to the smoothing agent, dicarboxylic acid and diamine of the present invention. Use as a brightener. PVP is generally used in cosmetics, food additives, serum substitutes, etc., but until now it was not known to be effective as an additive for copper plating. A copolymer of VP and VA is sold as Rubiscoll (product name: Mitsubishi Yuka Co., Ltd.), for example, but it is used in cosmetics such as hair conditioners and as a thickener, and this is also related to glare. The application of is new. The monomer ratio of VP and VA is VP/VA=70/
A ratio of about 30 to 20/80 (weight ratio) is appropriate. The brightener of the present invention has the characteristic of producing a clear gloss over a wide current density range, and a certain effect can be recognized with addition of 0.01 g/g. Although the effect can be observed even with a smaller amount, the gloss is inferior and is not practical.
Also, if you add 10g or more, roughness, pitting, and uneven plating may increase, so for practical purposes, 0.01~
A range of 0.1g/ is preferred. The brightening agent of the present invention is useful when used in combination with the smoothing agent of the present invention, but does not exhibit sufficient brightening effect when used alone without a smoothing agent.
Abnormal precipitation such as pit formation may occur. Furthermore, when added in the same amount, PVP and homopolymers have a greater effect than copolymers of VP and VA. The brightener of the present invention includes the above-mentioned PVP and VP and VA.
Although it is desirable to use copolymers of PVP and
It is also possible to replace part or all of the copolymer of VP and VA. Particularly suitable are organic thio compounds such as benzothiourea, diethyldithiocarbamic acid, thioglycolic acid, and the like. In this case, these known brighteners are added at 0.0005 to 2 g/
, preferably 0.001 to 0.01 g/use. Too much of these brighteners also causes abnormal precipitation such as roughness and uneven plating. Other conditions for plating according to the present invention are carried out in accordance with conventional plating methods. Plating temperature is usually 20-35℃
However, the higher the temperature, the lower the gloss and the greater the consumption of brightener. At low temperatures, the conductivity of the liquid decreases, and in severe cases, it may cause burns. When the smoothing agent and brightener of the present invention are used, the gloss range is wide, for example, when compared with a solution using polyethylene glycol, the gloss range is 0.5 to 8.0 A/d.
m 2 gloss range is greatly expanded in the present invention from 0 to 12 A/dm 2 . The smoothness of the electrodeposited surface was also improved, and the surface roughness was lower than that of the comparative example.
In the present invention, it is 0.9 to 1.3μ compared to 2.2μ. The plating time varies depending on the current density, for example,
At 4.5 A/dm 2 , the thickness is 1 μ in 1 minute, and by appropriately adjusting the plating time and current density, the commonly used 5 to 30 μ thick plating can be efficiently performed in large quantities. Furthermore, it becomes easier to process objects with complicated shapes, which have been problematic in the past. [Example] A Hull cell test was conducted using the following smoothing agent and brightening agent with basic liquid composition copper sulfate (pentahydrate) 100,200g/sulfuric acid 50,200g/sodium chloride 100mg/ The results are shown in Table 1. Hull cell test conditions: total current 2A, plating time 10
Stir for 1 minute at a liquid temperature of 25°C with air blowing. The gloss range is indicated by the current density range that indicates gloss, and the surface roughness was measured at a current density of 2 A/dm 2 using a surface roughness meter SE-3 manufactured by Kosaka Institute. [Smoothing agent, brightening agent] Diamine of the present invention Molecular weight 6000 Dicarboxylic acid of the present invention 〃 6000 Polyethylene glycol 〃 6000 PVP 〃 40000 Copolymer of VP and VA (Ruviskol, manufactured by Mitsubishi Yuka) Monomer ratio VP / VA = 70/30 Benzothiourea Diethyldithiocarbamate
【表】【table】
Claims (1)
き液において、一般式 HOOC CH2O−（CH2CH2O）o−CH2COOHで表
わされるジカルボン酸及び／又は、一般式 H2N−（CH2）3−Ｏ−（CH2CH2O）o−（CH2）3−
NH2で表わされるジアミン（いずれもｎ＝０〜
1000）を0.01〜30ｇ／含有することを特徴とす
る酸性銅めつき液。 ２ 硫酸銅及び硫酸を主成分とする銅めつき液に
おいて、(A)一般式 HOOC CH2O−（CH2CH2O）o−CH2COOH （ｎ＝０〜1000）で表わされるジカルボン酸 及び／又は一般式 H2N−（CH2）3−Ｏ−（CH2CH2O）o−（CH2）3−
NH2 （ｎ＝０〜1000）で表わされるジアミン0.01〜30
ｇ／と、(B)ポリビニルピロリドンまたはビニル
ピロリドン／酢酸エチル共重合物を0.001〜10
ｇ／含有することを特徴とする酸性銅めつき
液。[Claims] 1. In an acidic copper plating solution containing copper sulfate and sulfuric acid as main components, a dicarboxylic acid represented by the general formula HOOC CH 2 O-(CH 2 CH 2 O) o -CH 2 COOH and/or , general formula H2N- ( CH2 ) 3 -O-( CH2CH2O ) o- ( CH2 ) 3-
Diamine represented by NH 2 (all n = 0 ~
An acidic copper plating solution characterized by containing 0.01 to 30 g/1000). 2. In a copper plating solution containing copper sulfate and sulfuric acid as main components, (A) dicarboxylic acid represented by the general formula HOOC CH 2 O-(CH 2 CH 2 O) o -CH 2 COOH (n = 0 to 1000) and/or the general formula H2N- ( CH2 ) 3 -O-( CH2CH2O ) o- ( CH2 ) 3-
Diamine 0.01-30 expressed as NH 2 (n=0-1000)
g/ and (B) polyvinylpyrrolidone or vinylpyrrolidone/ethyl acetate copolymer from 0.001 to 10
An acidic copper plating solution characterized by containing g/g/.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1886982A JPS58136794A (en) | 1982-02-10 | 1982-02-10 | Acidic copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1886982A JPS58136794A (en) | 1982-02-10 | 1982-02-10 | Acidic copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58136794A JPS58136794A (en) | 1983-08-13 |
| JPS6352120B2 true JPS6352120B2 (en) | 1988-10-18 |
Family
ID=11983541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1886982A Granted JPS58136794A (en) | 1982-02-10 | 1982-02-10 | Acidic copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58136794A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1978051A1 (en) | 2007-04-03 | 2008-10-08 | Rohm and Haas Electronic Materials, L.L.C. | Metal plating compositions and methods |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0419845A3 (en) * | 1989-09-05 | 1991-11-13 | General Electric Company | Method for preparing metallized polyimide composites |
| JP4534460B2 (en) * | 2002-11-11 | 2010-09-01 | 凸版印刷株式会社 | Copper plating hardness maintenance agent, copper plating method, and gravure plate and lens mold using the same |
| KR20140135007A (en) * | 2013-05-15 | 2014-11-25 | 삼성전기주식회사 | Copper plating solution composition for printed circuit board and via hole filling method using the same |
| WO2017059564A1 (en) * | 2015-10-08 | 2017-04-13 | Rohm And Haas Electronic Materials Llc | Copper electroplating baths containing reaction products of amines, polyacrylamides and bisepoxides |
-
1982
- 1982-02-10 JP JP1886982A patent/JPS58136794A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1978051A1 (en) | 2007-04-03 | 2008-10-08 | Rohm and Haas Electronic Materials, L.L.C. | Metal plating compositions and methods |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58136794A (en) | 1983-08-13 |
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