JPS619578A - Method for chemically plating copper - Google Patents
Method for chemically plating copperInfo
- Publication number
- JPS619578A JPS619578A JP59127475A JP12747584A JPS619578A JP S619578 A JPS619578 A JP S619578A JP 59127475 A JP59127475 A JP 59127475A JP 12747584 A JP12747584 A JP 12747584A JP S619578 A JPS619578 A JP S619578A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating
- chemical
- copper plating
- chemical copper
- 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
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/187—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating means therefor, e.g. baths, apparatus
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は機械的性質に優れた銅めっき膜を析出させる化
学銅めっき方法に係り、特にプリント回路板製造の厚付
けめっきに好適な化学銅めっき方法に関する。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a chemical copper plating method for depositing a copper plating film with excellent mechanical properties, and in particular to a chemical copper plating method suitable for thick plating in the manufacture of printed circuit boards. Regarding the method.
従来より、銅塩、銅塩の錯化剤、銅塩の還元剤、PH調
整剤を基本成分とする化学銅めっき液が知られている。BACKGROUND ART Chemical copper plating solutions have been known that contain copper salts, complexing agents for copper salts, reducing agents for copper salts, and pH adjusters as basic components.
厚付けめっきにより、スルーホールめっきを行うプリン
ト配線板においては優れた機械的性質のめつき膜を与え
る化学銅めっき液が必要で、上述した基本成分の他にさ
らに添加剤を加えた組成の化学銅めっき液が知られてい
る。例えば、添加剤としてシアン化合物、2.2’−ビ
ピリジル、ポリエチレングリコールなどがある。A chemical copper plating solution that provides a plating film with excellent mechanical properties is required for printed wiring boards that perform through-hole plating due to thick plating. Copper plating solution is known. For example, additives include cyanide compounds, 2,2'-bipyridyl, polyethylene glycol, and the like.
しかしながらこれらの添加剤は取扱いが難しく、めっき
中に消費するので分析補給の必要もあった。However, these additives are difficult to handle and are consumed during plating, making it necessary to replenish them for analysis.
化学銅めっきで得る銅めっき皮膜の機械的性質を改善す
る方法が公表されている。その例は、特開昭54−19
430号公報に示されるように、上記主成分と2.2′
−ジピリジル、ポリエチレングリコール、アルカリ可溶
性無機ケイ素化合物を含む化学銅めっき液である。該化
学銅めっき液ではアルカリ可溶性無機ケイ素化合物を二
酸化ケイ素に換算し5〜100wq/L (8iとり、
テ0.08〜1、7 m mot/ L )含むと、化
学銅めっき皮膜の引張ル強さ50〜581!4 W /
1111” 、伸び4.4〜6.7%のものが得られ
るとしている。しかし、該化学銅めっき液を使用すると
きには次の欠点によって、使用不能であった。A method for improving the mechanical properties of copper plating films obtained by chemical copper plating has been published. An example of this is JP-A-54-19
As shown in Japanese Patent No. 430, the above main components and 2.2'
- A chemical copper plating solution containing dipyridyl, polyethylene glycol, and an alkali-soluble inorganic silicon compound. In the chemical copper plating solution, the alkali-soluble inorganic silicon compound is converted to silicon dioxide and is 5 to 100 wq/L (8i,
Including te 0.08~1.7 m mot/L), the tensile strength of the chemical copper plating film is 50~581!4 W/
1111" and an elongation of 4.4 to 6.7%. However, when using this chemical copper plating solution, it could not be used due to the following drawbacks.
化学銅めっき液を調製するには、上水道をイオン交換処
理したイオン交換水が用いられる。上水道には多量のケ
イ素化合物が含まれ、これが上水道中、イオン交換し難
い非イオン性ケイ素化合物もしくは重合陰イオンとして
存在する。このため−イオン交換処理しても、ケイ素化
合物は完全に除去し得す、イオン交換水中に含まれる。To prepare a chemical copper plating solution, ion-exchanged water obtained by ion-exchanging tap water is used. Waterworks contain a large amount of silicon compounds, which exist as nonionic silicon compounds or polymerized anions that are difficult to ion exchange. Therefore, even with ion exchange treatment, silicon compounds cannot be completely removed and are contained in ion exchange water.
発明者らの測定によれば、イオン交換水中のケイ素含有
量は3iとして、0.04〜0.43mmot/l(平
均0、2 mmot/ L )含まれる。ケイ素を含ま
ぬ水は蒸留によって得ることができる。しかし、化学銅
めっき液は・数100〜数1000tの規模で用いられ
るので、高価な蒸留水は使用できない。According to measurements by the inventors, the silicon content in ion-exchanged water is 0.04 to 0.43 mmot/l (average 0.2 mmot/L) as 3i. Silicon-free water can be obtained by distillation. However, since the chemical copper plating solution is used on a scale of several hundred to several thousand tons, expensive distilled water cannot be used.
化学銅めっきは繰シ返して使用されるので、これによっ
てめっき液中にケイ素が持ち込まれる。Since chemical copper plating is used repeatedly, silicon is introduced into the plating solution.
めっきを繰シ返して使用するとき、めっき液の主成分(
銅イオン、水酸イオン、ホルムアルデヒドなど)の濃度
を一定とするために、硫酸調水酸化ナトリウム、ホルマ
リンを溶解した水溶液として補給する。これら化合物の
補給量は、めっき1回を100−の面積にCuとして3
5μmめっきするとする場合、硫酸銅: 0.05 m
ot/ As水酸化ナトリウム: 0.2 moZ/
Z %ホルムアルデヒド=0.1mot/L、全水溶液
量:めつき液1を当り、0.1tとなる。例えば水酸化
ナトリウムのJIS規格(1級)によれば、水酸化す)
IJウム中の8fCh含有量は0.04%以下とされ
ているが、その他の化合物では規格化されておらず、8
10*は強熱残分もしくは硫化物で沈殿しない物質とし
て規制され、硫酸鋼二0.3%、ホルマリン:0.01
%である。よって、補給によって、Siは約0.3mm
ot/を持ち込まれ可能性がある。When plating is used repeatedly, the main component of the plating solution (
To maintain a constant concentration of copper ions, hydroxide ions, formaldehyde, etc., an aqueous solution containing sulfuric acid-containing sodium hydroxide and formalin is replenished. The replenishment amount of these compounds is 3 as Cu per plating area of 100
For 5 μm plating, copper sulfate: 0.05 m
ot/ As Sodium hydroxide: 0.2 moZ/
Z % Formaldehyde = 0.1 mot/L, total amount of aqueous solution: 1 t of plating solution is applied, 0.1 t. For example, according to the JIS standard (grade 1) for sodium hydroxide, hydroxide
The 8fCh content in IJium is said to be 0.04% or less, but it is not standardized for other compounds, and 8fCh content is
10* is regulated as a substance that does not precipitate as an ignition residue or sulfide, sulfuric acid steel 20.3%, formalin: 0.01
%. Therefore, by replenishment, Si is reduced by approximately 0.3 mm.
There is a possibility that ot/ may be brought in.
一方、めっき液の建浴は、主成分として、硫酸銅: 0
.04 mot/ t、水酸化ナトリウム:0.4mo
t/ t 、ホルマリン: 0.04 mot/ l、
銅イオンの錯化剤: 0.12 mol/ lを、前記
イオン交換水に溶かすことによってなされる。On the other hand, the main component of the plating solution is copper sulfate: 0.
.. 04 mot/t, sodium hydroxide: 0.4 mo
t/t, formalin: 0.04 mot/l,
Copper ion complexing agent: This is done by dissolving 0.12 mol/l in the ion-exchanged water.
銅イオンの錯化剤としてEDTA−2Naを代表すると
JIS規格(特級)の強熱成分は&8%である。よって
、建浴したのみで、めっき液中のStの最大含有量はs
、 i m mo4/lとなる。よって、めっきを繰シ
返すと、siのめっき液中の含有量は次式に従って増加
する。As a representative copper ion complexing agent, EDTA-2Na has an ignition component of &8% according to the JIS standard (special grade). Therefore, the maximum content of St in the plating solution is s after just preparing the bath.
, i m mo4/l. Therefore, when plating is repeated, the content of Si in the plating solution increases according to the following equation.
めっき液iz中のS i (m moL/1)=5.1
+0.3n−(1) (ただし、nはめっき回数)以
上から明らかなように、めっき液中へ不純物としてSi
が含有される要素は極めて多い。特開昭54−1943
0号公報によれば、式(1)よシ、めっき1回目(n=
1 )から、その最適量(Siとして0.08〜1.7
m mol/ L )を越える可能性があシ、その確
率も極めて大きい。純度の良い薬品を用いることはめつ
きコストを著しく高くすることになるので、JIS規格
以下の工業薬品が用いられる。よって、不純物としての
Siの含有は式(1)よシ、大幅に増大する。よって、
従来技術によれば、極めて高価な水と薬品を用い、かつ
厳密なる液成分濃度の管理を行なわないと、めっき初回
から目的を達成できるものではなかった。また、偶然め
っき可能となったとしても、Si濃度によってめっき皮
膜の特性が鋭敏に影響されるので、品質管理上、工業的
に最も重要な特性の安定化を得ることができなかった。S i (m mol/1) in plating solution iz = 5.1
+0.3n-(1) (where n is the number of times of plating) As is clear from the above, Si is introduced into the plating solution as an impurity.
contains an extremely large number of elements. Japanese Patent Publication No. 54-1943
According to Publication No. 0, according to formula (1), the first plating (n=
1), its optimum amount (0.08 to 1.7 as Si)
m mol/L), and that probability is also extremely large. Since using chemicals of high purity will significantly increase the plating cost, industrial chemicals that meet JIS standards or lower are used. Therefore, the content of Si as an impurity increases significantly compared to formula (1). Therefore,
According to the prior art, the objective could not be achieved from the first plating without using extremely expensive water and chemicals and strictly controlling the concentration of liquid components. Furthermore, even if plating were to be possible by chance, the properties of the plating film would be sensitively affected by the Si concentration, and it would not be possible to stabilize the properties, which is the most important industrially in terms of quality control.
さらに、手段を選ばず高価な最純枠の水と薬品を用いて
めっきする場合でも、次なる問題が生じた。従来技術に
よれば、めっき液中のSi濃度は鋭敏にめっき皮膜の特
性に影響するので厳密に19i濃度を管理する必要があ
る。3iの分析は極めて難しく、特に化学銅めっきのよ
うにNaが共存(液中NaはSiの235倍)すると、
siの分析は難しいと言われる。原子吸光法によっても
、その検出感度は約2 m mat/ lと言われる。Furthermore, even when plating is carried out using the most expensive pure water and chemicals, the following problem occurs. According to the prior art, the 19i concentration must be strictly controlled because the Si concentration in the plating solution acutely affects the characteristics of the plating film. Analysis of 3i is extremely difficult, especially when Na coexists as in chemical copper plating (Na in the liquid is 235 times as much as Si).
Analyzing SI is said to be difficult. The detection sensitivity of atomic absorption spectrometry is also said to be about 2 mmat/l.
よって、Si含有量が、検出感度板fのとき、精度の悪
い分析試料の濃縮操作を併用することになシ、厳密な分
析が不可能となった。この点からも、S3含有量の低い
めっき液は工業的に実現できるものではなかった。Therefore, when the Si content was at the detection sensitivity plate f, it became impossible to conduct a rigorous analysis unless an inaccurate analysis sample concentration operation was also used. Also from this point of view, a plating solution with a low S3 content has not been industrially possible.
本発明の目的はめっき液管理が容易でかつ機械的に優れ
ためつき膜の得られる化学銅めっき方法を提供するにあ
る。An object of the present invention is to provide a chemical copper plating method that allows easy control of the plating solution and provides a mechanically excellent matted film.
本発明の特徴とするところは銅塩、銅塩の錯化剤、銅塩
の還元剤、pH調整剤を含む化学銅めっき液を用いて化
学銅めっきを行う方法において、該化学銅めっき液に添
加剤として可溶性無機ケ身素化合物を加え、且つ該化学
銅めっき液に酸素含有ガスを吹込むこともしくは過酸化
水素、過硫酸塩などの酸化剤を添加することの少なくと
もいずれか一方を適用して化学銅めっきを行うところに
ある。The present invention is characterized by a method of performing chemical copper plating using a chemical copper plating solution containing a copper salt, a complexing agent for the copper salt, a reducing agent for the copper salt, and a pH adjuster. A soluble inorganic silicon compound is added as an additive, and at least one of blowing an oxygen-containing gas into the chemical copper plating solution or adding an oxidizing agent such as hydrogen peroxide or persulfate is applied. This is where chemical copper plating is performed.
素含有ガスもしくは酸化剤の少なくともいずれか一方を
併用することによって目的が達成できる。The purpose can be achieved by using at least one of an element-containing gas and an oxidizing agent.
従来よシ、水ガラス、メタケイ酸ナトリウム。Traditionally, water glass, sodium metasilicate.
オルトケイ酸゛ナトリウムの無機ケイ素化合物を化学銅
めっき液に添加することは知られているが、これだけで
は化学銅めっき液の安定性が不十分で本発明のように厚
付は化学銅めっきを行、うときはめつき半ばにしてめっ
き液が不安定になって十分な厚さのめっきを行うことが
実質的に不可能になる。この点は、金属表面技術誌、第
16巻、11月号(1965年)にめっき液の自己分解
を防止するのに効果はあるがめつき槽の底部に銅が析出
することが記載されていることから明らかである。It is known that an inorganic silicon compound such as sodium orthosilicate is added to a chemical copper plating solution, but this alone does not provide sufficient stability for the chemical copper plating solution, and as in the present invention, chemical copper plating is used for thick plating. When plating is done halfway through plating, the plating solution becomes unstable and it becomes virtually impossible to plate to a sufficient thickness. Regarding this point, the Metal Surface Technology Magazine, Volume 16, November issue (1965) states that although it is effective in preventing the self-decomposition of the plating solution, copper is deposited at the bottom of the plating bath. It is clear from this.
また、上記引例記載の化学銅めっき液から得られためつ
き膜についてめっき膜の物性を測定したが膜は脆く十分
な機械特性を示さなかった。Furthermore, physical properties of the plated film obtained from the chemical copper plating solution described in the above cited reference were measured, but the film was brittle and did not exhibit sufficient mechanical properties.
一方、化学銅めっき液に酸素含有ガス例えば空気を吹込
むことは特公昭36−9063号公報に記載されておシ
、化学銅めっき液の安定化に効果がおることか知られて
いる。しかし、酸素含有ガスを吹込むだけではめつき膜
の機械品性質の大幅向上は不可能である。On the other hand, blowing an oxygen-containing gas such as air into the chemical copper plating solution is described in Japanese Patent Publication No. 36-9063, and is known to be effective in stabilizing the chemical copper plating solution. However, it is not possible to significantly improve the mechanical properties of the plated film simply by blowing in oxygen-containing gas.
本発明は可溶性無機ケイ素化合物を添加し、且つ、酸素
含有ガスもしくは酸化剤の少なくとも一方を併用するこ
とによって、めっき膜の機械的性質が大幅に改善できる
という相乗効果を見出したことに基づくものである。The present invention is based on the discovery of a synergistic effect in which the mechanical properties of a plated film can be significantly improved by adding a soluble inorganic silicon compound and using at least one of an oxygen-containing gas or an oxidizing agent. be.
本発明において適用可能な可溶性無機ケイ素化合物とし
ては水ガラス、メタケイ酸ナトリウムなどのメタケイ酸
塩、オルトケイ酸ナトリウムなどのオルトケイ酸塩、ケ
イ酸ナトリウムやケイ酸カリウムなどのケイ酸塩、ポリ
ケイ酸ナトリウムなどのポリケイ酸塩、二酸化ケイ素、
ケイ素含有ガスなどがあげられる。めっき膜の機械的性
質向上゛に効果のある添加量としてはケイ素量として1
0my/を以上必要であシ、それ以下では顕著な効果は
期待できない。Examples of soluble inorganic silicon compounds that can be used in the present invention include water glass, metasilicates such as sodium metasilicate, orthosilicates such as sodium orthosilicate, silicates such as sodium silicate and potassium silicate, and sodium polysilicate. polysilicate, silicon dioxide,
Examples include silicon-containing gas. The amount of silicon added that is effective in improving the mechanical properties of the plating film is 1.
0 my/ or more is necessary; if it is less than that, no significant effect can be expected.
本発明で使用する可溶性無機ケイ素化合物は取扱上はと
んど問題ない。またBODやCoDO問題も無く、めっ
き中にほとんど消費しない。更に安価であるという点も
工業的には大きなメリットである。The soluble inorganic silicon compound used in the present invention causes no problems in handling. Furthermore, there are no BOD or CoDO problems, and almost no energy is consumed during plating. Furthermore, the fact that it is inexpensive is also a great industrial advantage.
本発明において、酸素含有ガスは一般的には空気が用い
られ、空気吹込みによって化学銅めっき液の安定性が保
たれる。また酸素含有ガスとしては純酸素も当然ながら
適用できる。また、酸化剤は過酸化水素、過硫酸カリウ
ムなどの過硫酸塩が適用できる。それらの添加量は酸化
剤の種類によつ“でも異るが約0.5g/を以上必要で
おる。それ以下では化学銅めっき液の安定性は十分保つ
ことができず、実質的に厚付けめっきを行うことは不可
能である。過酸化水素、過硫酸塩も取扱いは比較的容易
であシ、BOD−?COD上もあまシ問題とならない。In the present invention, air is generally used as the oxygen-containing gas, and the stability of the chemical copper plating solution is maintained by blowing the air into it. Naturally, pure oxygen can also be used as the oxygen-containing gas. Furthermore, persulfates such as hydrogen peroxide and potassium persulfate can be used as the oxidizing agent. The amount of these additives varies depending on the type of oxidizing agent, but it is necessary to add at least about 0.5 g/kg. If the amount is less than that, the stability of the chemical copper plating solution cannot be maintained sufficiently, and the thickness of the chemical copper plating solution will be substantially reduced. It is impossible to carry out additional plating.Hydrogen peroxide and persulfate are also relatively easy to handle and do not cause any problem on BOD-COD.
本発明において、めっき温度は50C以上が好ましく、
500未満では十分に良好な機械的性質のめつき膜が得
られない。In the present invention, the plating temperature is preferably 50C or higher,
If it is less than 500, a plated film with sufficiently good mechanical properties cannot be obtained.
更に1本発明で使用する化学銅めっき液は銅塩、銅塩の
錯化剤、銅塩の還元剤、pH調整剤を基本成分とするが
、銅塩は硫酸銅、塩化第二銅、酢酸銅など公知のものが
使用できる。′銅塩の錯化剤は>N −C−C−kを骨
格とするものが好適であシ、エチレンジアミン四酢酸、
N−ヒドロキシエチルエチレンジアミン三酢酸、1,2
−ジアミノプロパン四酢酸、ジエチレントリアミン五酢
酸、シクロヘキサンジアミン四酢酸などが適用できる。Furthermore, the basic components of the chemical copper plating solution used in the present invention are a copper salt, a complexing agent for the copper salt, a reducing agent for the copper salt, and a pH adjuster. Known materials such as copper can be used. 'The copper salt complexing agent is preferably one having a >N -C-C-k skeleton, ethylenediaminetetraacetic acid,
N-hydroxyethylethylenediaminetriacetic acid, 1,2
-Diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, etc. are applicable.
トリエタノールアミン、イミノ三酢酸、イミノ三酢酸な
どのモノアミン、あるいはロッセル塩などを使用した場
合は十分な機械的性質のめつき膜を得ることができなか
ったシ、またはめつき液の安定性が不十分で実質的な厚
付けめっきができなかったシする問題が生じる。銅塩の
還元剤は一般的に使用されるホルマリンが好適であシ、
更にpH調整剤には水酸化ナトリウムが適用できる。When using monoamines such as triethanolamine, iminotriacetic acid, iminotriacetic acid, or Rossel's salt, it may not be possible to obtain a plated film with sufficient mechanical properties, or the stability of the plating solution may deteriorate. A problem arises in which plating is insufficient and substantially thick plating cannot be achieved. As the reducing agent for the copper salt, formalin, which is commonly used, is suitable;
Furthermore, sodium hydroxide can be used as a pH adjuster.
次に本発明を実施例によシ具体的に説明する。 Next, the present invention will be specifically explained using examples.
実施例1〜13
表面を滑らかに研磨したステンレススチール板を脱脂し
、めっき反応の開始剤であるパラジウムを該表面に付着
させた。次に、第1表に示した化学銅めっき液組成、な
らびにめっき条件下で化学銅めっきを行い、約30μm
の厚さのめつき膜を得た。このめっき膜をステンレスス
チール板よシ剥離して幅105mに切断し、初期の引張
間隔を50■として東洋測量社製の引張試験機によシ破
断までの伸び率と引張強度とを測定した。その結果を第
2表に示した。Examples 1 to 13 A stainless steel plate whose surface was polished smoothly was degreased, and palladium, which is an initiator for a plating reaction, was attached to the surface. Next, chemical copper plating was performed using the chemical copper plating solution composition and plating conditions shown in Table 1, and the thickness was approximately 30 μm.
A plated film with a thickness of . This plating film was peeled off from a stainless steel plate and cut to a width of 105 m, and the elongation rate and tensile strength until break were measured using a tensile tester manufactured by Toyo Sokkyo Co., Ltd. with an initial tension interval of 50 cm. The results are shown in Table 2.
比較例1〜6
第1表の比較例欄に記載した条件下で、実施例1〜13
と同様にめっきし、評価した。その結果を第2表に合わ
せて示した。Comparative Examples 1 to 6 Under the conditions described in the Comparative Examples column of Table 1, Examples 1 to 13
It was plated and evaluated in the same manner as above. The results are also shown in Table 2.
実施例、比較例の結果を記載した第2表から明らかなよ
うに、本発明の化学銅めっき法によシ、機械的性質の優
れためつき膜を得ることができる。As is clear from Table 2, which lists the results of Examples and Comparative Examples, the chemical copper plating method of the present invention makes it possible to obtain a laminated film with excellent mechanical properties.
また、化学銅めっき液の安定性も良好に保たれ、実質的
な厚付けめっきが可能である。In addition, the stability of the chemical copper plating solution is maintained well, and substantial thick plating is possible.
Claims (1)
剤を含む化学銅めつき液を用いて化学銅めつきを行う方
法において、前記化学銅めつき液に添加剤として可溶性
無機ケイ素化合物を加え、かつこのめつき液に酸素含有
ガスを吹込み、及び/または酸化剤を添加することを特
徴とする化学銅めつき方法。 2、特許請求の範囲第1項記載において、添加剤の含有
量がケイ素量として10mg/l以上であることを特徴
とする化学銅めつき方法。 3、特許請求の範囲第1項記載において、めつき温度は
50℃以上であることを特徴とする化学銅めつき方法。 4、特許請求の範囲第1項記載において、銅塩の錯化剤
は>N−C−C−N<という化学構造を有することを特
徴とする化学銅めつき方法。[Claims] 1. A method of performing chemical copper plating using a chemical copper plating solution containing a copper salt, a complexing agent for the copper salt, a reducing agent for the copper salt, and a pH adjuster, wherein the chemical copper A chemical copper plating method characterized by adding a soluble inorganic silicon compound as an additive to a plating solution, blowing an oxygen-containing gas into the plating solution, and/or adding an oxidizing agent. 2. The chemical copper plating method according to claim 1, characterized in that the content of the additive is 10 mg/l or more as silicon content. 3. A chemical copper plating method according to claim 1, characterized in that the plating temperature is 50° C. or higher. 4. A chemical copper plating method as set forth in claim 1, wherein the copper salt complexing agent has a chemical structure of >N-C-C-N<.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59127475A JPS619578A (en) | 1984-06-22 | 1984-06-22 | Method for chemically plating copper |
KR1019850004219A KR920002710B1 (en) | 1984-06-18 | 1985-06-14 | Chemical copper plating method |
US06/746,099 US4632852A (en) | 1984-06-18 | 1985-06-18 | Process for electroless copper plating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59127475A JPS619578A (en) | 1984-06-22 | 1984-06-22 | Method for chemically plating copper |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS619578A true JPS619578A (en) | 1986-01-17 |
JPH0222153B2 JPH0222153B2 (en) | 1990-05-17 |
Family
ID=14960847
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59127475A Granted JPS619578A (en) | 1984-06-18 | 1984-06-22 | Method for chemically plating copper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS619578A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6035540B2 (en) * | 2012-12-21 | 2016-11-30 | 奥野製薬工業株式会社 | Conductive film forming bath |
US9951433B2 (en) | 2014-01-27 | 2018-04-24 | Okuno Chemical Industries Co., Ltd. | Conductive film-forming bath |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6337187A (en) * | 1986-08-01 | 1988-02-17 | Matsushita Electric Ind Co Ltd | Liquid crystal display device |
-
1984
- 1984-06-22 JP JP59127475A patent/JPS619578A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6337187A (en) * | 1986-08-01 | 1988-02-17 | Matsushita Electric Ind Co Ltd | Liquid crystal display device |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6035540B2 (en) * | 2012-12-21 | 2016-11-30 | 奥野製薬工業株式会社 | Conductive film forming bath |
US10036097B2 (en) | 2012-12-21 | 2018-07-31 | Okuno Chemical Industries Co., Ltd. | Conductive coating film forming bath |
US9951433B2 (en) | 2014-01-27 | 2018-04-24 | Okuno Chemical Industries Co., Ltd. | Conductive film-forming bath |
Also Published As
Publication number | Publication date |
---|---|
JPH0222153B2 (en) | 1990-05-17 |
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