JPS6033355A - Activating treatment liquid - Google Patents
Activating treatment liquidInfo
- Publication number
- JPS6033355A JPS6033355A JP13988783A JP13988783A JPS6033355A JP S6033355 A JPS6033355 A JP S6033355A JP 13988783 A JP13988783 A JP 13988783A JP 13988783 A JP13988783 A JP 13988783A JP S6033355 A JPS6033355 A JP S6033355A
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- activating
- activation treatment
- disc
- fabricating
- 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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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、例えばオーテイオ用あるいはビデオ用ディス
クのプレス用金型作製において原盤作製の為に用いられ
る無電解メッキ処理の前処理として行なわれる活性化処
理の為の活性化処理液に係り、パラジウム塩に対して錯
化物を形成する錯化剤を含丑せておくことにより、この
パラジウム塩を含む活性化処理液が安定したものとなり
、例えば活性化処理能力を高める為に、ｐＩ−１の高い
酸性域にしたり、液温を高くしても活性化処理液の安定
性に富んでおり、活性化処理が良好に行なわれ、そして
この活性化処理液を用いて処理した場合には、後工程に
おける無電解メッキが良好に行なわれ−〔、無電解メッ
キ膜が良好に形成されるものとなる活性化処理液を提供
することを目的とする。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an activation process that is performed as a pre-treatment for electroless plating used for producing a master disc, for example, in the production of press molds for audio or video discs. By including a complexing agent that forms a complex with palladium salt in the processing solution, the activation processing solution containing this palladium salt becomes stable, and for example, in order to increase the activation processing ability. In addition, the activation treatment solution is highly stable even when the acidic range of pI-1 is high or the solution temperature is raised, and the activation treatment is performed well. It is an object of the present invention to provide an activation treatment solution that allows electroless plating to be carried out in a subsequent step and to form an electroless plated film in a good manner.
例えは、オーデ、イオディスク又はビテオティスク製造
に用いられる原盤作製の為の無電解メツキーは、まず感
受性化処理工程、次いで活性化処理工程を経た後に行な
われる。For example, electroless metskiing for producing master discs used in the manufacture of audio discs, iodo discs, or video discs is performed after first undergoing a sensitization process and then an activation process.
そして、この活性化処理工程かうまく行なわれていなけ
れば、次工程の無電解メッキ処理工程がう甘く行なわれ
ない。例えば、二塩化パラジウム水溶液を用いた活性化
処理液による処理能率の向上を図る為に、ｐＨの高い酸
性領域にしたり、液６”、７１を高くしたりすると、こ
の活性化処理液は極めて不安定なものとなり、パラ／ラ
ムイオンの析出力利′、（好なものとならず、このよう
に不安定な状態の活性化処理液で活性化処理した後に、
無電解メッキ処理を行なうと、析出した無電解メッキ膜
の表向は粗く、さらには無電解メッキ膜の密着具合も充
分でなく、ウキとかハガレの問題が引き起こされる。さ
らには、このようにして形成された無電解メッキ膜を、
電鋳用の下地導電膜として用いた場合には、被メツキ基
材表面の高精度のレプリカ性が撰女われる恐れもある。If this activation process is not performed well, the next electroless plating process will not be carried out properly. For example, in order to improve the processing efficiency of an activation treatment solution using an aqueous palladium dichloride solution, if the pH is set to a high acidic region or the height of solutions 6" and 71 is increased, this activation treatment solution becomes extremely inefficient. It becomes stable, and the precipitation efficiency of para/ram ions is not good.
When electroless plating is performed, the surface of the deposited electroless plated film is rough, and the adhesion of the electroless plated film is also insufficient, causing problems such as flaking and peeling. Furthermore, the electroless plating film formed in this way,
When used as a base conductive film for electroforming, there is a risk that the highly accurate replica property of the surface of the substrate to be plated may be compromised.
このように無電解メッキ処理の前処理として用いられる
活性化処理は重要女工程であシ、従来活性化処理液は二
塩化パラジウムと塩酸との混合水溶液があるが、この活
性化処理液は、第１図に二塩化パラジウムの濃度が１
ｇ／ｌの場合の可視吸収スペクトルを示す如＜、ｐＨ変
化及び放置時間によって変化し、特にｐＨが３．１を越
えると急激に吸光度が増し、又例えばｐ Ｈ３，８では
放置時間の経過と共にｐＨが低下し、吸光度が増し、更
に放置していると液の濁化が起きてしまう程であり、特
にパラジウムイオンの濃度が高くなればなる程。The activation treatment used as a pretreatment for electroless plating is an important process. Conventionally, the activation treatment solution is a mixed aqueous solution of palladium dichloride and hydrochloric acid, but this activation treatment solution is Figure 1 shows that the concentration of palladium dichloride is 1.
As shown in the visible absorption spectrum in the case of g/l, the absorbance changes depending on the pH change and the standing time.In particular, when the pH exceeds 3.1, the absorbance increases rapidly, and for example, at pH 3.8, the absorbance increases as the standing time passes. The pH decreases, the absorbance increases, and if left standing, the solution becomes cloudy, especially as the concentration of palladium ions increases.
酸性域でｐＨの高い程、あるいは液温の高い程といった
ように、活性化処理液の活性化処理能力を高めると、活
性化処理液が不安定なものとなり、活性化処理がうまく
行方えなくなるといった致ａ的欠点がある。If the activation processing ability of the activation processing solution is increased, such as by increasing the pH in the acidic range or by increasing the liquid temperature, the activation processing solution will become unstable and the activation processing will not proceed smoothly. There are some fatal flaws.
本発明者は、パラジウム塩を含む活性化処理液中に、例
えば塩化ナトリウム、塩化カリウム、臭化カリウム、塩
化アンモニウム、硫酸アンモニウム、ロッシェル塩、ク
エン酸塩、ピロリン酸塩といったようなハロゲン化物、
アンモニア塩、有機酸塩等のパラジウムに対する錯化剤
を添加しておくと、例えばこの活性化処理液の活性化能
力を高める為に酸性域におけるｐ Ｉ−Ｉを高くしても
、活性化処理液が安定なものとなっていることを見い出
し、これに基いて本発明をなしとげたのである。The present inventor has discovered that halides such as sodium chloride, potassium chloride, potassium bromide, ammonium chloride, ammonium sulfate, Rochelle's salt, citrate, and pyrophosphate are added to the activation treatment solution containing palladium salt.
If a complexing agent for palladium such as an ammonia salt or an organic acid salt is added, for example, even if the pI-I in the acidic region is increased in order to increase the activation ability of the activation treatment solution, the activation treatment will still be effective. They discovered that the liquid was stable, and based on this they accomplished the present invention.
例えば、二塩化パラジウム１ ｇ／を水溶液に塩化ナト
リウム１０ｇ／ｌを添加し、ｐＨ上昇及び放置時間に伴
なう可視吸収スペクトルを、第２図に示す如く、塩化す
トリウムの添加により吸収ピークが長波長側ヘソフトシ
、吸光度の減少が認められるものの、ｐＨ上昇及び放置
時間による変化は極めて少なく、塩化すトリウムの添加
によって二塩化パラジウムを含む活性化処理液は安定性
に富んだものとなっている。For example, when 10 g/l of sodium chloride is added to an aqueous solution of palladium dichloride (1 g/l), the visible absorption spectrum as the pH increases and the standing time is as shown in Figure 2. Although a decrease in absorbance is observed at longer wavelengths, the change due to pH increase and standing time is extremely small, and the activation processing solution containing palladium dichloride is highly stable due to the addition of thorium chloride. .
又、第３図に、二塩化パラジウム１ ｇ／ｌ 水溶液に
塩化カリウム８ ｇ／を添加した活性化処理液の可視吸
収スペクトルを示す如く、塩化カリウムの添加によって
二塩化パラジウムを含む活性化処理液は安定性に富んだ
ものとなっている。Furthermore, as shown in Fig. 3, the visible absorption spectrum of an activation treatment solution in which 8 g/l of potassium chloride was added to a palladium dichloride 1 g/l aqueous solution, the activation treatment solution containing palladium dichloride by adding potassium chloride. is highly stable.
又、第４図に、二塩化パラジウム０．１ ｇ／を水溶液
に塩化ナトリウム０．５ ｇ／ｌと臭化カリウム５ ｇ
／を添加した活性化処理液の可視吸収スペクトルを、第
５図に、二塩化パラジウム０．１ ｇ／を水溶液に塩化
ナトリウム０．５ ｇ／ｌと塩化アンモニウム５．０ｇ
／を添加した活性化処理液の可視吸収スペクトルを、第
６図に、二塩化パラジウム０．１ ｇ／を水溶液に塩化
ナトリウム０．５ｇ／ｌと硫酸アンモニア塩ム１０ｇ／
を添加した活性化処理液の可視吸収スペクトルを、第７
図に、二塩化パラジウム０．１ ｇ／を水溶液に塩化す
ｌ・リウム０．５ｇ／Ｌとロッシェル塩、２５ｇ／ｌ添
加した活性化処理液の可視吸収スペクトルを示す」こう
に、これらの活性化処理液も安定性に富んでいることが
わかる。In addition, Fig. 4 shows that palladium dichloride 0.1 g/l is added to an aqueous solution of sodium chloride 0.5 g/l and potassium bromide 5 g/l.
Figure 5 shows the visible absorption spectrum of the activation treatment solution to which 0.1 g/l of palladium dichloride was added to an aqueous solution of 0.5 g/l sodium chloride and 5.0 g/l ammonium chloride.
Figure 6 shows the visible absorption spectrum of the activation treatment solution to which palladium dichloride (0.1 g/l) was added, sodium chloride (0.5 g/l) and ammonium sulfate (10 g/l) to an aqueous solution.
The visible absorption spectrum of the activation treatment solution added with
The figure shows the visible absorption spectrum of an activation treatment solution in which 0.1 g/l of palladium dichloride was added to an aqueous solution of 0.5 g/l of chloride and 25 g/l of Rochelle's salt. It can be seen that the chemical treatment solution is also highly stable.
伺、第８図に示す如く、二塩化パラジウム０１ｇ／を水
溶液に塩化ナトリウム０．５ ｇ／Ｌを添加し、ｐＩ−
１５に調整した活性化処理液の可視吸収スペクトルを示
す如く、塩化ナトリウムといった錯化剤の量がパラジウ
ムイオンに対して少なすぎると、時間の経過につれて多
少とも変化するようになり、活性化処理液の安定性が小
さくなる。As shown in FIG.
As shown in the visible absorption spectrum of the activation treatment solution adjusted to No. stability becomes smaller.
従って、錯化剤濃度としては約０．０１モル／を以上あ
ることが望せしい。又、さらには、錯化剤が約０．旧モ
ル／を以上であって、かつパラジウムイオンに対してモ
ル比で約１以上あることがより望ま（５い。Therefore, the concentration of the complexing agent is desirably about 0.01 mol/or more. Further, the complexing agent may be about 0. It is more desirable that the former mole/mole is at least 1 and the molar ratio to the palladium ion is about 1 or more (5 or more).
す、下、本発明の応用例について説明する。Below, application examples of the present invention will be explained.
１ず、光学的に記録され、そして現像処理され、乾燥し
たフォトレゾスト面を、例えば三酸化クロム２０ｇ／ｌ
と硫酸７０ｎｄ！、／ｌの組成のクロム硫酸混液に浸漬
する。1. First, the optically recorded, developed and dried photoresist surface is coated with, for example, 20 g/l of chromium trioxide.
And sulfuric acid 70nd! ,/l in a chromium sulfuric acid mixture.
次いて、塩化第一・スズ１０ｇ／ｌと塩酸４０ ｉｒｅ
／ ｔの組成の感受性処理液をスプレーにて吹き伺け
る。Next, 10 g/l of stannous chloride and 40 ire of hydrochloric acid
A sensitive treatment solution with a composition of /t can be sprayed.
このように処理されたフオトレジス］・面を、本発明の
活性化処理液、例えば二塩化パラジウム３ｇ／ｌと塩化
すトリウム１５ｇ／Ａとを・含み、かつｐｉ−１５に調
整された活性化処理液に約３分間浸漬する。The thus-treated photoresist surface is subjected to an activation treatment containing an activation treatment solution of the present invention, for example, 3 g/l of palladium dichloride and 15 g/A of thorium chloride, and adjusted to pi-15. Immerse in the liquid for about 3 minutes.
そし−上記の前処理が終ると、ニッケル液として、例え
ば硫酸ニッケル０．１ ＋ｎｏ Ｌ／ ｔ、塩化アンモ
ン０．３ｍｏＬ／１． ｉ’ｒ＋酸ナトツナトリウム０
ｏｔ／）−を、還元液として、例えばホウ水素化すｌ−
ＩＪウムＩｇ／Ｚ１アンモニア水１０ｍ１！／ｌ、酢酸
ナトリウム０２１ｎＯｔ／ｌを用いて、これらの２液を
被メツキ物上で混合されるようスプレーで吹き利け、無
電解ニッケルメッキを施す。After the above pretreatment is completed, the nickel solution is, for example, nickel sulfate 0.1 + no L/t, ammonium chloride 0.3 moL/1. i'r+acid natotsu sodium 0
ot/)- as a reducing liquid, for example, borohydride l-
IJum Ig/Z1 Ammonia water 10ml! Electroless nickel plating is applied by spraying these two solutions onto the object to be plated using 021 nOt/l of sodium acetate and 021 nOt/l of sodium acetate.
そして、このようにしてフォトレジスト面」二に析出し
７たニッケルメッキ膜を観察すると、このニッケルメッ
キ膜にはピンホールも形成されておらず、完全な鏡面で
あり、下地との密着性も良好で、ニッケルメッキ膜のウ
キ、ノ・ガレといった問題等全くないものである。When observing the nickel plating film that was deposited on the photoresist surface in this way, it was found that there were no pinholes formed in the nickel plating film, it had a perfect mirror surface, and it had good adhesion to the base. It is in good condition and there are no problems with the nickel plating film, such as flaking, cracking, etc.
すなわち、無電解メッキの前処理として行なう活性化処
理に際して、用いた活性化処理液の能力を高める為に、
例えばｐＨ５といったｐＨの高い酸性域に調整していて
も、活性化処理液が不安定ではないので、活性化処理が
良好に行なわれ、その結果次工程の無電解メッキが良好
に行なわれて、良好なメッキ膜が形成されたのである。In other words, in order to increase the ability of the activation treatment solution used during the activation treatment performed as a pretreatment for electroless plating,
For example, even if the pH is adjusted to a highly acidic range such as pH 5, the activation treatment solution is not unstable, so the activation treatment is performed well, and as a result, the electroless plating in the next step is performed well. A good plating film was formed.
上述の如く、本発明に係る活性化処理液は、パラジウム
塩を含む活性化処理液において、該パラジウムに対する
錯化剤を少なくとも含むので、活性化処理液の能力を高
める為に、例えば液温を高くしたりあるいはｐＨの高い
酸性域に調整したりしても、この活性化処理液は安定々
ものであり、従って能力を高めた状態において活性化処
理を行なっても良好に活性化処理が行なわれ、例えば次
工程で行々う無電解メッキによって形成されるメッキ膜
が良好かものであり、又従来の活性化処理液に、例えば
塩化すトリウムといった錯化剤を添加するのみであるか
ら、低コストなものである等の特長を有する。As described above, the activation treatment solution according to the present invention contains at least a complexing agent for palladium in the activation treatment solution containing a palladium salt. Even if the pH is increased or the pH is adjusted to a high acidic range, this activation treatment solution remains stable, so even if the activation treatment is performed in a state where the capacity is increased, the activation treatment will be performed well. For example, the plating film formed by electroless plating in the next step is good, and since a complexing agent such as thorium chloride is only added to the conventional activation treatment solution, it is less expensive. It has features such as low cost.
第１図〜第８図は、二塩化パラジウムを含む活性化処理
液の可視吸収スペクトルを示すものである。
特許出願人 日本ビクター株式会社
代理人 宇 高 克 己
ｔ３Ｅｊｌ
爽東、エフ
１−１テ２７畿・・・ン□1 to 8 show visible absorption spectra of activation treatment liquids containing palladium dichloride. Patent Applicant: Victor Japan Co., Ltd. Agent: Katsu Uko, t3Ejl Soto, F1-1T27Ki...n□
Claims (1)
ムに対する錯化剤を少なくとも含むことを特徴とする活
性化処理液。An activation treatment liquid containing a palladium salt, characterized in that the activation treatment liquid contains at least a complexing agent for the palladium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13988783A JPS6033355A (en) | 1983-07-30 | 1983-07-30 | Activating treatment liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13988783A JPS6033355A (en) | 1983-07-30 | 1983-07-30 | Activating treatment liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6033355A true JPS6033355A (en) | 1985-02-20 |
Family
ID=15255901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13988783A Pending JPS6033355A (en) | 1983-07-30 | 1983-07-30 | Activating treatment liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6033355A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219815A (en) * | 1991-09-23 | 1993-06-15 | Applied Electroless Concepts Inc. | Low corrosivity catalyst containing ammonium ions for activation of copper for electroless nickel plating |
| JP2018080702A (en) * | 2007-08-30 | 2018-05-24 | マイクロポンプ インク ア ユニット オブ アイデックス コーポレーションＭＩＣＲＯＰＵＭＰ，ＩＮＣ．，Ａ Ｕｎｉｔ ｏｆ ＩＤＥＸ Ｃｏｒｐｏｒａｔｉｏｎ | Pumps and pump-heads comprising internal pressure-absorbing member |
| US10883497B2 (en) | 2016-11-11 | 2021-01-05 | Micropump, Inc., A Unit Of Idex Corporation | Systems and methods of securing a compliant member in a pump |
-
1983
- 1983-07-30 JP JP13988783A patent/JPS6033355A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219815A (en) * | 1991-09-23 | 1993-06-15 | Applied Electroless Concepts Inc. | Low corrosivity catalyst containing ammonium ions for activation of copper for electroless nickel plating |
| JP2018080702A (en) * | 2007-08-30 | 2018-05-24 | マイクロポンプ インク ア ユニット オブ アイデックス コーポレーションＭＩＣＲＯＰＵＭＰ，ＩＮＣ．，Ａ Ｕｎｉｔ ｏｆ ＩＤＥＸ Ｃｏｒｐｏｒａｔｉｏｎ | Pumps and pump-heads comprising internal pressure-absorbing member |
| US10883497B2 (en) | 2016-11-11 | 2021-01-05 | Micropump, Inc., A Unit Of Idex Corporation | Systems and methods of securing a compliant member in a pump |
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