JPS5959870A - Electroless copper plating solution - Google Patents
Electroless copper plating solutionInfo
- Publication number
- JPS5959870A JPS5959870A JP16925082A JP16925082A JPS5959870A JP S5959870 A JPS5959870 A JP S5959870A JP 16925082 A JP16925082 A JP 16925082A JP 16925082 A JP16925082 A JP 16925082A JP S5959870 A JPS5959870 A JP S5959870A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plating solution
- cyanide
- electroless copper
- copper plating
- 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
Abstract
Description
【発明の詳細な説明】
本開明に、尚い伸び率ケもつめっき皮膜の得ら扛る無゛
屯解銅めっ＠液に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a uniformly decomposed copper plating solution which does not have a high elongation rate or a plating film.
プリント配森板ＱＪ製造ＴＬ於て、絶縁基板ｒ（回路形
ｈＶケ行９１ζめに無電解銅めっき液か１史用さ１１て
いる０無電蔚り伺めつき成業使用して絶縁か叡に回路形
成ケ竹９方法として王に次の２つの方法が行ｌわＩＬで
いゐ◇
丁ｌわら、杷縁々ζ敏υ回路とｌらｌｌ／′１部分にめ
っ政レジストを塗布し、絶縁基板を無電＊ｆ蚕１ｉ１め
っき液にし積して、めっきレジストが値イＩＪさ１てい
ない部分に無電角；１銅めっき皮膜の回路音形成させる
方法（ツルアティアイブ法）と、絶縁基板を無電解銅め
っき液にし＝ｒ貴して、全回Ｖ仁薄い無電解銅めっき皮
膜を形成し、 １ｉ３Ｊ政Ｊとｌらｌい部分にめっきレ
ジストに塗布し、ＩＭ、気朔めっき牙行いめっきレジス
トが塗布さ７１．ていない部分に電気銅めっき皮膜を形
成させ、めっきレジストを除去し２、更にクィックエッ
テンク′にＬり廖、気鋼めっき皮膜が形成さｆｌていな
いｆｌ１５＋の薄い無電７ｇ’ｆ銅めっき皮膜？除去し
て回路ケ形成させる方法（セミアデイテイブ法）とであ
る。In the printed wood distribution board QJ manufacturing TL, an electroless copper plating solution or an electroless copper plating solution was applied to the insulation board r (circuit type hV line 91ζ) to insulate it. In order to form the circuit, the following two methods are used to form the circuit. and a method of depositing an electroless *f silkworm 1i1 plating solution on the insulating substrate and forming a circuit sound of the copper plating film on the areas where the plating resist has no value (Tsuru Atiaib method); Apply an electroless copper plating solution to the insulating substrate to form a thin electroless copper plating film, apply it to the plating resist on the thin areas, and then apply IM and air plating. 71. An electrolytic copper plating film is formed on the parts where the plating resist has not been applied, and the plating resist is removed. This is a method (semi-additive method) in which a thin electroless 7g'f copper plating film is removed to form a circuit.
無石：解銅めっき液は、健酸第２銅ｌど０２価（／Ｊ
％１１塩、エチレンジアミン四酢１検など２１１１ｉ１
＋１＝ｉｌイオンのアルカリ０Ｊ浴性鉛化剤、ホルマリ
ンなどの還元剤および水／４＆化アルカリのＩ］調帯ハ
リから成っている。こｎから侍らｆ′１．Ｌｂ１１／）
つき反、膜に一般に献い（／、Ｊで、こｆ（會改嵜する
几めに、α、α′−ジピリジル、１．１０オルトフエナ
ンスロリン、無機シアン化物！、ポリアルキレ／グリコ
ールなど各イ虫の物買會除刀ＩＩ Ｊ”ゐことか提条憾
Ｉしてし）ゐが殆んどのものり、′また十分に改善烙ｆ
Ｌる九至っ゛こいない。Stone-free: Copper-decomposed plating solution is made of healthy acid cupric chloride (/J
%11 salt, ethylenediaminetetra vinegar 1 test etc. 2111i1
+1=il ion alkaline 0J bath-based lead-forming agent, reducing agent such as formalin, and water/4 & chloride alkali I] composition. From now on, the samurai f'1. Lb11/)
Generally dedicated to membranes, α, α'-dipyridyl, 1.10 orthophenanthroline, inorganic cyanides, polyalkylenes/glycols, etc. Most of the things are covered by the Caterpillar's Shopping Association II J" ゐ or the proposal I), and it is also sufficiently improved.
It's not here at all.
１り１１λば、無磯シアン化物ｒ松〃１１丁ゐ場げμ。If it is 11λ, there is no cyanide r pine 11th place.
めっき皮膜り伸び率が十分改善δＩＬない上にシアン化
物Ｖコ一般Ｖ？−頬い襟性ケもっているので多謝り１史
用σ好−ｆ Ｌ＜ Ｚ （１７こ、１０１１１居／ｅ〜
２０唄／ｌの濃度においても、めっき液の反応性成分と
シアン化物？袖光しなからめっき液を艮時間使用してい
くと、シアンイオンと他のめっきｉ成分との反応物（／
Ｊ蓄稙によるためと批建さＩＬるがめつき皮膜の伸びが
低下してシアン化物ｂ５加の効果が弱めら１するという
欠点かめる。The elongation rate of the plating film is not sufficiently improved δIL, and is cyanide V or general V? - Since I have a cheeky collar, I apologize a lot. σ is good for 1 history. -f L< Z (17 children, 10111 residence/e~
Even at a concentration of 20 songs/l, reactive components of the plating solution and cyanide? As the plating solution is used for a long time, reaction products (/
Due to J-accumulation, the elongation of the IL-glazed film decreases and the effect of adding cyanide B5 becomes weaker.
無機シアン化物とポリアルキレンクリコールケ添加丁々
場せも、めっき皮膜の伸び率が十分改善さＩしておらｆ
、 ｃこで用いらｒしてい＾ポリアルキレングリコール
しＪ芥（２）活性作用がないので、めっき析出表面で部
分的にか）っき叡りぬＩＩｌいＪＭ ｉ９ｒ （／Ｊ発
生丁ゐことがあり、そりためにめっき皮膜特性ｅこ均一
性が欠けＣｆｌ、 ’ｊｚ抑＋１ｉ１１ ｊる１こめに
、６≦加゛１バを：多く丁６Ｃとがおｃ７ｚわ１１−て
いるか価格の１１’（Ｉから不利にｌな。又、ポリアル
キレ／グリコールとし、て１万〜俺又百万＜ｖ（ｐ分子
門のもの音便用し１１いと無機シアン化物との併用の効
果がムづめも旧ない〇
又、のっき皮膜の伸ひ率り改宵メ１１るもりとしで、α
、α′−ジピリジル、ポリアルキレ／グリコールを腎≦
力１ｌ−Ｊ−るもりが提条さ７１ている。（特開ｆｌｆ
ｉ ５１−１０５９３２ ）。Even with the addition of inorganic cyanide and polyalkylene glycol, the elongation rate of the plating film was not sufficiently improved.
Since polyalkylene glycol is not used here and has no active effect, it may not be partially used on the plating surface. Due to warping, the plating film properties e are not uniform. (It is disadvantageous from I. Also, polyalkylene/glycol, 10,000 to 1,000,000<v (P molecules) is used in conjunction with 11 and inorganic cyanide. Old 〇Also, the expansion of the Nokki film is 11 Rumori and α
, α′-dipyridyl, polyalkylene/glycol ≦
Power 1l-J-rumori is the prerequisite 71. (Unexamined flf
i51-105932).
しＴ）−Ｌ ７１７５ｉら、この歯付は、ホリアルキレ
ングリコールヶ陵用１“るものであに７ｔめ、−ヒ述し
１こ工うに、均一なめっき皮膜特性を達成丁ゐため、又
、良好７ｚ Ｉｌｌひ率を得るためにＶユ、冷加賞ケ多
く［、Ｚり石はならない０更ｌＩｃ使用できるめっき液
温が面く、液（／Ｊ田が１２．５〜１５．０と茜い柁囲
でないとめっき皮膜υ晶い押ひ率が侍ら１１、ｌい０そ
（／Ｊ１ζめに使用でさるプリント配線基、板に制約が
あり、低１＋！Ｌｉ ％プリント配線板に使用ざｆして
いる常烏打ち抜き加工ロＪ龍１紙］℃ノール絶縁似など
が１￥用できない。T)-L 7175i, etc., this toothed type is 1" for polyalkylene glycol, and as described above, it achieves uniform plating film characteristics, and , In order to obtain a good 7z Ill ratio, the temperature of the plating solution that can be used is high, and the temperature of the plating solution that can be used is 12.5 to 15.0. If the plating film is not in an azure environment, the plating film υ crystal will have a hardness of 11, 10,000 (/J1ζ). Tokiarasu punching process RoJRyu 1 paper that is not intended for use] ℃ Nord insulation similar etc. cannot be used for 1 yen.
不発明１１’Ｊ ＣＵ−Ｊ ｊ ’）な点に鋺みてｌさ
１１．たもので。11. Inventiveness 11. With something.
ａ）デ１ｌｉｌ ４オン、卸４イオン０錯化剤、還ノじ
ハリお裏び田調整剤
ｂ）α、α′−シヒリジル
Ｃ）一般式
％式％
（ａ＋、Ｌ＊水素原子、炭素ｅ１〜１８Ｕ）アルキル基
、アルケニル基である０但しＲ１，ＲＩＩの両方か水素
原子の場せα言１１い。）
で次わ烙１′？、るホリオキシエテレ／エーテルケ含有
ｊ′る無電跡銅めっき液である〇
α、α′−ジヒリジル（ｔ、Ｊ濃度に、５〜６００■／
Ｉが好ましい。５ｎ睨／ｌ禾満であると、十分満足でき
る商い伸び率のめっき皮膜ｔｒ、ｘ イ４＋らｆ′Ｌ々
く又、５００ｍＦ、／ｌｌ超超るとめっき析出速度か低
−トするりが好筐しくない。１０〜１５０■／ｌがより
好１しく、１５〜５０ＩｒＩｇ／ｅ力穐マも好ましい〇
ポリオキシエチレンエーテルに、一般式％式％
両方か水素原子の礪付１Ｊ言１ない０）で表わ４ 肛る
ホリオキンエテレ／七ノエーテルあ々いＶゴホリメキシ
エチレンジエーテルである〇ポリオキシエチレンエーテ
ルに分子中に＋ＣＨ＊ ＣＨＩ （）） 。（Ｌ）ｍ水
性１１１５分とｌ＜ｔ ”１７ｔＶ’Ｘ Ｒｉ Ｈｍ
Ｕ）両方がよｎ己した炭素畝ＣｔＪ軛囲内におＶ）て程
耽の差ａあるもの（／−Ｊ疎水性ケ有しているので界面
活性作用のあるとｖＪ黄でめゐ。式中Ｕ ｎ ９２２〜
２００か良い。！ｌＩｌに好’Ｊ Ｌ、 （に４〜１５
０にも好１しくは１０〜１２０である。a) De1lil 4-on, Whole 4 ion 0 complexing agent, Kannojihari Ourabita regulator b) α, α'-Shichlidyl C) General formula % Formula % (a +, L * hydrogen atom, carbon e1 ~18U) An alkyl group or an alkenyl group, provided that both R1 and RII are hydrogen atoms. ) So next is 烙1′? 〇α, α′-dihyridyl (t, J concentration, 5-600μ/
I is preferred. If it exceeds 5n/l, the plating film will have a sufficiently satisfactory commercial elongation rate, tr, It's not nice. 10 to 150 ■/l is more preferable, and 15 to 50 IrIg/e is also preferable. 4. Polyoxyethylene ether has +CH* CHI ()) in the molecule, which is Gophorimexyethylene diether. (L)m aqueous 1115min and l<t ”17tV'X Ri Hm
U) There is a difference a in the degree of absorption within the carbon ridges CtJ where both of them are bent. Naka Un 922~
200 is good. ! Ill like 'J L, (to 4~15
It is preferably 10 to 120.
Ｒｉ 、 Ｒｍの炭素舷は、１〜１θυもりが、めっき
析出速ＩＡｔの抑制作用が少（さいυでＵｆｌしく、１
〜４ （／、ｌものが、更にめつ＠液υ安建化→・段と
してエアレーシッン會３！＋、耐ｎソに１丁つ物言に起
ｌ包性か低いのでエリ好ましい。For the carbon sides of Ri and Rm, when the thickness is 1 to 1θυ, the suppressing effect on the plating deposition rate IAt is small.
~4 (/, l is more preferable because it is more resistant to air racing 3!+, and has a low degree of coverage.
ポリオキシエチレンエーテルとしてｉ’；Ｊ、ｍ ｔＱ
えは、ホリオキシエチレンモノメテルエーデルＱＩ＊
（（）ＣＨＩＣＨ−）ｎ （ＪＨ−υ分子−（数平均分
子ｔＦ４’ 、以−ト回じ９００，２０００．５０００
のもの、ポリオキシエテレ／ジメナルエーテル
ＣＨｓ （＜）ＣＨｔＣＨｍ ）ｎ （ＪＣＨｓυ分子
ｉ＋ｒ４００ｔａもＱ、ポリオキシュテレ／メチルアリ
ルエーテル
ＣＨｓ （（）ＣＨ−ＣＨＩ ） ｎ −０−Ｃ１４−
−ＣＩ＝ ＣＨＩｖ−Ｊｊｆ子匍５ｏｏＱＪものＪくリ
オキ７エチレ／モノオレイルエーテル
ＣＨｓ （ＣＨ−）ｔ Ｃ１４＝（、：Ｈ（ＣＨｇ）ａ
（Ｕ ＣＨ／ＣＩＩＪ ｎ （ＪＨｑ〕分子お８００
．１０００のもの等が１シ゛用さ１１６゜
ポリオキシエチレンエーテルの市販品としては試薬品会
社？ｌＪえは４１九〃１（鉛工条（すわ、来示化ｈｋ■
お工ひアルトリツナ社なとから収光さｆ（てい小０１に
多くの７…ハ盲メーカーからも市販さｆＬｉｔｒｌＪｉ
？ｌｌ＊ｕホリオキシエナレ／七ノエーテルとしては日
本油脂四製のユニオツクスＭシリーズ（部品名）、 ′
１′ｔｃポリオキシエナレンジエーテルとしては同じく
日本７出力削り嗜りユニメツタスへ・１八今シリーズ（
部品名）ユニオツクスΔ４Ａシリーズ（１？−品名）な
とかおゐＯ
ポリオキシエチレンエーテルは一神又ハー独以上（／Ｊ
混付物が（史用さ１Ｌゐ０
ホリオキシエナレ／エーテル（／ＪμＵＰ、ＩＯ，１ｇ
／ｅ以上が好１しく、０−５ｇ／／！以上がより好筐し
い。史ＷＬ１ｇ／１以上が最も良い、１コ朱？与え６ｏ
Ｃ肚はこり値以上で析出界面における幽度が十分な値に
なるためと考えら７１６０多駒に砿加（，７′ても伸び
′４Ｃ／Ｊ向上か認めらＩＦないυで。i'; J, m tQ as polyoxyethylene ether
Eha, holoxyethylene monomethyl ether QI*
(()CHICH-)n (JH-υ molecule-(number average molecule tF4', hereafter 900, 2000.5000
polyoxyethele/dimenal ether CHs (<)CHtCHm )n (JCHsυ molecule i+r400ta also Q, polyoxyethele/methylallyl ether CHs (()CH-CHI) n -0-C14-
-CI= CHIv-Jjf子匍5ooQJmonoJkurioki7ethyle/monooleyl ether CHs (CH-)t C14=(,:H(CHg)a
(U CH/CIIJ n (JHq) 800 molecules
．． Is there a commercially available product of 116° polyoxyethylene ether available from a reagent company? lJ eha 419〃1 (lead work article)
The light collection f (from the manufacturer Altrituna) (there are many 7...
? ll*u phorioxyenare/seven ether is the Uniox M series (part name) manufactured by Nippon Oil & Fats & Co., Ltd.'
As for 1'tc polyoxyenalenediether, we also went to Japan's 7-output shaving enthusiast, Unimettus, and the 18-Ima series (
Part name) UNIOX Δ4A series (1?-Product name)
The admixture is (historical 1Lゐ0 phorioxyenare/ether (/JμUP, IO, 1g
/e or more is preferable, 0-5g//! The above is better. History WL 1g/1 or more is the best, 1 piece vermilion? Give 6o
It is thought that this is because the stiffness at the precipitation interface reaches a sufficient value when the C degree is higher than the stiffness value, so it is added to the 7160 multi-piece.
上限は経陽性の点から５ ｇ／ｌが最も只いか、＃Ｊ解
度筐で硝加丁ゐ乙とも出来る０
無機シアン化物として１Ｊ１ シアン化ナトリワム（Ｎ
ａＣＮ）、シアン化カリウム（ＫＣＮ）。The upper limit is 5 g/l from the point of view of menstrual positivity.
aCN), potassium cyanide (KCN).
シアン化ニッケル（ＮｉＣＮ）、シアン化コノ（ルト（
Ｃｏ（ＣＮ）ｍ）叫り金ハシアン化′１勿、７１０ンア
ン化ナトリウム（Ｎａ ａ （Ｆｅ（ＣＮ）ｓ■、フエ
ロシアン化カリウム（ｋｎ （Ｆｅ （ＣＮ） ｓ ）
） 、 ７ ｚリシアン化ナトリウム（Ｎ氏ｓ （Ｆ
ｅ（ＣＮ） ｓ ）、 フェリンアン什カリウム（Ｋ
ｓ （Ｆｅ（ＣＮ）Ｊ ） 、シアン化ニッケルカリウ
ム（ＫＩＮ ｉ （ＣＮ） ａ ） −ニトロフルンド
ナトリウム（ＮａＪＦｅ（ＣＮ）ｓ（ＮＯ））、 ’
＝’ｆ”シアｌ錯化′８′物が便用さｊｌ−ゐ。ＣＩＬ
ら乞↓−イ１１・又ｒＪ二セド以上の重付Ｗが便用さＩ
Ｌる０
無４触シアン化物（／Ｊ瀞展は０．０５〜５１１Ｉに／
ｌか好ましい。更に０．１〜５１１＠／ｌがＬり好まし
く。Nickel cyanide (NiCN), nickel cyanide (NiCN)
Co(CN)m) Gold hacyanide'1, 710N Sodium anide (Na a (Fe(CN)s■, Potassium ferrocyanide (kn (Fe(CN)s)
), 7z Sodium lysyanide (N's (F
e(CN)s), Felinant potassium (K
s(Fe(CN)J), potassium nickel cyanide (KINi(CN)a)-sodium nitroflund (NaJFe(CN)s(NO)),'
= 'f' sia l complex '8' compound is convenient jl-ii.CIL
Rabei ↓ - I 11 and rJ Two or more weighted W is convenient I
Lru0 No 4-tactile cyanide (/J Tonobu is 0.05 to 511I/
l is preferable. Further, 0.1 to 511@/l is more preferable.
０．２〜２暉／ｊか最も好ましい。0.2 to 2 h/j or most preferred.
このように少量（１）無伎シアン化物を史に副扉するＯ
とにエリ、無電解銅めっ＠液の田か広いｕ（粍囲−３−
７１２）ｂ １ １．５ 〜１ ３．ＯｖｉＰＨ＄
Ｑ７Ｖｃ＆いても、また常温打ち抜き加工５１０ヒ１紙
フェノール帖縁基板を使用した場せｔも、めっき皮膜り
晶い伸び率か・ｆｏらｎる裏うになる。またシアン化物
Ｃ／Ｊ＠度は低い濃度なりでシアンイオンと他Ｏめっ＠
液成分とり反応速度も低（Ｃ（ｔＪ反応物りめっ＠液中
へＱＪ蓄積速度も低くなるのｔ、シアン化物冷加（／Ｊ
効来が弱めらｆＬゐという欠点はほとんどなくなる。In this way, a small amount (1) of cyanide is introduced into history.
Toni Eri, electroless copper plating
712) b 1 1.5 ~ 1 3. OviPH$
Even if Q7Vc& is used, the plating film crystal elongation rate will be lower than that of the plated film when using a 510H1 paper phenol edge board that is punched at room temperature. In addition, cyanide C/J@ degree is at a low concentration and contains cyanide ions and other O.
The reaction rate of the liquid component is also low (C
Since the effect is weakened, the fL2 disadvantage almost disappears.
鋼イメ゛ンμｓ＋７ｆｔＬ瞼鋼、硝酸朔、塩化第２銅。Steel image μs + 7ftL eyelid steel, nitric acid, cupric chloride.
美化第２餉、酢酸鋼等ｑ林−１無磯酸の第２銅塩ｊ
ｖ供＃８ざ］Ｌる。Beautification No. 2, acetic steel, etc. q Lin-1 Acid-free cupric salt j
v Customer #8] L.
銅イオンの錯化剤に、第２絹イオンと錯体ケ形ノ戊しア
ルカリ水溶ｇに口ｊ浴ど丁ゐもので、エチレンジアミン
四酢酸及びそのナトリクム塩。As a complexing agent for copper ions, ethylenediaminetetraacetic acid and its sodium salt are used as a complexing agent for the second silk ion and aqueous alkali solution.
ロッシエル塩、Ｎ、Ｎ、Ｎ′、Ｎ′−テトラキス−（２
−ヒドロキシプロヒル）−エチレンジアミン、トリエタ
ノールアミン、エテレンニトリロテト２エタノ・−ル等
が使用さｆｌ、る〇
還元剤とじてに、ホルムアルデヒド、バラホルムアルデ
ヒドが１史用δＩＬる０
Ｆ４（調贅削としてｒＪ、水酸化ナトリワム５水酸化カ
リウム等の水酸化アルカリが１丈用芒）ｌ、る。Rossiel salt, N, N, N', N'-tetrakis-(2
-Hydroxyproyl)-ethylenediamine, triethanolamine, ethylenenitrilotetate-2-ethanol, etc. are used as reducing agents, and formaldehyde and paraformaldehyde are used as reducing agents. As a sharpening agent, alkali hydroxide such as sodium hydroxide and potassium hydroxide is used for one length.
無電ｐＨ鋼めりき液（１）基本組成としてｅＪ１硫磯＠
５ ｇ／ｌ〜１５ ｇ／１． めっ＠ａｍ６０〜８０
”に、 ）４（＋ １．６〜１３．０．錯化ハリとして
エチレンジアミン四酢酸では１５ｇ／ｅ〜６０ ｇ／ｌ
。Electroless pH steel polishing liquid (1) Basic composition: eJ1 sulfur @
5 g/l to 15 g/1. Me @ am 60-80
”, ) 4 (+ 1.6 to 13.0. For ethylenediaminetetraacetic acid, it is 15 g/e to 60 g/l as a complexing agent.
.
また還元剤とじてはホルムアルテヒドＶＪ５７％歩俗液
とｔ、テ２ ｍｌ／ ｌ 〜２０ ｍｌ／ １（１）も
のが約１しい。As for the reducing agent, formaldehyde VJ 57% general solution and 2 ml/l to 20 ml/1(1) are about 1 t.
以上読切し窺工うｖＬＳ本発明の無電解めっき欣ｒＩ肯
い１甲び率のめっき皮膜が侍らノＬプリント配線板の製
造に於ける回路形成等に広く用いら才ｌ々０
実施例１
無′ＦＩＩ屡銅めりき欣の基本組成として、硫酸鋼１０
ｇ／ｌ、エチレンジアミン四酢酸４５ｇ／ｌ＆Ｌ（）
５７％ホルマリン３．５ＩＩｌｌ／ｌりものに癌加剤と
して、α、α′−ジヒリジルゲそ１【ぞｆＬ３０１１１
ｇ／ｌ、２０■／７１． ４０■／Ｅ及びポリオをジエ
チレンエーテル’ｔ−ｆ：ｎぞＩＩｌ、ポリオキンエチ
レンモノメナルエーテル（分子：＆ｉ、２０００１」木
油Ｊ賄（１′ｌｉｌ剃ｇｓｓ品名、ユニオックスＭ２Ｏ
００）２ ｇ／ ｌ ＊ポリオキシエチレンメチルアリ
ルエーテル（分子嘔噌８００１日本Ｙ１１１脂＋４’ｉ
７商品名、ユニオックスＭＡ８００ ） Ｉ ｇ／１％
ポリオキシエナレンモノオレイルエーテル（分子量７０
０東京化成工菓咽Ｊ製、試薬）０．５ｇ／ｊ！ケ疹加し
、めりき液ｌ第１を２０℃で１２．６υめっき創ｎ４整
した０
（−１ＬらりめっｒＡ液にめっ芦反応開始のためのめっ
き反応触媒処理ケおＣなつグミステンレス叡紮浸償して
めっき液温７０℃でめっき＋７丁いＪｖみ２５μｍ〜６
５μｍυめっさ皮膜會倚１ζ０め−）き析出速ＩＪＪ、
めっさ皮膜伸び率、めっさ皮膜外観全別表に示す。As you can see above, the electroless plating of the present invention shows that the plating film with a coating rate of 1 is widely used for circuit formation, etc. in the production of Samurai printed wiring boards.Example 1 As the basic composition of Mu'FII copper-plated steel, sulfuric acid steel 10
g/l, ethylenediaminetetraacetic acid 45g/l&L ()
57% formalin 3.5IIll/l α,α'-dihyridilgeso 1 [zofL30111
g/l, 20/71. 40■/E and polio diethylene ether't-f:nzo IIl, polyoxine ethylene monomenal ether (molecule: &i, 20001) wood oil J bribe (1'lil shaved gss product name, Uniox M2O
00) 2 g/l *Polyoxyethylene methyl allyl ether (molecular weight 8001 Japan Y111 fat + 4'i
7 Product name, Uniox MA800) I g/1%
Polyoxyenalene monooleyl ether (molecular weight 70
0 Tokyo Chemical Industry Co., Ltd., reagent) 0.5g/j! In addition, the plating solution L1 was heated to 20℃ to prepare 12.6υ plating holes. Gummy stainless steel was immersed and plated at a plating solution temperature of 70°C + 7 mm Jv thickness 25 μm ~ 6
Deposition speed IJJ of 5μmυ Messa film formation 1ζ0m-),
The elongation rate of the metal film and the appearance of the metal film are shown in the attached table.
めっき皮膜伸び率は、めりき皮＃會ステンレーＸ板＞ら
剥離り、テ幅ＩＱｍｎｔ、−１４さ１００ ｍｍ（ｔＪ
引張り試験測定用試験体とし東洋ボールドライン製テン
シロン引張り試験装ｗ、會使用して、引張り速ｍ ｌ
ｎ１ｎｌ ／分、チャック間ｒ＃ｊ１５ｍｍ″ｔ″側建
會２こｌっｌこ〇
実施例
実施例１と同じ羞木組成り欲にシアン化ナトリウムＩ
ｎ’ｇ／ ｊ！ ＊ ｅｘ、ａ’−ジピリジルＢＯＱ／
１゜３Ｌひホリオキシエナレンモノメテルエーテル（分
子佃、２０００、日本油脂−袈商品名ｙ二オソクスＭ２
０００）２ｇ／Ｊ硝加し、めっ＠欣田會２０℃でｌ ＋
、、７ 、 ＋ ２．０ 、１２．３ 、１２．６ 。The elongation rate of the plating film is determined by peeling from the plated skin #ai stainless steel
Tensilon tensile test equipment manufactured by Toyo Bold Line was used as the test specimen for tensile test measurement, and the tensile speed m l was used.
n1nl/min, between chucks r #j 15mm "t" side construction 2 〇Example Same wood composition as Example 1 Sodium cyanide I
n'g/j! * ex, a'-dipyridyl BOQ/
1゜3L hiphoryoxyenalene monomether ether (Mokken Tsukuda, 2000, Nippon Oil & Fats - Kema product name y Niosox M2
000) Add 2g/J of sulfur, and add @Kintakai at 20°C.
,,7,+2.0,12.3,12.6.
１６．０と５槓のめり＠液ｋｖ４費し実施例１と同様に
してめっき皮膜を得７ｔ。A plating film of 7 tons was obtained in the same manner as in Example 1 using 16.0 mm and 5 tons of liquid at a cost of 4 kv.
め−）き析出速度、めっき皮膜伸び率、めっき皮膜外観
全別表に示す。The deposition rate, plating film elongation rate, and plating film appearance are all shown in the attached table.
比較例１
実軸？ＩＪ１と同じか木組成り無電解のっき液にシアン
化ナトリ９ム２０ Ｑ／ Ｉ ｋｆｘｓ刀口し、めっき
散所會２０℃で１２．０のめっき液を調整し。Comparative example 1 Real axis? Sodium cyanide 9M 20 Q/I kfxs was added to an electroless plating solution with the same wood composition as IJ1, and a plating solution of 12.0 was prepared at 20°C at a plating site.
実施？ｌｌ ｌと同様にしてめりき皮膜ケ得た。めっき
析出速度、めっき皮膜伸び率、めっき皮膜外−？別表に
示す。implementation? A plated film was obtained in the same manner as in ll. Plating deposition rate, plating film elongation rate, plating film outside -? Shown in the attached table.
比較例２
実Ｍ例１と同じ基本組成の無゛亀解めっき液にα、α′
−ジピリジル５０■／ｌヶ添加し、めっき散所に２０℃
で１２．０ 、 ＋２．６ 、のめつき散音調整し、実
施ｖす１とｌｌ’ｌＪ様にしてめっき皮＠を得た。めっ
き析出速度、めっき皮膜伸び率、めっき皮膜外観を別表
にホ丁。Comparative Example 2 α, α′ in the non-glare plating solution with the same basic composition as Actual M Example 1
-Add 50μ/l of dipyridyl and 20°C in the plating area.
At 12.0, +2.6, the plating sound was adjusted, and the plating skin was obtained as in the case of VS1 and ll'lJ. The plating deposition rate, plating film elongation rate, and plating film appearance are listed in a separate table.
比奴？！１３
央７１！１例１と回し基本組成の無゛邂解めりき液にシ
アン化ナトリウム１ｎ！ｇ／ｇ、α、α′−ジヒリジル
６０■／ｌを添加し、めっ＠Ｍ）ｍ（’ｉ２０℃で１２
．０りめっ＠ａｔ調整し、実施νす１と１目」株にして
めっき皮膜上前だ。めっきぜ１出速度、めっき皮膜伸び
率、めっき皮膜外観全別表に示”’ｆ （ｉ比較例４
実施例１と同じ基本組成り無電ルめっさ欣Ｖこα、α′
−ジピリジル３０１１１ｇ／７１１．及びポリエチレン
クリコール（分子１ｉｔ６００）ｋそｎぞｆＬ１ｇ／１
％ １ｇ／ｌ、１０ｇ／ｌｋ添／ＩＩＪ シ、 ｋｂ
Ｑ ＠（Ｐｉ、Ｎｌ？２０℃でそ才１ぞｒｉ、１２．０
、 ｌ ２．６ 、１２゜６０めっき故６独を調賢し
、実施例１とＩＨＩ徐にし、てめっさ皮膜を侍九〇めっ
き析出速度、めっき皮膜伸び率、めっき皮膜外観を別表
に示す。Hiko? ! 13 Central 71! 1 example 1 and 1 n of sodium cyanide in the basic composition of the invincible melting liquid! g/g, α, α′-dihyridyl 60 μ/l,
．． Adjust the plating @at, and then apply the plating film to the 1st and 1st stock. The plating speed, the elongation rate of the plating film, and the appearance of the plating film are all shown in the attached table.
-Dipyridyl 30111g/711. and polyethylene glycol (molecule 1it600) ksonzofL1g/1
% 1g/l, 10g/lk addition/IIJ, kb
Q @ (Pi, Nl? At 20℃, the temperature is 1, 12.0
, l 2.6, 12゜60 plating was examined, Example 1 and IHI were adjusted, and the plating film was made into a samurai 90. Plating deposition rate, plating film elongation rate, and plating film appearance are listed in a separate table. show.
比較ｖｌＪ５
実施例１と同じ羞木組取り無電解めっき液にシアン化ナ
トリウム１■／１．ポリエチレングリコール（分子量６
００）Ｉｇ／ｇ紮冷加し。Comparison vlJ5 Sodium cyanide 1/1. Polyethylene glycol (molecular weight 6
00) Ig/g ligature cold.
めっき欣Ｉ８會２０℃で１２．ＯＧＪめっき液を脚釡し
、実施？ｌＪ １と同様ＶＣシてめっき皮膜ケ侍た〇め
っき析出速度、めっき皮膜伸び率、めっき皮膜外観を別
表に示す。Plating condition I8 at 20℃ 12. Do you apply OGJ plating solution to the pot? The plating film was coated with VC as in J1. The plating deposition rate, elongation rate of the plating film, and appearance of the plating film are shown in the attached table.
比較例６
実施例１と同じ基本組成の無′＃７Ｌ解めっき液にシア
ン化ナトリウム１ ｒＩＪｇ／ ｌ 、α、α′−ジピ
リジル３０ｎＷ／Ｌポリエチレングリコール（分子量６
００）Ｉｇ／ｌｊケ隋加し、めっき液ＰＨを２０℃で１
２．０ＵＪめっき液會副祭し、実施例１と同様にしてめ
っき皮膜會イ＃１こ。めっき析出速度。Comparative Example 6 Sodium cyanide 1 rIJg/l, α,α'-dipyridyl 30 nW/L polyethylene glycol (molecular weight 6
00) Add Ig/lj and adjust the plating solution pH to 1 at 20°C.
A 2.0 UJ plating solution was used as a substitute, and plating film #1 was prepared in the same manner as in Example 1. Plating deposition rate.
め−）さ皮膜伸び率、めっき皮膜外観を別表に示す０ 以下示白The elongation rate of the coating and the appearance of the plating coating are shown in the attached table. Explanation below
Claims (1)
田肖整剤 ｂ）α、α′−ジピリジル Ｃ）一般式 ％式％） （Ｒ＋、Ｒｍμ水素原子、炭素敬１〜１８のアルキル基
、アルケニル基である。但しＲ＋、Ｒ＊ｑ）両方が水素
原子の場合は含まｌい０）で衣わさ１１ゐポリオキシエ
チレンエーテルを宮調丁ゐ無１ｈ；解銅めつき液。 ２、少石有効摂（１）無電シアン化物を特徴とする特許
請求の範囲第１項記載の無’ＩＩＵ解鋼めっき液０ ６、 α、α′−ジピリジルｔ５〜５００ｍ１！、／１
．ホリオキシエテレンエーテル會０１ｇ／Ｊ以上宮有す
るｑ：ｆｉＦｆ珀釆υ範囲弔１歩、又は第２狽記載の無
電解めっき液０ ４、無機シアン化物’ｉ０．０５〜５■／！含有する特
許請求の範囲第２項又は第６墳ｎＣ載υ無電解めっ＠液
。[Scope of Claims] 1. a) Copper ion, copper ion complexation, reducing agent, and polishing agent b) α, α'-dipyridyl C) General formula % formula %) (R+, Rmμ hydrogen Atom, alkyl group, alkenyl group having 1 to 18 carbon atoms.However, if R+, R*q) are both hydrogen atoms, it is not included. 1h; Copper plating solution. 2. Effective intake of small stones (1) Non-IIU steel decomposition plating solution 0 according to claim 1, characterized by electroless cyanide 6, α, α'-dipyridyl t5-500ml! ,/1
．． Porioxyethylene ether 01 g/J or more: fiFf 珀釆υ 1 step, or electroless plating solution 0 4, inorganic cyanide 'i 0.05-5 ■/! Claim 2 or 6 contains an electroless plating solution.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16925082A JPS5959870A (en) | 1982-09-28 | 1982-09-28 | Electroless copper plating solution |
| US06/535,057 US4548644A (en) | 1982-09-28 | 1983-09-23 | Electroless copper deposition solution |
| DE8383109644T DE3367940D1 (en) | 1982-09-28 | 1983-09-27 | Electroless copper deposition solution |
| EP83109644A EP0107087B1 (en) | 1982-09-28 | 1983-09-27 | Electroless copper deposition solution |
| KR1019830004572A KR880000471B1 (en) | 1982-09-28 | 1983-09-28 | Electrodysisless copper deposition solution |
| SG49087A SG49087G (en) | 1982-09-28 | 1987-06-03 | Electroless copper deposition solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16925082A JPS5959870A (en) | 1982-09-28 | 1982-09-28 | Electroless copper plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5959870A true JPS5959870A (en) | 1984-04-05 |
| JPS61909B2 JPS61909B2 (en) | 1986-01-11 |
Family
ID=15883022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16925082A Granted JPS5959870A (en) | 1982-09-28 | 1982-09-28 | Electroless copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5959870A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011231382A (en) * | 2010-04-28 | 2011-11-17 | Nagoya Plating Co Ltd | Plating liquid for polymer fiber, method for plating polymer fiber using the same, and method for producing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0586507U (en) * | 1992-04-28 | 1993-11-22 | 日工株式会社 | Concrete mixer shaft sealing device |
| JP2592953Y2 (en) * | 1993-10-08 | 1999-03-31 | 日工株式会社 | Shaft sealing device for concrete mixer |
-
1982
- 1982-09-28 JP JP16925082A patent/JPS5959870A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011231382A (en) * | 2010-04-28 | 2011-11-17 | Nagoya Plating Co Ltd | Plating liquid for polymer fiber, method for plating polymer fiber using the same, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61909B2 (en) | 1986-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4265943A (en) | Method and composition for continuous electroless copper deposition using a hypophosphite reducing agent in the presence of cobalt or nickel ions | |
| US3962494A (en) | Sensitized substrates for chemical metallization | |
| US3095309A (en) | Electroless copper plating | |
| JPH029110B2 (en) | ||
| EP0698130A1 (en) | Palladium layers deposition process | |
| JPH01168871A (en) | Chemical copper plating solution and formation of copper plating film with same | |
| JPH0247551B2 (en) | ||
| DE3000526A1 (en) | BATH FOR ELECTRONIC DEPOSITION OF PALLADIUM, AUTOCATALYTIC PALLADIUM DEPOSITION METHOD AND PALLADIUM ALLOY | |
| EP0133800A1 (en) | Electroless copper plating solution | |
| US4279951A (en) | Method for the electroless deposition of palladium | |
| US4830668A (en) | Acidic bath for electroless deposition of gold films | |
| US4877450A (en) | Formaldehyde-free electroless copper plating solutions | |
| US4814009A (en) | Electroless copper plating solution | |
| JPS5959870A (en) | Electroless copper plating solution | |
| US5076840A (en) | Electroless copper plating solution | |
| CH655132A5 (en) | AQUEOUS BATH FOR ELECTRIC GOLD PLATING. | |
| US4138267A (en) | Compositions for chemical copper plating | |
| US4720404A (en) | Aqueous alkaline bath for the chemical deposition of copper, nickel, cobalt and their alloys | |
| US3754940A (en) | Electroless plating solutions containing sulfamic acid and salts thereof | |
| US3667972A (en) | Chemical nickel plating baths | |
| US4539044A (en) | Electroless copper plating | |
| US3671289A (en) | Pre-etch treatment of acrylonitrile-butadiene-styrene resins for electroless plating | |
| US3748166A (en) | Electroless plating process employing solutions stabilized with sulfamic acid and salts thereof | |
| JPS58153767A (en) | Stabilizing mixture for chemical copper plating bath | |
| US3516848A (en) | Process and solution for sensitizing substrates for electroless plating |