JPS6220877A - Electroless nickel plating method - Google Patents
Electroless nickel plating methodInfo
- Publication number
- JPS6220877A JPS6220877A JP15932685A JP15932685A JPS6220877A JP S6220877 A JPS6220877 A JP S6220877A JP 15932685 A JP15932685 A JP 15932685A JP 15932685 A JP15932685 A JP 15932685A JP S6220877 A JPS6220877 A JP S6220877A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- nickel
- electroless
- plastic
- plated
- 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
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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）
本発明は一般的にプラスチック表面に無電解でニッケル
をメッキする方法に関するものであシ、特に光ディスク
等の；［ｉＦＩ＠ｅ−情報記録担体製造用原盤に電鋳を
する場合の導電層の形成や、記録層自体の形成に使用可
能な無電解ニッケルメッキ方法洗関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention generally relates to a method for electroless plating of nickel onto a plastic surface, and particularly relates to a method for electroless plating of nickel onto a plastic surface, and in particular to a method for electroless plating of nickel on a plastic surface. The present invention relates to an electroless nickel plating method that can be used to form a conductive layer when electroforming a manufacturing master or to form the recording layer itself.
〔従来技術）
絶縁物上に金属被膜を形成する際に使用される方法とし
て無電解メッキは尚知のものである。しかし、従来の無
電解メッキは絶縁物表面の金属化あるい＃−ｉ専電化を
目的としたものが主であフ、得られた無電解メッキ被膜
の均一性には厳密な要求がなされていなかった。ところ
が、最近注目を集めている光（磁気）ディスクのプラス
チック表すブストレートヲ成形、例えば注型、射出、圧
縮成形等で製造するｖＡＶＣ使用されるレプリカ金型い
わゆるスタンバ−の表面精度には極めて高いものが要求
されている。仁のスタンパ−は一般にガラス原盤にレジ
ストを頒布し、所定パターンに露光−硬化し、未硬化部
分を除去して製作された原盤からｉｎによって製作され
るが、このレジスト原盤は絶縁体であるため、電鋳作業
の前に導電層を形成する必要がある。従来、この導電層
は銀ト（反応によυ形成されてきたが、銀鏡面は化学的
に不安定で、空気中のル素で酸化を起して粗面化し、物
理的強度も弱いため電鋳後に銀鏡層を取り除かねばなら
ず、その結果スタンパー面の表面１１４度が低下すると
いう欠点かあった。そのため、奄鮪後でも除去する必要
のない化学的・物理的に安定な銀鏡反応以外による導％
Ｌ膜を原盤上に無’Ｍｌ解メッキによ多形成することが
強く要刃くされている。[Prior Art] Electroless plating is a well-known method used to form a metal film on an insulator. However, conventional electroless plating is mainly intended for metallization of the surface of insulators or for #-i electric coating, and strict requirements are not placed on the uniformity of the resulting electroless plating film. There wasn't. However, the surface accuracy of the so-called stub bar, the replica mold used in vAVC, which is manufactured by molding plastics for optical (magnetic) disks that has recently attracted attention, such as cast molding, injection molding, and compression molding, is extremely high. something is required. Jin's stamper is generally manufactured by in-processing the master disc by distributing resist onto a glass master disc, exposing it to a predetermined pattern, curing it, and removing the uncured parts. However, since this resist master disc is an insulator, , it is necessary to form a conductive layer before the electroforming operation. Traditionally, this conductive layer has been formed by a silver reaction, but the mirror surface of silver is chemically unstable and becomes rough due to oxidation by fluorine in the air, and its physical strength is weak. The silver mirror layer had to be removed after electroforming, which resulted in a decrease in the surface angle of 114 degrees on the stamper surface.Therefore, other than the chemically and physically stable silver mirror reaction, which does not need to be removed even after the Amazuna process, the silver mirror layer had to be removed. lead% by
It is strongly required to form a large amount of L film on the master disc by Ml-free plating.
１−かじ、従来鳩知の無１４３Ｉ解ニツケルメツキ方法
を単純に上記のようなサブミクロ１ンオーダーの凹凸を
有する超鞘密厄形品へ適用しても渦足な結果は得られな
い。すなわち、メッキにょろり「出粒子が粗くな力番い
表面精度が得られず、メッキ膜とプラスチック面とのＲ
滑性が杓いため、仮の′電鋳工程が均一に行えない。1 - Simply applying the conventional 143I-solution nickel plating method to the above-mentioned super-densely shaped product having submicron-order irregularities will not yield satisfactory results. In other words, the surface precision of the plating film is rough due to coarse particles, and the R between the plating film and the plastic surface is poor.
Due to poor lubricity, the preliminary electroforming process cannot be performed uniformly.
（発明の目的）
従って、本発明９目的は緻密な析出粒子で且つプラスチ
ック基材への密着力の強い無電解ニッケルメッキ膜を得
る方法を提供すＡことにある。(Object of the Invention) Therefore, the ninth object of the present invention is to provide a method for obtaining an electroless nickel plating film with dense precipitated particles and strong adhesion to a plastic substrate.
（発明の構成）
本発明によるプラスチック表面上にニッケルを無電解メ
ッキする方法は、メッキ浴を際性状態に維持し且つその
ｉｆ、ｆ’ｅ６０℃以下に維持し、さらに、メッキ浴に
周波数２５〜６０ ＫＨｚ の超音波振動を加えなが
ら行うこと全特徴としている。(Structure of the Invention) The method of electroless plating nickel on a plastic surface according to the present invention is to maintain a plating bath in an extreme state and maintain its if, f'e at 60°C or less, and further to apply a plating bath with a frequency of 25 All features are that it is performed while applying ultrasonic vibrations of ~60 KHz.
一般に、無電）眸ニッケルメッキに用いられるメッキ液
は可溶性のニッケル塩と、次亜リン酸塩と。Generally, the plating solution used for electroless nickel plating consists of soluble nickel salt and hypophosphite.
ｐＨ緩愉液とを主成分とし、通常は６０℃以上、例えば
８０℃に加温して析出速Ｕｔ−大きくして用いられるが
、メッキ液の分解を防止し、緻密なメッキ膚全得るため
にはメッキ液ｔ−酸性条件にするのが有効である。しか
し、メッキ液を酸性条件にすると析出温度が小さくなシ
、また析出が均一に開始しないためメッキむらの無いメ
ッキ層を作ることかで＠ない。このことは特に１．００
０〜２．０００ Ｘ程度の薄いメッキ層を均一に形成す
る場合には重大な問題となる。The main component is a pH-reducing solution, and it is usually heated to 60°C or higher, for example 80°C, to increase the precipitation rate, but in order to prevent the decomposition of the plating solution and obtain a dense plating layer. It is effective to use acidic conditions for the plating solution. However, if the plating solution is made under acidic conditions, the deposition temperature will be low and the deposition will not start uniformly, making it difficult to form a plating layer with no uneven plating. This is especially true for 1.00
This becomes a serious problem when uniformly forming a thin plating layer of about 0 to 2.000X.
そこで、本発明者は緻密で且つ密着力に優れた無電解ニ
ッケルメッキ膜を形成する方法全研究した結果、メッキ
浴に超音波振動を加えることによって問題が解決するこ
とを見出し、本発明に達した。Therefore, the inventor of the present invention has conducted extensive research on methods for forming an electroless nickel plating film that is dense and has excellent adhesion, and has discovered that the problem can be solved by applying ultrasonic vibration to the plating bath, and has arrived at the present invention. did.
すなわち次亜リン酸を還元剤として用いたニッケルの無
電解析出反応は次式のように行われる：Ｃへｔ
Ｎｉ” ＋ Ｈ，ＰＯ，−＋ Ｈ，Ｏ−＋Ｎｉ 、＋
Ｈ！ＰＯ，−＋２Ｍ”析出したニッケルは自己触媒とし
て働き反応が促進される。That is, the electroless deposition reaction of nickel using hypophosphorous acid as a reducing agent is carried out as follows: C to t Ni'' + H, PO, -+ H, O- + Ni, +
H! PO, -+2M'' precipitated nickel acts as an autocatalyst and promotes the reaction.
析出初期はメッキ物の表面力・らのり、カス発生が烈し
く通常の撹拌ではこの発生カスが表面に停滞しているた
め粗い表面になる。超ｆ波の効１釆はこの初期の段階に
ガスの停滞をなくすためでおり、均一なニッケル面が析
出した後（１〜２分後）であれば通常の撹拌でも緻密な
面が得られる。In the early stages of precipitation, the surface strength, sluggishness, and scum generation of the plated material are severe, and with normal agitation, the generated scum stays on the surface, resulting in a rough surface. The effect of ultra-f waves is to eliminate gas stagnation at this early stage, and once a uniform nickel surface has been deposited (after 1 to 2 minutes), a dense surface can be obtained even with normal stirring. .
また初期のＨ，ガスの停滞は撹拌を強くしても完全に除
く事ができないだけでなく流速を高めることによシメッ
キａ！ｌＪ表面に流速ムラができ、均一な析出が起らな
いなどの弊害もでてくる。In addition, the initial stagnation of H and gas cannot be completely removed even with strong stirring; There are also disadvantages such as flow velocity unevenness on the lJ surface and uniform precipitation not occurring.
上記超音波の周波数は一般に２５〜６０ ＫＨｚであり
、この直より低くては効果が症く、高過ぎると清書が出
てくる。また、この超音波加振に加えてメッキ浴をフィ
ルターを介して循環するのが好ましい。The frequency of the above-mentioned ultrasonic waves is generally 25 to 60 KHz, and if the frequency is lower than this, the effect will be poor, and if it is too high, a fine copy will come out. In addition to this ultrasonic vibration, it is also preferable to circulate the plating bath through a filter.
本発明による無’に解ニッケルメッキ方法は特にレジス
ト硬化面、特にこの上記レジスト効果面が高密開情報記
録担体製造用原盤表面である場合に有利である。The zero-resolution nickel plating method according to the present invention is particularly advantageous when the resist-hardened surface, particularly the resist-effect surface, is the master surface for producing a high-density open information recording carrier.
以下実施例を用いて本発明を説明する。The present invention will be explained below using Examples.
（実施例）
メッキ浴組成 ね、１化ニツケル ２４９７ｅ次
亜リン酸ナトリウム ２１
塩化アンモニウム ２．５
酢酸ナトリウム ４．９
ホウ酸 １２
ピノトレス ４ｒｎｌ
ｐｉ（４５〜５
上紀の組成’ｋｌｌ！ビーカーでスターラーで撹拌しな
がらメッキ浴温を４２〜４５℃に保ち、アクリル板（７
０Ｘ３０Ｘ１．５ｍｍ）’！ｒ用いて市販の脱脂剤に５
分浸漬じ（室温）、次にセンシタイザン、アクチペータ
ー液にそれぞれ１分間浸漬した後、メッキ時間を１０分
としてアクリル板上に１６００Ｘ厚さの無電％ ニッケ
ルメッキ層全形成した。この際本発明による超音波振動
（５０Ｋ）（ｔ。(Example) Plating bath composition Nickel monochloride 2497e Sodium hypophosphite 21 Ammonium chloride 2.5 Sodium acetate 4.9 Boric acid 12 Pinotres 4rnl pi (45~5 Composition of the upper period 'kll! In a beaker with a stirrer Keep the plating bath temperature at 42-45℃ while stirring, and place an acrylic plate (7
0X30X1.5mm)'! Add 5 to a commercially available degreaser using r.
After being immersed in the sensitizer solution and the activator solution for 1 minute each (at room temperature), the plating time was set to 10 minutes, and an electroless nickel plating layer of 1600× thickness was entirely formed on the acrylic plate. At this time, ultrasonic vibration (50K) (t) according to the present invention.
４０Ｗ４上超音波発生器）と、通常のスターラーとを用
いてメッキ浴に振動あるいは撹拌力を加えた。得られた
メッキ面の評価は（１）表面粗さと（２）密着性によっ
た。Vibration or stirring force was applied to the plating bath using a 40W4 ultrasonic generator) and an ordinary stirrer. The obtained plated surface was evaluated based on (1) surface roughness and (2) adhesion.
表面粗さは表面膜差計を用いた。その際の針先は０．２
μＲで、針先は５ｍｍｇにした。その結果は第１．２図
に示してあり、第１図は本発明による超音波振動を加え
た場合でる力、第２図は通常の撹拌によるものである。Surface roughness was measured using a surface film difference meter. The needle tip at that time is 0.2
The needle tip was 5 mmg in μR. The results are shown in Figure 1.2, where Figure 1 shows the force generated when applying ultrasonic vibration according to the invention, and Figure 2 shows the force generated by normal stirring.
この結末からもわかるように撹拌法によるものは表面が
租ぐ、光沢もない。As you can see from this result, the surface of the product made using the stirring method is grainy and lacks luster.
なお、超音波を加えながら２分間メッキした後スターラ
ー撹拌に切替えて８分間〔計１０分）メッキしたが、光
沢を析出向の粗さも＆音波単独と差はなかった。In addition, after plating for 2 minutes while applying ultrasonic waves, switching to stirrer agitation was performed for 8 minutes (total 10 minutes), but there was no difference in gloss, roughness in the direction of deposition, and sonic waves alone.
このことは無電解ニッケルメッキ浴を用いて優れたメッ
キ膜をする場合にはメッキ初期の段階で超音波を用いる
ことが効果的であるかを示している。This indicates that it is effective to use ultrasonic waves at the initial stage of plating when forming an excellent plating film using an electroless nickel plating bath.
蜜篇力は２０ｘｍ幅のセロテープをメッキ面に貼りこれ
を一気にはがした時のアクリル板とメッキ物との剥離状
態を比較した。結果は第４図の如く超音波の方が優れて
いた。Mitsuhenriki compared the state of peeling between the acrylic board and the plated material when a 20xm wide sellotape was applied to the plated surface and removed at once. As shown in Figure 4, the results showed that ultrasound was superior.
第１図は本発明による超音波加部法によシ得られた無電
解ニッケルメッキ表面の段差計の結果を示す図。
第２図は従来法のスタージー攪拌法による第１図と同様
な図。
第３図はテープ剥離テスト結果を示す写真の才梨写図で
、３−１は本発明による５ ０ Ｋｌ（ｚ （４０Ｗ）
の超音波加部を行った場合、３−２と３−３はスターラ
ーにより各々１００ ｒｐｍ、 ２０ Ｏｒｐｍ
でメッキ浴を撹拌した場合である。
第１図
手 続 補 正 占 （方式）％式％
１、事件の表示
昭和６０年特許願第１５９３２６号
２、発明の名称
、Ｗ電解ニッケルメッキ方法
３、補正をする者
事件との関係 特許出願人
郵便番号 ５９０
住 所 大阪府堺市鉄砲町１番地
名 称 （２９０＞ ダイセル化学工業株式会社
昭和６０年１０月９日
５、補正の対象
Ｊ３よび「図面」
一−−− ＼−
６、補正の内容
１）明細ζＤ第８頁第８〜９行口の「比較した。・・・
でいた。」を下記の通りに補正する。
［比較したが、本発明による５０にｌｌｚ （４０ｗ）
の超音波加撮を行った場合にはメッキ膜の剥離は全くな
かった。一方、従来法によるスターラーを用いて１１０
０ｐｐおよび２００ｒＤＩｌｌで撹拌したものはそれぞ
れ約９５％、約５０％の膜面積が剥離してしまった。」
２）同第８頁第１６行〜２０行目の「第３図は・・・で
ある。」を削除する。
３）添附図面の中で第３図を削除する。FIG. 1 is a diagram showing the results of a level difference measurement on an electroless nickel plated surface obtained by the ultrasonic addition method according to the present invention. FIG. 2 is a diagram similar to FIG. 1 using the conventional Sturgy stirring method. Fig. 3 is a photograph showing the results of the tape peeling test, and 3-1 is a 50Kl(z (40W)) according to the present invention.
3-2 and 3-3 are heated at 100 rpm and 20 Orpm respectively using a stirrer.
This is the case when the plating bath is stirred. Figure 1 Procedures Amendment Divination (Method) % Formula % 1. Indication of the case 1985 Patent Application No. 159326 2. Title of the invention, W electrolytic nickel plating method 3. Person making the amendment Relationship with the case Patent application Postal code: 590 Address: 1 Teppo-cho, Sakai City, Osaka Prefecture Name (290> Daicel Chemical Industries, Ltd. October 9, 1985 5, Subject of amendment J3 and "Drawings" 1--- \- 6, Amendment Contents 1) Details ζD, page 8, lines 8-9, “Compared...
It was. ' shall be corrected as follows. [Compared to 50llz (40w) according to the present invention
When ultrasonic imaging was performed, there was no peeling of the plating film at all. On the other hand, using a stirrer according to the conventional method,
About 95% and about 50% of the membrane area peeled off when stirred at 0 pp and 200 rDIll, respectively. ”
2) Delete "Figure 3 is..." from lines 16 to 20 on page 8. 3) Figure 3 will be deleted from the attached drawings.
Claims (1)
方法において、メッキ浴を酸性状態に維持し且つその温
度を６０℃以下に維持し、さらに、メッキ浴に周波数２
５〜６０ＫＨｚの超音波振動を加えながら行うことを特
徴とする無電解ニッケルメッキ方法。 ２）メッキ液をフィルターを介して循環ポンプにより循
環させることをさらに含むことを特徴とする特許請求の
範囲第１項記載の方法。 ３）上記プラスチック表面がレジスト硬化面であること
を特徴とする特許請求の範囲第１項記載の方法。 ４）上記レジスト硬化面が高密度情報記録担体製造用原
盤表面であることを特徴とする特許請求の範囲第３項記
載の方法。[Claims] 1) In a method of electroless plating nickel on a plastic surface, the plating bath is maintained in an acidic state and its temperature is maintained at 60°C or less, and the plating bath is further provided with a frequency of 2
An electroless nickel plating method characterized by performing the process while applying ultrasonic vibrations of 5 to 60 KHz. 2. The method according to claim 1, further comprising: 2) circulating the plating solution through a filter using a circulation pump. 3) The method according to claim 1, wherein the plastic surface is a resist hardened surface. 4) The method according to claim 3, wherein the resist cured surface is a master surface for manufacturing a high-density information recording carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15932685A JPS6220877A (en) | 1985-07-19 | 1985-07-19 | Electroless nickel plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15932685A JPS6220877A (en) | 1985-07-19 | 1985-07-19 | Electroless nickel plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6220877A true JPS6220877A (en) | 1987-01-29 |
Family
ID=15691363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15932685A Pending JPS6220877A (en) | 1985-07-19 | 1985-07-19 | Electroless nickel plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6220877A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112281144A (en) * | 2020-10-26 | 2021-01-29 | 中国电子科技集团公司第四十三研究所 | Ultrasonic plating method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5750867A (en) * | 1980-09-08 | 1982-03-25 | Masaru Onbe | Preparation of dressing seasoned with "ume" |
| JPS5829834A (en) * | 1981-08-18 | 1983-02-22 | Kokusan Kinzoku Kogyo Co Ltd | Method for plating polyacetal resin |
-
1985
- 1985-07-19 JP JP15932685A patent/JPS6220877A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5750867A (en) * | 1980-09-08 | 1982-03-25 | Masaru Onbe | Preparation of dressing seasoned with "ume" |
| JPS5829834A (en) * | 1981-08-18 | 1983-02-22 | Kokusan Kinzoku Kogyo Co Ltd | Method for plating polyacetal resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112281144A (en) * | 2020-10-26 | 2021-01-29 | 中国电子科技集团公司第四十三研究所 | Ultrasonic plating method |
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