JPS5923862A - Electroless copper plating solution and its manufacture - Google Patents
Electroless copper plating solution and its manufactureInfo
- Publication number
- JPS5923862A JPS5923862A JP13259782A JP13259782A JPS5923862A JP S5923862 A JPS5923862 A JP S5923862A JP 13259782 A JP13259782 A JP 13259782A JP 13259782 A JP13259782 A JP 13259782A JP S5923862 A JPS5923862 A JP S5923862A
- Authority
- JP
- Japan
- Prior art keywords
- soln
- solution
- copper plating
- plating solution
- ions
- 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
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
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】
本発明は、無電解な（・しは自己触媒作用による銅めっ
き液に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electroless (or autocatalytic) copper plating solution.
一般に、無電解ないしは自己触媒作用による金属析出液
は、電気めっき液と異なり、パイプの内面や小孔の内部
にまで均一にめっきできること、プラスチック等の不導
体の表面にもめつきできることから電気めっきの下地と
して、印刷配線板等に広く利用されている。最近、印刷
配線板の製造方法として、絶縁板に無電解銅めっきだけ
で導電回路を形成する方法、（・わゆるアディティブプ
ロセスが採用されるようになっている。アディティブプ
ロセスに使用される無電解銅めっき液の代表的な溶液は
、溶媒としての水と、析出させようとする金属イオン（
銅イオン）の供給源と、析出させようとする金属イオン
の錯化剤と、金属イオンを金属に還元する還元剤とＰＨ
ｐｌ整剤とから成って（・る。In general, electroless or autocatalytic metal deposition solutions are different from electroplating solutions because they can uniformly plate the inner surfaces of pipes and small holes, and they can also plate the surfaces of nonconductors such as plastics. It is widely used as a base for printed wiring boards, etc. Recently, as a manufacturing method for printed wiring boards, a method in which conductive circuits are formed only by electroless copper plating on an insulating board (so-called additive process) has been adopted. A typical copper plating solution consists of water as a solvent and metal ions (
a source of copper ions), a complexing agent for the metal ions to be precipitated, a reducing agent to reduce the metal ions to metal, and a pH
It consists of pl adjustment agent (・ru.
ところが、無電解銅めっき液は銅の析出速度が遅い。こ
のため、厚（・析出膜の形成を必要とする場合には、プ
ラスチックなどの被めっき物を無電解めっき液に比較的
長く浸漬しておかなければならない。銅の析出速度を加
速する方法は、周知のように、通常無電解銅めっき液の
Ｐ Ｈ値を高アルカリ性に維持すると共に、銅イオンの
濃度とホルムアルデヒドのような銅イオンの還元剤の濃
度を高くし、無電解銅めっき液の温度を高く保持するこ
とがなされている。However, the electroless copper plating solution has a slow copper deposition rate. For this reason, if it is necessary to form a thick deposited film, the object to be plated, such as plastic, must be immersed in the electroless plating solution for a relatively long time. As is well known, the PH value of the electroless copper plating solution is usually maintained at a highly alkaline level, and the concentration of copper ions and the concentration of a copper ion reducing agent such as formaldehyde are increased to improve the electroless copper plating solution. Efforts are being made to keep the temperature high.
しかし、これらの従来の方法では、（イ）一般に銅めっ
き液を不安定状態にする、（ロ）ある（・は銅析出膜の
引張り強さ、伸び率等の物性に逆効果をもたらす、かの
（・ずれかの欠点を示す。However, these conventional methods (a) generally make the copper plating solution unstable; (b) have an adverse effect on the physical properties such as tensile strength and elongation of the copper deposited film; (・Indicates one of the disadvantages.
前者の無電解めっき液の安定度を促進する従来の方法に
は、シアン化合物、２−メルカプトベンゾチアゾール等
の化合物をめっき液に添加する方法があり周知であるが
、これらの化合物は、めっき液に添加されると銅の析出
速度を著しく低下させる欠点がある。A conventional method for promoting the stability of the former electroless plating solution is to add compounds such as cyanide and 2-mercaptobenzothiazole to the plating solution. It has the disadvantage that when added to copper, it significantly reduces the copper precipitation rate.
本発明の目的は、前述した従来欠点を改良し、特に安定
でしかも物性（引張り強さ、伸び率）の優れた析出膜を
与える無電解銅めっき液を提供することにある。An object of the present invention is to provide an electroless copper plating solution that improves the above-mentioned conventional drawbacks and provides a deposited film that is particularly stable and has excellent physical properties (tensile strength, elongation).
本発明の無電解銅めっき液は、水と、析出されるべき銅
イオンと、銅イオンに対する錯化剤と還元剤およびＰＨ
調整剤とから成る無電解銅めっき液に、α−α′−ジピ
リジルーアルコール溶液と硫化カリウムまたは硫化ナト
リウム水溶液から成り、特にα、α′−ジピリジルーア
ルコール溶液と硫化カリウムまたは硫化ナトリウム水溶
液を混合した後、混合溶液ＯＰＨ値を１２．５以上に混
合溶液が透明になるまで保持した後、混合溶液のＰＨ値
を２〜１２．５に再調整した混合溶液とシアン化合物を
添加したことを％徴とする。The electroless copper plating solution of the present invention comprises water, copper ions to be deposited, a complexing agent and a reducing agent for the copper ions, and a pH
An electroless copper plating solution consisting of a conditioning agent is mixed with an α-α′-dipyridyl-alcohol solution and a potassium sulfide or sodium sulfide aqueous solution, especially an α,α′-dipyridyl-alcohol solution and a potassium sulfide or sodium sulfide aqueous solution. After that, the OPH value of the mixed solution was maintained at 12.5 or more until the mixed solution became transparent, and then the mixed solution with the PH value readjusted to 2 to 12.5 and the addition of cyanide were added. be a sign.
本発明にお（・て、無電解銅めっき液の銅イオン源とし
ては、硫酸鋼あるいは塩化第二銅が使用され、その添加
量は、５〜２０５’／−ｅが適当である。In the present invention, sulfuric acid steel or cupric chloride is used as a copper ion source in the electroless copper plating solution, and the appropriate amount of addition is 5 to 205'/-e.
銅イオンの錯化剤としては、エチレンジアミンテトラ酢
酸のナトリウム塩、ロッセル塩、Ｎ、Ｎ、Ｎ／。Examples of complexing agents for copper ions include sodium salt of ethylenediaminetetraacetic acid, Rossel's salt, N, N, N/.
Ｎ′−テトラキス−２（２−ヒドロキシプロピル）エチ
レンジアミン等の銅イオンを錯化する化合物を単独また
は２種以上混合して使用される。その添加量は、銅イオ
ンを錯化するのに十分な量、通常銅イオンのグラム肖量
の１〜３倍の量が適当である。還元剤としては、ホルム
アルデヒドあるいはホルムアルデヒドの早期硬化物、例
えばパラホルムアルデヒド等が適当である。ＰＨ調整剤
としては、水酸化ナトリウムあるいは水酸化カリウムが
適当で、めっき液のＰＨ値を１１．５〜１２，５に調整
する量が添加される。Compounds that complex copper ions, such as N'-tetrakis-2(2-hydroxypropyl)ethylenediamine, are used alone or in combination of two or more. The amount added is sufficient to complex the copper ions, usually 1 to 3 times the gram weight of the copper ions. As the reducing agent, formaldehyde or a prematurely cured product of formaldehyde, such as paraformaldehyde, is suitable. As the pH adjuster, sodium hydroxide or potassium hydroxide is suitable, and is added in an amount to adjust the pH value of the plating solution to 11.5 to 12.5.
本発明の無電解銅めρき液には、前述のような成分の他
に、さらに次で述べる方法で調整されるσｔα′−ジピ
リジル、アルコール、硫化カリウムとＰＨ調整剤とから
成る混合液１〜１０ ｍＪ３／Ｊ３とシアン化ナトリウ
ム１０〜５０ｍｔＡが添加される。In addition to the above-mentioned components, the electroless copper plating solution of the present invention further contains a mixed solution 1 consisting of σtα'-dipyridyl, alcohol, potassium sulfide, and a PH adjuster, which are prepared by the method described below. ~10 mJ3/J3 and 10-50 mtA of sodium cyanide are added.
α、σｌ−ジピリジル１〜１ｏｙ−を１００ｍノのエチ
ルアルコールに溶解して、α、α −ジピリジル−アル
コール溶液を準備する。次に硫化カリウム０．０１〜０
．１ｙ−を７００ｍｐの純水に溶解し、硫化カリウム水
溶液を準備する。次に、α、α′−ジピリジルーアルコ
ール溶液と硫化カリウム水溶液を混合し、この混合液の
ＰＨ値を１２５以上にする。An α,α-dipyridyl-alcohol solution is prepared by dissolving 1 to 1 oy of α,σl-dipyridyl in 100 m of ethyl alcohol. Next, potassium sulfide 0.01-0
．． 1y- in 700 mp pure water to prepare a potassium sulfide aqueous solution. Next, the α,α'-dipyridyl alcohol solution and the potassium sulfide aqueous solution are mixed, and the pH value of this mixture is adjusted to 125 or more.
この時点では、混合溶液は白濁している。混合溶液のＰ
Ｈ値を白濁が消失するまで１２．５以上に保持する。混
合溶液を４０ｒ以上に加温すると、混合溶液の白濁の消
火を促進することができる。混合溶液の白濁が消失した
ら硫酸でＰＨ値を２〜１２．５に調整し、純水を加えて
全量を１１とする。この時、混合溶液は桃色〜赤色透明
を呈している。なお、アルコールはα、α′−ジピリジ
ルの溶解を促進し、硫化カリウムまたは硫化ナトリウム
とα。At this point, the mixed solution is cloudy. P of mixed solution
Maintain the H value at 12.5 or higher until the cloudiness disappears. When the mixed solution is heated to 40 r or more, extinguishing of the cloudiness of the mixed solution can be promoted. When the cloudiness of the mixed solution disappears, adjust the pH value to 2 to 12.5 with sulfuric acid, and add pure water to bring the total volume to 11. At this time, the mixed solution has a transparent pink to red color. In addition, alcohol promotes the dissolution of α,α′-dipyridyl, and α,α′-dipyridyl is dissolved in potassium sulfide or sodium sulfide.
α′−ジピリジルの反応を促進するために使用される。Used to accelerate the reaction of α'-dipyridyl.
次に、本発明を実施例により詳細に説明する。Next, the present invention will be explained in detail using examples.
表面を滑らかに研磨したステンレス板の表面を脱脂し、
塩化パラジウムと塩化第一錫の混合塩の脱脂し、塩化パ
ラジウムと塩化第一錫の混合塩の酸性水溶液で活性化処
理をした。次に、第１表に示される各組成のめっき液で
、液温７０Ｃにしてめっきを行な（・３５〜４０μｍの
厚さの銅析出膜を得た。めっき速度は、所定時間内に付
着した皮膜質量から求めた。この後、ステンレス板より
剥離した銅析出膜を幅Ｉ Ｑ ｒｒｒｍ 、長さ８０ｗ
ｎに切断した試料を引張り試験機で抗張力、伸び率を測
定し以上、本発明の実施例（第１表）から明らかなよう
に、シアン化合物と、α、α′−ジピリジルとアルコー
ルと硫化カリウムから成る混合溶液と、タリウム化合物
の３者を同時に添加しためつき液（ＮＱ１〜Ｎ１２）か
ら得られる銅析出膜は、添加し１工（・めっき液（陶３
〜陥８）から得られる銅析出膜より、物性が優れている
ことが判明した。Degrease the surface of the stainless steel plate, which has been polished to a smooth surface.
A mixed salt of palladium chloride and stannous chloride was degreased and activated with an acidic aqueous solution of a mixed salt of palladium chloride and stannous chloride. Next, plating was performed using a plating solution with each composition shown in Table 1 at a solution temperature of 70C (a copper deposited film with a thickness of 35 to 40 μm was obtained. After that, the copper deposited film peeled off from the stainless steel plate had a width I Q rrrm and a length of 80w.
The tensile strength and elongation of the sample cut into n-thickness were measured using a tensile tester, and as is clear from the examples of the present invention (Table 1), cyanide, α,α'-dipyridyl, alcohol, and potassium sulfide A copper deposited film obtained from a mixed solution consisting of a mixed solution and a plating solution (NQ1 to N12) to which three thallium compounds were added simultaneously was obtained by adding 1 plating solution (Plating solution (Plating solution)
It was found that the physical properties were superior to those of the copper deposited film obtained from 8).
３３７337
Claims (2)
する錯化剤と還元剤およびＦｕｌｌ整剤とから成る無電
解銅めっき液に、シアン化合物と、ＰＨ値が２〜１２．
５に調整されたα、α′−ジピリジルーアルコール溶液
と硫化カリウムまたは硫化ナトリウム水溶液の混合溶液
を添加して構成されたことを特徴とする無電解銅めっき
液。(1) A cyanide compound is added to an electroless copper plating solution consisting of water, copper ions to be deposited, a complexing agent for the copper ions, a reducing agent, and a full conditioning agent, and a pH value of 2 to 12.
An electroless copper plating solution characterized in that it is constituted by adding a mixed solution of an α,α'-dipyridyl-alcohol solution and an aqueous potassium sulfide or sodium sulfide solution adjusted to a pH of 5.
化カリウムまたは硫化ナトリウム水溶液を混合する工程
と、該混合溶液が透明になるまで混合溶液のＰＨ値を１
２．５以上に保持する工程と、該混合溶液のＰＨ値を２
〜１２．５に再調整した混合溶液とシアン化合物を水と
、析出されるべき銅イオンと、銅イオンに対する錯化剤
と還元剤およびＰＨ調整剤とから成る無電解銅めつき液
に添加する工程を含むことを特徴とする無電解銅めっき
液の製造方法。(2) The step of mixing α-α′-dipyridyl alcohol solution and potassium sulfide or sodium sulfide aqueous solution, and the PH value of the mixed solution is adjusted to 1 until the mixed solution becomes transparent.
A step of maintaining the pH value of the mixed solution at 2.5 or higher and a step of maintaining the pH value of the mixed solution at 2.5 or higher.
Add the mixed solution readjusted to ~12.5 and the cyanide compound to an electroless copper plating solution consisting of water, copper ions to be deposited, a complexing agent for copper ions, a reducing agent, and a PH adjusting agent. A method for producing an electroless copper plating solution, the method comprising the steps of:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13259782A JPS5923862A (en) | 1982-07-29 | 1982-07-29 | Electroless copper plating solution and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13259782A JPS5923862A (en) | 1982-07-29 | 1982-07-29 | Electroless copper plating solution and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5923862A true JPS5923862A (en) | 1984-02-07 |
Family
ID=15085056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13259782A Pending JPS5923862A (en) | 1982-07-29 | 1982-07-29 | Electroless copper plating solution and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5923862A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105932A (en) * | 1975-03-14 | 1976-09-20 | Hitachi Ltd | |
| JPS53144837A (en) * | 1977-05-25 | 1978-12-16 | Toshiba Corp | Electroless copper plating bath |
-
1982
- 1982-07-29 JP JP13259782A patent/JPS5923862A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51105932A (en) * | 1975-03-14 | 1976-09-20 | Hitachi Ltd | |
| JPS53144837A (en) * | 1977-05-25 | 1978-12-16 | Toshiba Corp | Electroless copper plating bath |
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