JPH0317277A - Formation of plating composition and black electroless nickel-plating membrane - Google Patents
Formation of plating composition and black electroless nickel-plating membraneInfo
- Publication number
- JPH0317277A JPH0317277A JP2047102A JP4710290A JPH0317277A JP H0317277 A JPH0317277 A JP H0317277A JP 2047102 A JP2047102 A JP 2047102A JP 4710290 A JP4710290 A JP 4710290A JP H0317277 A JPH0317277 A JP H0317277A
- Authority
- JP
- Japan
- Prior art keywords
- concentration
- composition
- plating
- saccharin
- composition according
- 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 34
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000012528 membrane Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940081974 saccharin Drugs 0.000 claims abstract description 15
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims abstract description 15
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019204 saccharin Nutrition 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000000872 buffer Substances 0.000 claims abstract description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 66
- 229910052759 nickel Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 15
- 239000011651 chromium Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- -1 nitrate ions Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000006172 buffering agent Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- MQLJIOAPXLAGAP-UHFFFAOYSA-N 3-[amino(azaniumylidene)methyl]sulfanylpropane-1-sulfonate Chemical compound NC(=N)SCCCS(O)(=O)=O MQLJIOAPXLAGAP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910003944 H3 PO4 Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PHJJWPXKTFKKPD-UHFFFAOYSA-N [Ni+3].[O-]P([O-])[O-] Chemical compound [Ni+3].[O-]P([O-])[O-] PHJJWPXKTFKKPD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- C23C18/32—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)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は黒色無電解ニッケルメッキに関する。[Detailed description of the invention] [Industrial application field] The present invention relates to black electroless nickel plating.
［従来の技術とその課題コ
無電解ニッケルメッキは従来から知られている。無電解
ニッケルメッキで被覆した物品は例えば米国特許出願第
３０８８８４６号に開示がある。現在では黒色無電解ニ
ッケルメッキに対する一般的な市場ニーズがあり、主と
して装飾目的に使用されているが、必ずしもこれだけに
限定されるわけではない。かかるメッキは例えばテレビ
ジョン、ビデオカセットレコーダーおよびｈｉ−ｆｌ装
置の金属露出部品および／またはケーシングの表面に使
われる。[Prior art and its problems] Electroless nickel plating has been known for a long time. Articles coated with electroless nickel plating are disclosed, for example, in US Patent Application No. 3,088,846. Currently, there is a general market need for black electroless nickel plating, which is primarily used for decorative purposes, but is not necessarily limited to this. Such plating is used, for example, on the surfaces of exposed metal parts and/or casings of televisions, video cassette recorders and hi-fl devices.
ＥＰ特許出願第（１６）９４１２７号では、黒色無電解
ニッケルメッキを形成させる際の問題点の解決方法を提
案している。ここでは無電解ニッケルメッキ済み物品を
クロメートイオン、リン酸イオンおよび任意成分として
の硫酸イオンを含む洛中で処理し定期的に電流を逆転さ
せる方法を提案している。ＥＰ特許出願第（１６）９４
１２７号では、Ｅｎｔｈｏｎｅ社から商品名ｒＥＮＰＬ
ＡＴＥ ４１５Ｊとして市販される浴の使用を提案して
いる。しかし、商品名ｒＥＮＰＬＡＴＥ ４１５Ｊ浴か
ら形成させ、次いでこれを転化させて形成させた被膜は
、無電解メッキ浴の金属交換回数が２〜３の場合のみに
適切な黒色層を与えるだけであることが判明している（
金属交換回数は最初に浴中に存在した金属イオンの全重
量がメッキされ尽くした時点で一単位をとる；メッキ期
間中、一般には還元剤と共に金属イオンを浴中に補給す
る。）。EP patent application no. (16)94127 proposes a solution to the problems in forming black electroless nickel plating. Here, we propose a method in which electroless nickel-plated articles are treated in a solution containing chromate ions, phosphate ions, and optionally sulfate ions, and the current is periodically reversed. EP Patent Application No. (16)94
In issue 127, Enthone's product name rENPL
It is proposed to use a bath commercially available as ATE 415J. However, it has been found that coatings formed from and then converted from the rENPLATE 415J bath provide a suitable black layer only when the electroless plating bath has a few metal exchange cycles. It is clear (
The metal exchange frequency takes one unit when the entire weight of metal ions initially present in the bath has been plated out; during plating, metal ions are generally replenished into the bath along with a reducing agent. ).
この無電解メッキ浴は金属交換回数ｌの場合には有効で
はなく金属交換回数２〜３の場合だけ有効に使用できる
為に、もし析出ニッケルメッキを黒色化する必要がある
場合には、金属交換回数１の場合および４以降の場合に
おいて該浴を他の目的に流用しない限り浴材料の著しい
損失を招くという問題点がある。This electroless plating bath is not effective when the number of metal exchanges is l, but can be used effectively only when the number of metal exchanges is 2 to 3. Therefore, if it is necessary to blacken the deposited nickel plating, it is necessary to replace the metal. In the case of number 1 and number 4 or later, there is a problem in that unless the bath is diverted to another purpose, a significant loss of bath material will result.
［課題を解決するための手段コ
無電解ニッケルメッキ浴中にサッカリンを存在させると
浴の寿命期間に亙ってニッケルが析出し、析出したニッ
ケルーリン合金メッキ膜は引き続いて均一に黒色化され
るか、または少なくとも従来可能であった程度よりも優
れた状態で黒色化されるということが判明した。[Means for solving the problem] When saccharin is present in the electroless nickel plating bath, nickel will precipitate over the life of the bath, and the deposited nickel-phosphorus alloy plating film will continue to be uniformly blackened. It has been found that blackening is possible, or at least better than previously possible.
本発明の第１の提案によれば、サッカリンを含有する無
電解ニッケルメッキ浴が提供される。このサッカリンは
一般的には析出ニッケルメブキ映を引き続いて黒色化す
るのに有効な量で存在する。According to a first proposal of the invention, an electroless nickel plating bath containing saccharin is provided. The saccharin is generally present in an amount effective to subsequently blacken the deposited nickel coating.
ここで使用する”ニッケルメッキ”なる用語には、例え
ばリンのような或る種の他の元素とニッケルとの合金メ
ッキをも包含しており、この合金メッキは無電解メッキ
分野では通常生産される典型的なメッキ膜である。The term "nickel plating" as used herein also includes alloy plating of nickel with certain other elements, such as phosphorus, which are not commonly produced in the electroless plating field. This is a typical plating film.
ニッケル源としては、硫酸ニッケルまたはその他の溶解
性ニッケル塩である。洛中のニッケル濃度としては０．
１〜５０ｇ／ノ、例えば１〜２５ｇ／ｌ、典型的には２
〜１０ｇ／ｌである。The source of nickel is nickel sulfate or other soluble nickel salts. The nickel concentration in Rakuchu is 0.
1 to 50 g/l, such as 1 to 25 g/l, typically 2
~10 g/l.
無電解金属メッキ浴中では、金属イオンは電解的のみな
らず化学的にも還元される。ニッケルイオン用還元剤で
あれば還元剤の種類はとわないが、実際には次亜リン酸
ナトリウムが好ましく、このものはニッケルーり冫合金
メッキ膜を形成させる。還元剤の濃度は１−１（１６）
ｇ／ｌｖ例えば５〜５０ｇ／ｔｓ典型的には２０〜４０
ｇ／ｊである。In electroless metal plating baths, metal ions are reduced not only electrolytically but also chemically. Any type of reducing agent can be used as long as it is a reducing agent for nickel ions, but sodium hypophosphite is actually preferred, as it forms a nickel-tin alloy plating film. The concentration of reducing agent is 1-1 (16)
g/lv e.g. 5-50 g/ts typically 20-40
g/j.
バルク溶液中でのニッケルイオンの還元が速すぎないよ
うに、通常は浴組成物中にニッケルイオン用錯化剤を含
有させる。錯化剤の種類は問わないが、好ましい錯化剤
は酪酸である。（以下、酪酸または他の弱有機酸と呼称
した場合には酪酸イオンもしくは他の該当イオンをも包
含するものとし、実際に存在する形態は浴のそのときの
１）Ｈに依存する。）酪酸以外で有用な錯化剤には、コ
ハク酸、グリコール酸、リンゴ酸、クエン酸が考慮でき
る。錯化剤の濃度は１−１（１６）ｇ／ｌ，例えば５〜
５ ０ ｇ／ ７％ ！ＩＩＩ型的には２０〜４０ｇ／
ｌである。混合物を包含する他の錯化剤も使用可能であ
る。A complexing agent for nickel ions is usually included in the bath composition to prevent the reduction of nickel ions in the bulk solution too quickly. Although the type of complexing agent does not matter, a preferred complexing agent is butyric acid. (Hereinafter, when butyric acid or other weak organic acids are referred to, butyric acid ions or other relevant ions are also included, and the form actually present depends on 1) H in the bath at that time. ) Useful complexing agents other than butyric acid may include succinic acid, glycolic acid, malic acid, and citric acid. The concentration of the complexing agent is 1-1 (16) g/l, e.g.
50g/7%! For type III, 20-40g/
It is l. Other complexing agents can also be used, including mixtures.
サッカリンは溶解型として洛中に添加するのが普通であ
る。溶解型として適当なものはナトリウム塩であるが、
他の溶解性塩も使用できる。好ましい結果を得る為にサ
ッカリンは少なくとも０．７ｇ／ｌの濃度で使用するべ
きである。２ｇ／ノ以上の濃度で使用すると、時として
黒化後に斑紋現象が現われる。サッカリン濃度として特
に好ましい濃度はｌ．Ｏ〜１．８ｇ／ｌ、例えば１．５
ｇ／ｌであることが分かった。これ以外の指針としては
、消耗するニッケルのｇ当たり２５〜２（１６）ｍｇの
サッカリンの存在が浴を維持する関係で好適な結果を生
むことが実験室的に見いだされ；ニッケルのｇ当り７５
〜１２５ｍｇｓ特にニッケルのｇ当り約１（１６） 一
ｇが好ましい比率であることが判明した。Saccharin is usually added in a dissolved form. The suitable soluble form is sodium salt,
Other soluble salts can also be used. To obtain favorable results, saccharin should be used in a concentration of at least 0.7 g/l. When used at a concentration of 2 g/no or more, a mottling phenomenon sometimes appears after darkening. A particularly preferred saccharin concentration is l. O~1.8g/l, e.g. 1.5
g/l. As a further guideline, it has been found laboratoryly that the presence of 25 to 2 (16) mg of saccharin per gram of nickel consumed produces favorable results in relation to maintaining the bath;
~125 mgs per gram of nickel, particularly about 1 (16) gram per gram of nickel, has been found to be a preferred ratio.
緩衝剤を浴中に存在させることもできる。緩衝剤として
は例えば弱有機酸およびその塩を使用できるが、主とし
て酢酸／酢酸塩系が使用される。Buffers can also be present in the bath. For example, weak organic acids and their salts can be used as buffers, but acetic acid/acetate systems are mainly used.
この緩衝剤濃度は１〜５０ｇ／！、例えば５〜４ ０
ｇ／ｌ、典型的には２０〜３０ｇ／ｌである。This buffer concentration is 1-50g/! , for example 5 to 40
g/l, typically 20-30 g/l.
緩衝剤として酢酸ナトリウムを使用する場合には、３水
和物として供給する。If sodium acetate is used as a buffer, it is supplied as the trihydrate.
この組成物は一種または２種以上の安定剤をさらに含有
してもよい。無電解ニッケル系に対しては適量の鉛が好
ましい安定剤であることが分かった。鉛は酢酸鉛として
供給するか、または他の適当な水溶性鉛塩として添加す
る。鉛の濃度は０．１〜５ｍｇ／Ｊ、例えば０．２〜３
曽ｇ／ １ １典型的には０．６〜１．５ｍｇ／／であ
る。The composition may further contain one or more stabilizers. A moderate amount of lead has been found to be the preferred stabilizer for electroless nickel systems. Lead may be supplied as lead acetate or added as other suitable water-soluble lead salts. The concentration of lead is 0.1-5 mg/J, for example 0.2-3
So g/1 1 is typically 0.6 to 1.5 mg//.
イオウ含有化合物も他の部類に属する有用な安定剤であ
る。この部類で有用な安定剤には、３一（（アミノーイ
ンミノメチノレ）チオ）−１−プロパンスルフオン酸で
あるが，必ずしも該化合物のみに限定されない。このイ
オウ化合物の濃度は、０．１〜１ ０ ｍｇ／ ７ １
例えば０．２〜５ ｔｉｅ／ ｌ、典型的には０．５〜
３一ｇ／ｌである。Sulfur-containing compounds are another class of useful stabilizers. Useful stabilizers in this class include, but are not necessarily limited to, 3-((aminoiminomethyl)thio)-1-propanesulfonic acid. The concentration of this sulfur compound is 0.1 to 10 mg/71
For example 0.2-5 ties/l, typically 0.5-5
31 g/l.
通常無電解ニッケルメッキｉ■成物のｐＨは酸性側であ
る。３〜６、例えば４〜５，５、典型的には４，５〜５
である。Usually, the pH of electroless nickel plating products is on the acidic side. 3-6, such as 4-5,5, typically 4,5-5
It is.
本発明の第２の提案によれば、黒色無電ニッケルッキ膜
の形成方法が提供され、該方法によればサッカリンを含
む無電解ニッケルメッキ組成物と素地とを接触させ、次
いでクロムを含む転化層を形成させる。この転化層はリ
ンおよび任意にイオウ成分を含んでいる。特に該転化層
はＣｒＰＯ４およびＣｒ（ＯＨ）ｉ成分から成り場合に
よりＣｒ２ （８０４）！！成分をも含みうる層であ
って、かつＣｒ：Ｐ：Ｓ＝１： （０．２ 〜１．５）
：（０〜０．５））の重量比を示す塩基性永和リン酸ク
ロム層から成っている。According to a second proposal of the present invention, a method for forming a black electroless nickel plating film is provided, in which an electroless nickel plating composition containing saccharin is brought into contact with a substrate, and then a conversion layer containing chromium is applied. Let it form. This conversion layer contains phosphorus and optionally sulfur components. In particular, the conversion layer consists of CrPO4 and Cr(OH)i components, optionally Cr2 (804)! ! A layer that can also contain components, and Cr:P:S=1: (0.2 to 1.5)
: (0 to 0.5)).
無電解ニッケルメッキ膜の形成において、浴温は４０〜
９９℃、例えば６０〜９５’Ｃ，典型的には８５〜９０
℃である。メッキ時間は特に限定されないが、例えば５
分ないし５時間であり所望するメッキ厚さに依存する。In the formation of electroless nickel plating film, the bath temperature is 40~
99°C, e.g. 60-95'C, typically 85-90'C
It is ℃. The plating time is not particularly limited, but for example, 5
minutes to 5 hours, depending on the desired plating thickness.
通常のメッキ時間は２時間であるが、約１０ミクロン厚
さを得る為には３０〜４５分が普通である。Typical plating time is 2 hours, but 30-45 minutes is common to obtain a thickness of about 10 microns.
転化にはクロム、リンおよびイオウを含み、典型的には
Ｃｒ：Ｐ：Ｓ＝１：１ （０ 〜０．２）の重量比お示
す。The conversion includes chromium, phosphorus and sulfur, typically in a weight ratio of Cr:P:S=1:1 (0-0.2).
一般に該転化層は無電解ニッケルメッキ済み物品を定期
的な逆電流で処理したときに形成され、これに関しては
ＥＰ特許出願第（１６）９４１２７号に記載がある。逆
電流の周期は０．１〜５０１１ｚ、例えば０． ５〜２
５ Ｈｚ ，典型的には約１ ［１ｚである。Generally, the conversion layer is formed when electroless nickel plated articles are subjected to periodic reverse current, as described in EP patent application no. (16) 94127. The period of the reverse current is 0.1 to 5011z, for example 0. 5-2
5 Hz, typically about 1 [1 z].
与えられた電流サイクルにおいて、無電解ニッケルメッ
キ済み物品がカソードである期間とアノードである期間
との比率（１．．１／ｌ．．）は１に等しいことを必要
としない。一般的にはｔｏ．ｔ／ｔ０比は０．０５〜２
０が適当であるが、１以下が好ましい。０．１〜０．８
が特に好ましいことが判明した。In a given current cycle, the ratio (1..1/l..) of the period of time during which the electroless nickel plated article is the cathode to the period during which it is the anode does not need to be equal to one. Generally to. t/t0 ratio is 0.05-2
0 is appropriate, but 1 or less is preferred. 0.1-0.8
was found to be particularly preferred.
電流密度は０．１〜Ｉ ＡＳＤ，例えば０．２〜０．
５ ＡＳＤ，典型的には約０． ２５ １ＳＤである
。The current density is 0.1-I ASD, for example 0.2-0.
5 ASD, typically about 0. 25 1SD.
本発明のｆｆｉ要なる特徴は、この転化浴組成物中に硝
酸イオンが存在すると性能が向上する；すなわち均一電
着性が向上することが観察され、かつ高電流密度領域で
緑色化する傾向が減少するということである。したがっ
て転化浴組成物中に鞘酸イオンを含有させるのが好まし
＜、該硝酸イオン源としては硝酸を用いる。添加量とし
ては６５％硝酸としてｌ〜１０１１１／ｌ、例えば５〜
１０■１／ １，典型的には約７．５ 閣！である。The ffi essential feature of the present invention is that the presence of nitrate ions in the conversion bath composition improves the performance; that is, it has been observed that uniform electrodeposition is improved, and there is no tendency for greening in the high current density region. This means that it will decrease. Therefore, it is preferable to include sheath acid ions in the conversion bath composition, and nitric acid is used as the nitrate ion source. The amount added is l~10111/l as 65% nitric acid, for example 5~
10■1/1, typically about 7.5 kaku! It is.
転化浴組成物中のクロメートイオン濃度は１〜４０ｇ７
１％例えば２〜２０ｇ／ｌ、典型的には５〜１５ｇ／ｌ
である。リン酸イオン濃度は濃リン酸として１〜Ｂｏｗ
ｌ／ｌ，例えば２〜４０ｍｌ／ｌ，典型的には１０〜３
０閣１／ｌを供給したときの濃度である。硫酸イオン濃
度は濃硫酸０〜１０ｌｌ１例えば０．１〜５■１／ｌ，
典型的には０．５〜３ｔｍｌ／！を供給したときの濃度
である。The chromate ion concentration in the conversion bath composition is 1 to 40 g7
1% e.g. 2-20g/l, typically 5-15g/l
It is. Phosphate ion concentration is 1 to Bow as concentrated phosphoric acid.
l/l, e.g. 2-40 ml/l, typically 10-3
This is the concentration when 0.1/l is supplied. The sulfate ion concentration is concentrated sulfuric acid 0 to 10 1/l, for example 0.1 to 5 1/l,
Typically 0.5-3tml/! This is the concentration when supplied.
［実施例］
尖１ば（Ｌ
無電解ニッケルメッキ水性組成物を次の処方で調製した
。[Example] Point 1 (L) An electroless nickel plating aqueous composition was prepared according to the following formulation.
ＣｒＯ３
１０ｇ／ｌ
Ｈ３ ＰＯ４ （８５％） ２０ ■１７１
Ｈ．８０． （９８％） ’２ｓｌ／ｌＮ
ｉ ” （硫酸ニッケルとして） ８． ２ｇ／ｌ酪
酸（ ８ ０ ％Ｗ ／ Ｖ ） ３ ０ ．
０ 富！ ／ １酢酸ナトリウム●３水和物 ２
４．０ｇ／ ｊ次亜リン酸ナトリウム ３０．０ｇ
，＃Ｐｂ”（酢酸鉛として） １．３＠ｇ／ｌ
３−（（アミノインムノメチル）チオ）一ｌ−プロパン
スノレフオンａ ２． Ｏ ｔａｇ／ｌＮａＯＨ
３． ８ ｇ／ ＩＮａ
−サッカリン １．５ｇ＃ｐＨ
４．８
鋼製パネルを上記の組成物で３５分間、ｐＨ４．９、浴
温８９℃でメッキした。CrO3 10g/l H3 PO4 (85%) 20 ■171
H. 80. (98%) '2sl/lN
i'' (as nickel sulfate) 8.2 g/l butyric acid (80% W/V) 30.
0 Wealth! / 1 Sodium acetate trihydrate 2
4.0g/j Sodium hypophosphite 30.0g
, #Pb” (as lead acetate) 1.3@g/l
3-((aminoinmunomethyl)thio)-1-propanesnorefone a 2. O tag/lNaOH
3. 8 g/INa
-Saccharin 1.5g#pH
4.8 Steel panels were plated with the above composition for 35 minutes at pH 4.9 and bath temperature 89°C.
実ＩＬｄ』１
実施例１に従って作ったニッケルメッキ済み鋼製パネル
を次の処方による溶液で処理した。Actual ILd'1 Nickel plated steel panels made according to Example 1 were treated with a solution according to the following formulation.
アノード時間 カソード時間 電流密度 浴温 ０．８秒 ０． ２秒 ０． ２５ＡＳＤ ２０〜２２℃ 電解処理を３０分間継続した。anode time cathode time Current density bath temperature 0.8 seconds 0. 2 seconds 0. 25ASD 20-22℃ The electrolytic treatment continued for 30 minutes.
優れた均一Ａ黒色被膜が得られた。An excellent uniform A black coating was obtained.
見飯匙エ
実施例１に記載のように鋼製パネルをメッキした。メッ
キの間、ニッケルと余分の次ｉＵン酸ナトリウムおよび
安定剤を添加して各成分を初期濃度に戻した。副生が避
けられないニッケルオルト亜リン酸塩の沈殿を防止する
ために、さらに酪酸を加えた。Steel panels were plated as described in Example 1. During plating, nickel and extra sodium hypophosphate and stabilizers were added to restore each component to its initial concentration. Butyric acid was further added to prevent precipitation of nickel orthophosphite, which is an inevitable by-product.
金属交換回数１１２、３、４および５後、この鋼製パネ
ルを実施例２に記載の転化方法に従って処理した。優れ
た均一な黒色披膜が得られた。After 112, 3, 4 and 5 metal exchanges, the steel panels were processed according to the conversion method described in Example 2. An excellent and uniform black arytenoid was obtained.
丸艷匙
実施例１に記載の組成物中で鋼製パネルの無電解メッキ
を行なったが、ナトリウムサッカリンは添加しなかった
。金属交換回数ｌ後、この鋼製パネルを取り出し実施例
２に記載の転化方法で処理した。転化ニッケル被膜の高
電流密度部分はＵ！Ｉ緑色、中電流密度部分は若干玉虫
色の黒色、低電流密度部分は玉虫色をした黒色を呈し、
満足できる黒色被膜は得られなかった。Electroless plating of steel panels was carried out in the composition described in Round Spoon Example 1, but without the addition of sodium saccharin. After l metal exchanges, the steel panels were removed and treated using the conversion method described in Example 2. The high current density part of the converted nickel film is U! I green, the medium current density area is slightly iridescent black, and the low current density area is iridescent black.
A satisfactory black film was not obtained.
Claims (22)
。(1) Electroless nickel plating composition containing saccharin.
記載の組成物。(2) Claim 1, wherein the nickel concentration is 1 to 25 g/l.
Compositions as described.
たは２記載の組成物。(3) The composition according to claim 1 or 2, which contains a reducing agent at a concentration of 5 to 50 g/l.
３記載の組成物。(4) The composition according to claim 3, wherein the reducing agent is sodium hypophosphite.
で含む請求項１または２記載の組成物。(5) Concentration of complexing agent for nickel ions from 5 to 50 g/l
The composition according to claim 1 or 2, comprising:
である請求項１記載の組成物。(7) the concentration of said saccharin is at least 0.7 g/l;
The composition according to claim 1.
項１記載の組成物。(8) The composition according to claim 1, wherein the concentration of the saccharin is 2 g/l or less.
載のの組成物。(9) The composition according to claim 1, which contains a buffering agent at a concentration of 5 to 40 g/l.
物。(10) The composition according to claim 9, wherein the buffer is acetic acid.
記載の組成物。(11) Claim 1 containing one or more stabilizers
Compositions as described.
物と素地とを接触させ、かつクロムを含む転化層を形成
させることから成る黒色無電解ニッケルメッキ膜の形成
方法。(12) A method for forming a black electroless nickel plating film, which comprises bringing an electroless nickel plating composition containing saccharin into contact with a substrate and forming a conversion layer containing chromium.
の硫黄を含む請求項１２記載の方法。13. The method of claim 12, wherein the conversion layer contains phosphorus and optionally sulfur.
成分から成る塩基性水和リン酸クロムから成り、場合に
よりＣｒ＿２（ＳＯ＿４）＿３をも含み得る転化層であ
ってＣｒ：Ｐ：Ｓ＝１：（０．２〜１．５）：（０〜０
．５）の重量比を示す請求項１３記載の方法。(14) The conversion layer is CrPO_4 and Cr(OH)_3
Cr:P:S=1:(0.2-1.5):(0- 0
．． 14. The method according to claim 13, wherein the weight ratio of 5) is indicated.
逆転させて処理することにより形成されて成る請求項１
２記載の方法。(15) Claim 1, wherein the conversion layer is formed by periodically reversing the current in the conversion composition.
The method described in 2.
求項１５記載の方法。(16) The method according to claim 15, wherein the current reversal period is 0.5 to 25 Hz.
ケルメッキ物品がカソードである期間とアノードである
期間との比（Ｔ＿ｏ＿ａ＿ｔ／Ｔ＿ａ＿ｎ）が０．１〜
０．８である請求項１２記載の方法。(17) The ratio of the period during which the electroless nickel plated article is a cathode to the period during which it is an anode in a given current cycle (T_o_a_t/T_a_n) is 0.1 to
13. The method according to claim 12, wherein the ratio is 0.8.
接触させて形成されて成る請求項１２記載の方法。18. The method of claim 12, wherein the conversion layer is formed in contact with a conversion composition containing nitrate ions.
（６５％）の供給により提供される濃度である請求項１
８記載の方法。(19) Claim 1, wherein the nitrate ion concentration is a concentration provided by supplying 5 to 10 ml/l of nitric acid (65%).
8. The method described in 8.
触させることにより転化反応を生起させて成る請求項１
２記載の方法。(20) Claim 1, wherein the conversion reaction is caused by contacting with a composition containing 2 to 20 g/l CrO_3.
The method described in 2.
られる濃度のリン酸イオンを含む組成物と接触させるこ
とにより転化反応を生起させて成る請求項１２記載の方
法。(21) The method according to claim 12, wherein the conversion reaction is caused by contacting with a composition containing phosphate ions at a concentration obtained by supplying 2 to 40 ml/l of concentrated phosphoric acid.
られる濃度の硫酸イオンを含む組成物と接触させること
により転化反応を生起させて成る請求項１２記載の方法
。(22) The method according to claim 12, wherein the conversion reaction is caused by contacting with a composition containing sulfate ions at a concentration obtained by supplying 0.1 to 5 ml/l of concentrated sulfuric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8904435A GB2231063A (en) | 1989-02-27 | 1989-02-27 | Electroless plating composition containing saccharin |
| GB8904435.8 | 1989-02-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0317277A true JPH0317277A (en) | 1991-01-25 |
Family
ID=10652386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2047102A Pending JPH0317277A (en) | 1989-02-27 | 1990-02-27 | Formation of plating composition and black electroless nickel-plating membrane |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPH0317277A (en) |
| BE (1) | BE1003583A5 (en) |
| CH (1) | CH680449A5 (en) |
| DE (1) | DE4005088A1 (en) |
| ES (1) | ES2021949A6 (en) |
| GB (1) | GB2231063A (en) |
| IT (1) | IT1240776B (en) |
| NL (1) | NL9000308A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004124261A (en) * | 2002-10-04 | 2004-04-22 | Enthone Inc | Electroless precipitation method for metal |
| JP2006169605A (en) * | 2004-12-17 | 2006-06-29 | Nippon Kanizen Kk | Method for forming electroless-plated nickel film having phosphate coating, and formed film thereby |
| KR20120050999A (en) * | 2009-07-03 | 2012-05-21 | 엔쏜 인코포레이티드 | Beta-amino acid comprising electrolyte and method for the deposition of a metal layer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850534B (en) * | 2020-06-16 | 2022-03-01 | 中国石油天然气集团有限公司 | Martensite stainless steel oil pipe low-stress pre-passivation film and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3088846A (en) * | 1962-01-24 | 1963-05-07 | Gen Am Transport | Processes of treating nickel-phosphorus alloy coatings and the resulting modified coatings |
| US3215700A (en) * | 1964-02-03 | 1965-11-02 | Harshaw Chem Corp | Certain 2-(hydroxyalkynyl)-substituted saccharins |
| US3586524A (en) * | 1969-07-10 | 1971-06-22 | Shell Oil Co | Consolidation of formations by electroless metal plating process |
| DE2111136A1 (en) * | 1971-03-09 | 1972-09-28 | Kalle Ag | Process for the production of metallized moldings from macromolecular material |
| JPS5437088B2 (en) * | 1972-02-18 | 1979-11-13 | ||
| CA1016488A (en) * | 1974-04-01 | 1977-08-30 | Oxy Metal Industries Corporation | Electrodeposition of bright nickel-iron deposits |
| GB1553503A (en) * | 1976-05-14 | 1979-09-26 | Oxy Metal Industries Corp | Electrodeposition of bright nickel-iron deposits |
| US4179343A (en) * | 1979-02-12 | 1979-12-18 | Oxy Metal Industries Corporation | Electroplating bath and process for producing bright, high-leveling nickel iron electrodeposits |
| NL8201849A (en) * | 1982-05-06 | 1983-12-01 | Philips Nv | ARTICLE WITH A NICKEL-PHOSPHORUS ALLOY COAT AND CONVERSION COAT. |
| JPS6075583A (en) * | 1983-09-29 | 1985-04-27 | Komatsu Ltd | Electroless plating method of ultra abrasive |
| JPS60248882A (en) * | 1984-05-24 | 1985-12-09 | Aisin Seiki Co Ltd | Electroless plating bath for plating high-phosphorus nickel alloy |
| CA1274754A (en) * | 1985-09-06 | 1990-10-02 | Gary A. Reghi | Passivation process and composition for zinc-aluminum alloys |
-
1989
- 1989-02-27 GB GB8904435A patent/GB2231063A/en not_active Withdrawn
-
1990
- 1990-02-09 NL NL9000308A patent/NL9000308A/en not_active Application Discontinuation
- 1990-02-17 DE DE4005088A patent/DE4005088A1/en active Granted
- 1990-02-21 ES ES9000522A patent/ES2021949A6/en not_active Expired - Lifetime
- 1990-02-23 BE BE9000202A patent/BE1003583A5/en not_active IP Right Cessation
- 1990-02-23 IT IT47670A patent/IT1240776B/en active IP Right Grant
- 1990-02-27 JP JP2047102A patent/JPH0317277A/en active Pending
- 1990-02-27 CH CH609/90A patent/CH680449A5/de not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004124261A (en) * | 2002-10-04 | 2004-04-22 | Enthone Inc | Electroless precipitation method for metal |
| JP2006169605A (en) * | 2004-12-17 | 2006-06-29 | Nippon Kanizen Kk | Method for forming electroless-plated nickel film having phosphate coating, and formed film thereby |
| KR20120050999A (en) * | 2009-07-03 | 2012-05-21 | 엔쏜 인코포레이티드 | Beta-amino acid comprising electrolyte and method for the deposition of a metal layer |
| JP2013508538A (en) * | 2009-07-03 | 2013-03-07 | エンソン インコーポレイテッド | β-amino acid-containing electrolyte and metal layer deposition method |
| JP2017166073A (en) * | 2009-07-03 | 2017-09-21 | マクダーミッド エンソン インコーポレイテッド | Plating formulation for depositing metal layer on substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2021949A6 (en) | 1991-11-16 |
| GB8904435D0 (en) | 1989-04-12 |
| DE4005088A1 (en) | 1990-08-30 |
| BE1003583A5 (en) | 1992-04-28 |
| NL9000308A (en) | 1990-09-17 |
| IT9047670A0 (en) | 1990-02-23 |
| CH680449A5 (en) | 1992-08-31 |
| GB2231063A (en) | 1990-11-07 |
| IT9047670A1 (en) | 1990-08-28 |
| IT1240776B (en) | 1993-12-17 |
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