JPS6328877A - Electroless copper plating solution - Google Patents
Electroless copper plating solutionInfo
- Publication number
- JPS6328877A JPS6328877A JP17205786A JP17205786A JPS6328877A JP S6328877 A JPS6328877 A JP S6328877A JP 17205786 A JP17205786 A JP 17205786A JP 17205786 A JP17205786 A JP 17205786A JP S6328877 A JPS6328877 A JP S6328877A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating solution
- soln
- copper plating
- electroless 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 32
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 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 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 150000004808 allyl alcohols Chemical class 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- -1 copper sulfate Chemical class 0.000 abstract 1
- 239000003002 pH adjusting agent Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
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
- C23C18/405—Formaldehyde
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、めっき液の再生使用を数回にわたって繰り返
すことのできる無電解銅めっき液に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an electroless copper plating solution that can be recycled and used several times.
従来の技術
近年、無電解銅めっき液は、印刷配線板の製造やプラス
チックの金属化の分野で広くτ１１用されている。無電
解銅めっき液は、銅塩、銅の錯化剤、水酸化アルカリ、
および、還元剤としてホルムアルデヒドやほう素化水素
等からなる水溶液よりなる。このような公知のめっき液
から得られる析出銅は、−ｍに暗赤色を呈し電解銅と（
らべると、ａ械的な強度も劣る。また、めっき液は、め
っき反応中に銅の微粒子が生成して次第に自然分解する
ため使用を困難にしている。このような銅の色調の悪化
や自然分解現象は、めっき液を再生して使用する場合に
一層促進される傾向があるため、このめっき液の再生使
用を繰り返すことを困難にしている。このような問題を
解決する方法として特開昭５２−２１２２６号公報には
、この種のめっき液にアリルアルコール類を添加して析
出銅の伸びを改良する方法、特公昭４６−２１６１号公
報には、ジピリジルとフェナントロリンの添加剤をめっ
き液に添加することが述べられている。BACKGROUND OF THE INVENTION In recent years, electroless copper plating solutions have been widely used in the fields of printed wiring board manufacturing and plastic metallization. Electroless copper plating solution contains copper salt, copper complexing agent, alkali hydroxide,
and an aqueous solution containing formaldehyde, hydrogen borohydride, etc. as a reducing agent. The deposited copper obtained from such a known plating solution exhibits a dark red color at -m and is similar to electrolytic copper (
When compared, the mechanical strength is also inferior. Furthermore, the plating solution is difficult to use because fine copper particles are generated during the plating reaction and gradually decompose naturally. Such deterioration of copper color tone and natural decomposition phenomenon tend to be further accelerated when the plating solution is recycled and used, making it difficult to repeatedly recycle and use the plating solution. To solve this problem, Japanese Patent Application Laid-Open No. 52-21226 discloses a method of adding allyl alcohol to this type of plating solution to improve the elongation of deposited copper, and Japanese Patent Publication No. 46-2161 discloses describes adding dipyridyl and phenanthroline additives to the plating solution.
発明が解決しようとする問題点
しかしながら、前記の方法は、いずれもめっき液の安定
性も十分ではなく、とくにめっき液を再生して繰り返し
使用する場合には、自然分解が顕著になり、また、析出
銅の色も再生の度に、暗色化が進行するという間闘点を
有していた。Problems to be Solved by the Invention However, in all of the above methods, the stability of the plating solution is not sufficient, and especially when the plating solution is recycled and used repeatedly, natural decomposition becomes noticeable. The color of the deposited copper also had the problem of becoming darker each time it was regenerated.
本発明は、上記の問題点に鑑みて、めっき液の再生が数
回にわたって可能で、かつ、析出銅の光沢にも優れる無
電解銅めっき液を提供するものである。In view of the above-mentioned problems, the present invention provides an electroless copper plating solution that allows the plating solution to be regenerated several times and also provides excellent gloss of deposited copper.
問題点を解決するための手段
本発明は、上記のような欠点のない無電解銅めっき液を
提供することを意図するものであって、銅塩とその錯化
剤、水酸アルカリ、および、ホルムアルデヒドの水溶液
よりなる従来のめっき液に、アリルアルコールとジピリ
ジル、フェナントロリン、または、これらの誘導体のひ
とつ以上を同時に含めてなることを特徴とするめっき液
である。Means for Solving the Problems The present invention is intended to provide an electroless copper plating solution free from the above drawbacks, which comprises a copper salt, a complexing agent thereof, an alkali hydroxide, and This plating solution is characterized by containing allyl alcohol, dipyridyl, phenanthroline, or one or more of these derivatives simultaneously in a conventional plating solution consisting of an aqueous formaldehyde solution.
銅塩には、硫酸銅、硝酸銅、酢酸銅などの銅イオン源が
いずれも使用可能であり、その濃度範囲は、０．００７
〜０．１５モル／ｌが有効である。Any copper ion source such as copper sulfate, copper nitrate, or copper acetate can be used as the copper salt, and the concentration range is 0.007
~0.15 mol/l is effective.
銅の錯化剤には、酒石酸若しくは、その塩、あるいは、
エチレンジアミンテトラ酢酸（ＥＤＴＡ）若しくは、そ
の塩などが用いられるが、なかでもＥＤＴＡは常温から
１００℃付近の比較的に広い温度範囲で有効に使用でき
る点できわめて優れている。錯化剤の使用量は、銅イオ
ンを十分に錯体化するに足る量以上であればよいが、場
合によっては、銅の５〜６倍程度を用いることがある。Copper complexing agents include tartaric acid or its salts, or
Ethylenediaminetetraacetic acid (EDTA) or a salt thereof is used, but EDTA is particularly excellent in that it can be effectively used in a relatively wide temperature range from room temperature to around 100°C. The amount of the complexing agent to be used may be at least an amount sufficient to complex copper ions, but in some cases, about 5 to 6 times the amount of copper may be used.
水酸化アルカリは、めっき液のｐＨを調節するために用
いるもので、そのｐＨ域は、１１．５〜１３．０が適当
である。還元剤としては、ホルムアルデヒド、あるいは
、その代替としてのパラホルムアルデヒドは、０．０３
〜０．７５モル／１の濃度範囲が好ましい。Alkali hydroxide is used to adjust the pH of the plating solution, and its pH range is suitably from 11.5 to 13.0. As a reducing agent, formaldehyde or paraformaldehyde as a substitute thereof is 0.03
A concentration range of ˜0.75 mol/1 is preferred.
本発明において、添加剤として使用するアリルアルコー
ル類は、１〜１２０ｇ／ｌにわたって使用が可能であり
、好ましくは、５〜８０ｇ／ｊ！の濃度範囲である。ま
た、ジピリジル、フェナントロリン、または、これらの
誘導体は、０．００１〜１ｇ／ｌにわたって使用できる
が、最適濃度範囲は、０．０１〜０．３０ｇ／βである
。めっき液の操作の最適温度範囲は、２０〜９０℃であ
る。In the present invention, the allyl alcohol used as an additive can be used in a range of 1 to 120 g/l, preferably 5 to 80 g/l! concentration range. Also, dipyridyl, phenanthroline, or their derivatives can be used in a range of 0.001 to 1 g/l, but the optimum concentration range is 0.01 to 0.30 g/β. The optimum temperature range for operation of the plating solution is 20-90°C.
作用
上記の添加剤を添加した本発明の無電解銅めっき液は、
添加剤の相乗効果が発揮されて、めっき液の再生使用の
回数を格段に大きくすることができる。また、再生浴か
らの析出銅も新規に建浴しためっき浴からの析出銅に比
べてほとんど遜色のない銅光沢を有している。さらには
、数回にわたって再生した再生浴においても自然分解は
、きわめて少な（、作業性は良好である。めっき浴の再
生は、めっき液の成分がめつき反応によって枯渇し、銅
の析出がもはや行なわれなくなった時に行なうものであ
り、このときの銅めっき液を分析してめっき液の構成成
分である銅塩、ホルムアルデヒド、および、水酸化アル
カリの消費成分を補充してこれらを建浴時の初期濃度に
戻すことにあるのである。そのさい、ＥＤＴＡのような
錯化剤および添加剤は、めっき反応に直接的には関与し
ないので消費されず、とくに、補給の必要はない。Function: The electroless copper plating solution of the present invention containing the above-mentioned additives has the following properties:
The synergistic effect of the additives is exhibited, making it possible to significantly increase the number of times the plating solution can be recycled. Further, the copper deposited from the regenerated bath has a copper luster almost comparable to that of the copper deposited from a newly prepared plating bath. Furthermore, even in a regenerated bath that has been regenerated several times, spontaneous decomposition is extremely small (and workability is good. This is done when the copper plating solution has run out, and the consumed components of the plating solution, such as copper salt, formaldehyde, and alkali hydroxide, are replenished by analyzing them, and these are added to the initial state at the time of bath construction. At this time, complexing agents and additives such as EDTA do not directly participate in the plating reaction and are not consumed, and in particular, there is no need to replenish them.
実施例
本発明の銅めっき液は、次表に示すような特性を有する
ことが実験的に確認された。同表において使用されため
っき基本浴の組成は、硫酸銅０．０６４モル／１、ＥＤ
ＴＡｏ、０７５モル／１、苛性ソーダ０．０６５モル／
１１ホルムアルデヒド０．１２モル／２である。浴の温
度は、 ７５℃で行なった。浴の再生限度の回数は、既
述の方法でめっき液の再生を繰り返しているうちに、め
っき反応および副反応で生成する物質によってめっき液
の安定性が次第に低下して使用不可能になるまでの回数
である。EXAMPLE It was experimentally confirmed that the copper plating solution of the present invention had the characteristics shown in the following table. The composition of the basic plating bath used in the same table is copper sulfate 0.064 mol/1, ED
TAo, 075 mol/1, caustic soda 0.065 mol/1
11 formaldehyde 0.12 mol/2. The bath temperature was 75°C. The maximum number of times the bath can be regenerated is the number of times that the plating solution can be repeatedly regenerated using the method described above, until the stability of the plating solution gradually decreases due to the substances produced by the plating reaction and side reactions and becomes unusable. is the number of times.
（以 下 余 白）
上記の表において、実施例１ないし６は、本発明の添加
剤を用いた本発明の無電解銅めっき液の実施例である。(Left below) In the table above, Examples 1 to 6 are examples of the electroless copper plating solution of the present invention using the additive of the present invention.
比較例１ないし７は、１種類の添加剤を用いた従来の銅
めっき液、これらは、いずれも本発明の２種類の添加剤
のうちひとつを欠除している。比較例８は、添加剤のな
い従来の銅めっき液である。Comparative Examples 1-7 are conventional copper plating solutions using one type of additive; they all lack one of the two types of additives of the present invention. Comparative Example 8 is a conventional copper plating solution without additives.
発明の効果
本発明の無電解銅めっき液は、従来の銅めっき液に比較
して、再生による繰り返し使用できる点できわめて優れ
ており、再生浴からの析出銅の光沢も新しく建浴しため
っき浴からの析出銅と比較して殆んど遜色がない、また
、再生浴における自然分解鋼の量は、建浴時のそれと同
程度であり、再生を数回にわたって操り返しても十分安
定で、それだけ経済的である。Effects of the Invention The electroless copper plating solution of the present invention is extremely superior to conventional copper plating solutions in that it can be recycled and used repeatedly, and the shine of deposited copper from the regenerated bath is also superior to that of a newly prepared plating bath. In addition, the amount of naturally decomposed steel in the regenerated bath is comparable to that at the time of bath construction, and it is stable enough even after repeated regeneration several times. That's how economical it is.
Claims (1)
アルデヒドの水溶液からなる銅めっき基本液に、アリル
アルコール類とジピリジル、フェナントロリンまたはそ
れらの誘導体のひとつ以上を同時に含めてなることを特
徴とする無電解銅めっき液。A copper plating base solution consisting of an aqueous solution of a copper salt, its complexing agent, alkali hydroxide, and formaldehyde simultaneously contains allyl alcohol and one or more of dipyridyl, phenanthroline, or their derivatives. Electrolytic copper plating solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17205786A JPS6328877A (en) | 1986-07-22 | 1986-07-22 | Electroless copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17205786A JPS6328877A (en) | 1986-07-22 | 1986-07-22 | Electroless copper plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6328877A true JPS6328877A (en) | 1988-02-06 |
Family
ID=15934734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17205786A Pending JPS6328877A (en) | 1986-07-22 | 1986-07-22 | Electroless copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6328877A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320474A (en) * | 1989-06-15 | 1991-01-29 | Matsushita Electric Ind Co Ltd | Electroless copper plating solution |
| CN103243316A (en) * | 2013-04-22 | 2013-08-14 | 胜宏科技（惠州）股份有限公司 | Preservation method of recycled copper deposition liquid |
-
1986
- 1986-07-22 JP JP17205786A patent/JPS6328877A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0320474A (en) * | 1989-06-15 | 1991-01-29 | Matsushita Electric Ind Co Ltd | Electroless copper plating solution |
| CN103243316A (en) * | 2013-04-22 | 2013-08-14 | 胜宏科技（惠州）股份有限公司 | Preservation method of recycled copper deposition liquid |
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