JPH0213036B2 - - Google Patents
Info
- Publication number
- JPH0213036B2 JPH0213036B2 JP57147498A JP14749882A JPH0213036B2 JP H0213036 B2 JPH0213036 B2 JP H0213036B2 JP 57147498 A JP57147498 A JP 57147498A JP 14749882 A JP14749882 A JP 14749882A JP H0213036 B2 JPH0213036 B2 JP H0213036B2
- Authority
- JP
- Japan
- Prior art keywords
- lead
- tin
- acid
- plating bath
- bath
- 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.)
- Expired
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 55
- 238000007747 plating Methods 0.000 claims description 45
- -1 aliphatic aldehyde Chemical class 0.000 claims description 29
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- 229910001174 tin-lead alloy Inorganic materials 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 239000004615 ingredient Substances 0.000 claims description 10
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 2
- 238000005275 alloying Methods 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 claims 1
- 229930195729 fatty acid Natural products 0.000 claims 1
- 239000000194 fatty acid Substances 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 9
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 description 1
- AXZKCQSGDARVRL-UHFFFAOYSA-N 2-hydroxy-5-methylbenzenesulfonic acid Chemical class CC1=CC=C(O)C(S(O)(=O)=O)=C1 AXZKCQSGDARVRL-UHFFFAOYSA-N 0.000 description 1
- ODLIHNXQTJXBDT-UHFFFAOYSA-N 2-hydroxy-6-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(O)=C1S(O)(=O)=O ODLIHNXQTJXBDT-UHFFFAOYSA-N 0.000 description 1
- YIQGLTKAOHRZOL-UHFFFAOYSA-N 2-methoxynaphthalene-1-carbaldehyde Chemical compound C1=CC=CC2=C(C=O)C(OC)=CC=C21 YIQGLTKAOHRZOL-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- YCOXCINCKKAZMJ-UHFFFAOYSA-N 4-hydroxy-3-methylbenzenesulfonic acid Chemical compound CC1=CC(S(O)(=O)=O)=CC=C1O YCOXCINCKKAZMJ-UHFFFAOYSA-N 0.000 description 1
- ITPDYQOUSLNIHG-UHFFFAOYSA-N Amiodarone hydrochloride Chemical compound [Cl-].CCCCC=1OC2=CC=CC=C2C=1C(=O)C1=CC(I)=C(OCC[NH+](CC)CC)C(I)=C1 ITPDYQOUSLNIHG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPIIGEJBVZHNIN-UHFFFAOYSA-N [Cu].[Sn].[Pb] Chemical compound [Cu].[Sn].[Pb] PPIIGEJBVZHNIN-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
Description
本発明は種々の生地上へすず−鉛合金を析出せ
しめるための改良めつき浴に関する。特に本発明
は塩類と相容性の酸すなわちフツ化ホウ素酸と共
に、フツ化ホウ素酸すず（）とフツ化ホウ素酸
（）のような浴相容性のすず塩及び鉛塩を特殊
添加剤と共に浴成分として用いた改良浴から光沢
のある金属性のすず−鉛合金を析出せしめること
に関する。
すず−鉛合金めつき浴及びめつき方法に関する
先行特許は多数みられる。そのうち本発明と関連
が深いものは米国特許第3730853号；同第3749649
号；同第3769182号；同第3785939号；同第
3850765号；同第3875029号；同第3905878号；同
第3926749号；同第3954573号；同第3956123号；
同第3977949号；同第4000047号；同第4135991
号；同第4118289号；及び英国特許第1351875号と
同第1408148号である。
このように多数の文献があり、かつ多くの浴組
成が提案されているにも拘らず、光沢があり金属
質のすず−鉛合金めつきを種々の生地上へ効率良
く析出せしめるための浴についてはなお改良の余
地があり、他の重要な特性は高速めつき性とレベ
リング性である。従来から提案されてきたすず−
鉛合金浴組成の多くのものが、浴の調製に用いる
総ての成分はめつき光沢だけでなく前記のような
他の特性についても同時に考慮を払う必要がある
ことを示している。
本発明の目的の一つは各種の生地上に光沢性の
すず−鉛合金を析出せしめうるめつき浴の提供に
ある。
本発明の他の目的は比較的高速においても、な
おかつ改良せられた光沢を有するすず−鉛合金め
つきが得られる電気めつき浴の提供にある。
本発明のさらにその他の目的を析出せられたレ
ベリング性を有するすず−鉛合金めつきを生成せ
しめうる電気めつき浴の提供にある。
この発明のさらに多くの目的は、次の記載と実
施例とを理解することにより自明となるはずであ
る。
この発明によれば可溶性すず塩と鉛塩ならびに
これらと相容性の酸と共に特殊な添加剤が組み合
わせたものを使用すると改良めつき浴が得られる
ことが分つた。この発明によるめつき浴は各種の
生地上に光沢のある金属性のすず−鉛合金を高速
にて析出させることができる。
浴への添加物の必要な組み合せは、芳香族アミ
ン光沢剤、芳香族アルデヒド光沢剤、脂肪族アル
デヒド光沢剤及び非イオン界面剤系粒子リフアイ
ナーである。
この発明の他の提案によれば、このめつき浴か
らすず及び鉛と共に銅もしくはロジウム金属を三
元合金の形で効果的に共析することができる。
この発明のめつき浴は、好ましくは同じアニオ
ンを有し、特に好ましくはフツ化ホウ素酸すず及
びフツ化ホウ素酸鉛のような浴可溶性の形の２価
のすず及び鉛化合物を用いて調製する。フツ化ホ
ウ素酸すず及びフツ化ホウ素酸鉛を使用するとき
にはこれらに相容性の酸、特に好ましくはフツ化
ホウ素酸を十分な量だけ共存させて導電性を付与
し、また金属塩類の溶解度を維持せしめる。浴中
のすずと鉛の量は所望のすず−鉛合金を効果的に
析出せしめるのに少なくとも十分な量ないしは浴
への最大溶解度以下である。
塩化物、スルフアミン酸塩、フエノールスルホ
ネート及びその他のような他の浴可溶性２価すず
塩ならびに２価鉛塩もまたこの発明の浴の調製に
使用しうる。異種のアニオンを有するすず塩及び
鉛塩でも使用は可能であるが、同種アニオンを有
する塩類の使用が好ましい。更に、塩化水素酸、
スルフアミン酸、フエノールスルホン酸及びその
他のような他の相容性酸類もまたフツ化ホウ素酸
の代りに、またフツ化ホウ素酸と共に使用しう
る。使用する酸はすず塩及び鉛塩のそれとは異な
つたアニオンを持つこともできるが、同じアニオ
ンであることが好ましい。しかしながら、最も好
ましい実施態様ではすず及び鉛のフツ化ホウ素酸
塩がフツ化ホウ素酸と共に用いられる。
この発明における光沢剤組成物は芳香族アミ
ン、芳香族アルデヒド及び脂肪族アルデヒドの組
み合わせである。これら光沢剤のそれぞれの含有
量は少なくともすず−鉛合金めつきに光沢を付与
するのに十分な量ないしは浴中へのそれぞれの最
大溶解度以下である。当該光沢剤組成物において
の芳香族アミン対芳香族アルデヒドの重量比は
1.25：１ないし100：１以内、特に好ましくは約
５：１ないし20：１の範囲以内である。
この発明の目的達成に対して有用な芳香族アミ
ンもしくはアリルアミンにはｏ−トルイジン、ｐ
−トルイジン、ｍ−トルイジン、アニオン及びｏ
−クロルアニリンが包含せられる。殆どの目的で
はｏ−クロルアニオンの使用が特に好ましい。例
えば芳香族アルデヒドには１−ナフタルデヒド、
２−ヒドロキシ−１−ナフタルデヒド、２−メト
キシ−１−ナフタルデヒド及びその他が包含せら
れる。このうちで好ましい芳香族アルデヒドは１
−ナフタルデヒドである。好ましい脂肪族アルデ
ヒドは炭素数１ないし４のもので、例えばホルム
アルデヒド、アセトアルデヒド、プロピルアルデ
ヒド、ブチルアルデヒド、クロトンアルデヒド及
びその他が包含せられる。この発明における好ま
しいアルデヒドはホルムアルデヒドであるが、ホ
ルムアルデヒドを37重量％含有するホルマリンを
使用すると便利である。
粒子リフアイナーとしての非イオン界面活性剤
の添加もまた必要である。この含有量はすず−鉛
合金めつきの粒子に緻密性を付与するのに十分な
量ないしは浴への最大溶解度以下である。
好ましい非イオン界面活性剤は市販のものであ
つて、例えばノニルフエノキシポリエチレンオキ
サイドエタノール（Ipepal Ｃ 0630及びTriton
QS 15、商標名）；エトキシアルキロールアミド
（Amidox L5及びC3、商標名）；アルキルポリグ
リコールエーテルエチレンオキサイド
（Neutronyx 675 商標名）及びその他である。
この発明において最も効果がある非イオン界面活
性剤は、そのアルキレン基中の炭素数が２ないし
20であるポリオキシアルキレンエーテルである。
親油基のモル当り、エチレンオキサイドの10な
いし20モルを有するポリオキシエチレンエーテル
が好ましく、このなかにはブリジ35−SP（商標
名、Buij35−SP）として市販されているポリオ
キシエチレンラウリルエーテルのような界面活性
剤が包含される。
浴の補給に用いた第１すず塩が第２すず化合物
へ酸化されて沈澱を生ずるの防止するための酸化
防止剤も浴中に添加してよい。めつき浴が示す酸
性のPHにおいて有効であり、かつこの発明方法の
遂行をさまたげたり、生成めつきに悪影響を及ぼ
さないようなものであればいかなる酸化防止剤で
も使用できる。酸化防止剤の使用量は通常、約
0.5ないし50ｇ/、好ましくは約５ないしは10
ｇ／である。
特に好ましい酸化防止剤は芳香族スルホン酸類
である。代表的な芳香族スルホン酸にはｏ−クレ
ゾールスルホン酸、ｍ−クレゾールスルホン酸及
びフエノールスルホン酸が包含せられる。
フエノールやクレゾールの他のスルホン酸、例
えば：
２，６−ジメチルフエノールスルホン酸
２−クロル−６−メチルフエノールスルホン酸
２，４−ジメチルフエノールスルホン酸
２，４，６−トリメチルフエノールスルホン酸
ｐ−クレゾールスルホン酸
なども使用できる。α−及びβ−ナフトールのス
ルホン酸誘導体もまた使用できる。
この発明の水性めつき浴の好ましい成分を総括
すれば次のようである。
This invention relates to an improved plating bath for depositing tin-lead alloys onto various substrates. In particular, the present invention uses salt-compatible acids, namely fluoroboric acid, as well as bath-compatible tin and lead salts such as tin fluoroborate and fluoroboric acid, together with special additives. This invention relates to the precipitation of bright metallic tin-lead alloys from improved baths used as bath components. There are many prior patents related to tin-lead alloy plating baths and plating methods. Among these, those closely related to the present invention are U.S. Patent Nos. 3730853 and 3749649.
No. 3769182; No. 3785939; No. 3785939;
No. 3850765; No. 3875029; No. 3905878; No. 3926749; No. 3954573; No. 3956123;
Same No. 3977949; Same No. 4000047; Same No. 4135991
No. 4118289; and British Patent No. 1351875 and British Patent No. 1408148. Although there are many literatures and many bath compositions have been proposed, there is still no research regarding the bath for efficiently depositing shiny, metallic tin-lead alloy plating onto various fabrics. There is still room for improvement; other important properties are high-speed plating and leveling. Tin that has been proposed for a long time
Many of the lead alloy bath compositions indicate that all components used in the preparation of the bath must be considered not only for plating gloss, but also for other properties such as those mentioned above. One of the objects of the present invention is to provide a lubricating bath that deposits a bright tin-lead alloy on various fabrics. Another object of the invention is to provide an electroplating bath which provides tin-lead alloy plating with improved gloss even at relatively high speeds. Still another object of the present invention is to provide an electroplating bath capable of producing a tin-lead alloy plating having leveling properties. Further objects of the invention will become apparent from the following description and examples. In accordance with the present invention, it has been found that an improved plating bath can be obtained by using a combination of soluble tin and lead salts and special additives with compatible acids. The plating bath according to the present invention is capable of depositing a shiny metallic tin-lead alloy on various fabrics at high speed. The required combination of additives to the bath is an aromatic amine brightener, an aromatic aldehyde brightener, an aliphatic aldehyde brightener, and a nonionic surfactant-based particle refiner. According to another proposal of the invention, copper or rhodium metal can be effectively eutectoided from this plating bath together with tin and lead in the form of a ternary alloy. The plating baths of the invention are preferably prepared using divalent tin and lead compounds having the same anions, particularly preferably in bath-soluble form, such as tin fluoroborate and lead fluoroborate. . When tin fluoroborate and lead fluoroborate are used, a compatible acid, particularly preferably fluoroboric acid, is allowed to coexist in a sufficient amount to impart conductivity and to improve the solubility of the metal salts. maintain it. The amounts of tin and lead in the bath are at least sufficient to effectively precipitate the desired tin-lead alloy or less than its maximum solubility in the bath. Other bath-soluble divalent tin and lead salts such as chlorides, sulfamates, phenolsulfonates, and others may also be used in preparing the baths of this invention. Although it is possible to use tin salts and lead salts having different types of anions, it is preferable to use salts having the same type of anions. Furthermore, hydrochloric acid,
Other compatible acids such as sulfamic acid, phenolsulfonic acid and others may also be used in place of and with fluoroboric acid. The acids used can have different anions than those of the tin and lead salts, but preferably they are the same. However, in the most preferred embodiment, tin and lead fluoroborate salts are used with fluoroboric acid. The brightener composition in this invention is a combination of an aromatic amine, an aromatic aldehyde, and an aliphatic aldehyde. The content of each of these brighteners is at least sufficient to impart brightness to the tin-lead alloy plating or is below its respective maximum solubility in the bath. The weight ratio of aromatic amine to aromatic aldehyde in the brightener composition is
It is within the range of 1.25:1 to 100:1, particularly preferably within the range of about 5:1 to 20:1. Aromatic or allyl amines useful in achieving the objectives of this invention include o-toluidine, p-toluidine,
-toluidine, m-toluidine, anion and o
- Chloraniline is included. The use of o-chloranion is particularly preferred for most purposes. For example, aromatic aldehydes include 1-naphthaldehyde,
Included are 2-hydroxy-1-naphthaldehyde, 2-methoxy-1-naphthaldehyde and others. Among these, the preferred aromatic aldehyde is 1
- Naphthaldehyde. Preferred aliphatic aldehydes have 1 to 4 carbon atoms and include, for example, formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, crotonaldehyde, and others. Although the preferred aldehyde in this invention is formaldehyde, it is convenient to use formalin containing 37% by weight formaldehyde. The addition of nonionic surfactants as particle refiners is also necessary. This content is sufficient to impart compactness to the particles of the tin-lead alloy plating or is below the maximum solubility in the bath. Preferred nonionic surfactants are commercially available, such as nonylphenoxy polyethylene oxide ethanol (Ipepal C 0630 and Triton
QS 15, trade name); ethoxyalkylolamide (Amidox L5 and C3, trade name); alkyl polyglycol ether ethylene oxide (Neutronyx 675 trade name) and others.
The most effective nonionic surfactant in this invention has 2 or more carbon atoms in its alkylene group.
20 is a polyoxyalkylene ether. Preferred are polyoxyethylene ethers having 10 to 20 moles of ethylene oxide per mole of lipophilic group, including polyoxyethylene lauryl ether, commercially available as Buij 35-SP. Surfactants are included. Antioxidants may also be added to the bath to prevent the stannous salts used to replenish the bath from oxidizing to stannous compounds and forming precipitates. Any antioxidant can be used as long as it is effective at the acidic pH of the plating bath and does not interfere with the process of this invention or adversely affect the resulting plating. The amount of antioxidant used is typically approx.
0.5 to 50 g/, preferably about 5 to 10
g/. Particularly preferred antioxidants are aromatic sulfonic acids. Representative aromatic sulfonic acids include o-cresol sulfonic acid, m-cresol sulfonic acid, and phenolsulfonic acid. Other sulfonic acids of phenol and cresol, such as: 2,6-dimethylphenolsulfonic acid 2-chloro-6-methylphenolsulfonic acid 2,4-dimethylphenolsulfonic acid 2,4,6-trimethylphenolsulfonic acid p-cresol Sulfonic acids and the like can also be used. Sulfonic acid derivatives of α- and β-naphthol can also be used. The preferred components of the aqueous plating bath of the present invention are summarized as follows.
【表】
これらの濃度での浴のPHは通常約１以下、一般
には約１ないし約0.05であるが、１以上でも使用
は可能である。浴温及び電流密度はそれぞれ約10
℃ないし40℃及び約0.5A/Dm2（5ASF）ないし53
Ａ／Ｄm2（500ASF）、好ましくは15℃ないしは25
℃及び2.6A/Dm2（25ASF）ないし21A/Dm2
（200ASF）である。
この発明によるめつき浴及び方法はすず−鉛合
金組成を広範に変更できる。約（99重量％すずと
１重量％鉛）ないし約（99重量％鉛と１重量％す
ず塩）の合金皮膜を得ることができる。異なる組
成の合金皮膜を生成せしめたい場合には当然のこ
と乍ら浴成分の相関量を変更して所望の組成の合
金に対しての最適の光沢と延性ならびに他の特性
が付与されるようにすべきである。実用的見地か
らして、約（95重量％と５重量％鉛）の組成のす
ず−鉛合金皮膜及び約（60重量％すずと40重量％
鉛）の組成を有するはんだ皮膜が特に有用であり
いずれもこの発明による浴と方法によつて容易に
生成させることができる。
ほとんどのめつき操作ではかくはんし、しばし
ば急速かくはんが好ましく適用される。更にアノ
ード：カソード比は約１：１ないし10：１であ
り、約４：１が好ましい。この発明の浴と方法は
銅、銅合金、鋼、ニツケル、ニツケル合金及びそ
の他に適用される。
前述したようにこの発明の浴を用いることによ
つて、追加的な添加物又は錯化剤を加えないでも
銅及びロジウム金属をすずと鉛の合金中に共析さ
せることができる。ニツケル、鉄及びインジウム
のような金属は同じ条件下では共析しなかつた。
通常、銅又はロジウムはすず及び鉛と同じアニ
オンを有する浴可溶性化合物として浴中に添加す
るのが好ましい。添加量はすず−鉛合金中に約５
重量％の銅又はロジウムが共析するのに十分な量
である。かかる共析皮膜を得るための銅及びロジ
ウムの浴濃度はそれぞれ約0.2ないし４ｇ/及び
0.2ないし２ｇ/である。
この発明の他の提案によれば、脂肪族アルデヒ
ドに追加してか、または脂肪族アルデヒドの50重
量％までを、対応する脂肪族酸によつて置換する
ことができ、この際はんだ用皮膜の光沢や他の皮
膜特性には悪影響を与えない。例えばホルムアル
デヒドの50重量％以下をギ酸によつて置換しても
この発明の基本的なすず−鉛浴の性能を維持して
いる。比較のために、前記したホルムアルデヒド
量の50重量％以下しか含まない浴は添加したギ酸
の量に拘りなく皮膜の外観が悪くなる。一方、添
加するギ酸の量はホルムアルデヒドの排除量と正
確に一致しなくてもよく、またホルムアルデヒド
の排除なしでも添加することができる。更にホル
ムアルデヒドを全く添加しないでもギ酸はその発
明の浴にほとんど悪影響を与えないか又は無影響
である。
50重量％以下のホルムアルデヒドをギ酸により
置換することの利点は、めつき操作中でのホルム
アルデヒドの消耗量が減少することであり、これ
により比較的少量のホルムアルデヒドの補給でこ
とが足りる点にある。
ある運転条件においては浴中にホウ酸を添加し
て遊離のフツ化水素酸の生成を防止又は減少せし
めるのが有利な場合がある。ホウ酸の添加量は遊
離のフツ化水素酸の生成を実質的に減少せしめる
のに十分な量であればよい。通常約60ｇ/、好
ましくは30ｇ/である。この発明によるすず−
鉛めつき浴は界面活性剤を含有しており、この活
性剤はある種の用途に用いると発泡を起こすこと
がある。この発泡の問題は適当な消泡剤を約0.06
c.c.／ないし浴中への溶解度の範囲で含有せしめ
ることにより解決できる。特に好ましい消泡剤は
オクチルアルコールであり、このアルコールは他
の浴成分とは化学的に、また電気化学的にも相容
しないが、このすず−鉛皮膜にはなんら悪影響を
与えない。
この発明は次の実施例の判読によつて更に理解
が容易になるはずである。
実施例 １
次に記載の諸成分からめつき浴を調製した。
成 分 量
すず塩（フツ化ホウ素酸第１すずとして添加）
30ｇ/
鉛（フツ化ホウ素酸鉛として添加） ４ｇ/
フツ化ホウ素酸 172ｇ/
ｏ−クロルアニオン 0.5ｇ/
ホルマリン 20c.c./
ポリオキシエチレンラウリルエーテル 2.5ｇ/
１−ナフタアルデヒド 0.05ｇ/
水 バランス
調製された浴は安定であり20℃、60ASF（６A/
Ｄm2）において、かくはん下で銅試験片上にめつ
きした。生成したすず−鉛皮膜は95重量％の鉛か
ら成り、著しい光沢を呈していた。
実施例 ２
実施例１の処方において、0.5ｇ/のフツ化ホ
ウ素酸銅を添加した。この浴を用いて６A/Dm2
にてめつきを行つたところ約１重量％の銅、89重
量％のすず及び５重量％の鉛から成る光沢性のす
ず−鉛−銅合金めつきが得られた。
上記の２価のすず−鉛浴において銅に代えて鉄
及びインジウム金属を用いたところ、これらの金
属類の共析は全く起こらなかつた。
実施例 ３
次の成分を用いて浴を調製した。
成 分 量
すず（フツ化ホウ素酸第１すずとして添加）
30ｇ/
鉛（フツ化ホウ素酸鉛として添加） ４ｇ/
フツ化ホウ素酸 172ｇ/
ホウ酸 20ｇ/
ホルマリン 20c.c./
ｏ−クロルアニリン 0.5ｇ/
１−ナフタアルデヒド 0.05ｇ/
ポリオキシエチレンラウリルエーテル 2.5ｇ/
ギ酸（88重量％） ２c.c./
浴は室温、６A/Dm2、急速かくはん下ですず
−鉛アノードを用いて操作した。ホルムアルデヒ
ド濃度は実施例１と全く同じであるがギ酸を添加
することにより引き続くホルムアルデヒドの補給
をしないでもよいようにした。生成したすず−鉛
めつきは著しく光沢がありすずを95重量％と鉛を
５重量％含有していた。
実施例 ４
次の諸成分を用いてすず−鉛めつき浴を調製し
た。
成 分 量
すず（フツ化ホウ素酸第１すずとして添加）
30ｇ/
鉛（フツ化ホウ素酸鉛として添加） ４ｇ/
フツ化ホウ素酸 172ｇ/
ホウ酸 20ｇ/
ホルマリン 10c.c./
ｏ−クロルアニリン 0.5ｇ/
１−ナフタアルデヒド 0.05ｇ/
ポリオキシエチレンラウリルエーテル 2.5ｇ/
ギ酸（88重量％） ５c.c./
この浴を実施例３に記載の条件で操作した。も
ともと必要なホルムアルデヒド量の50重量％をギ
酸により置換したにも拘らず、20c.c./のホルマ
リンを含みギ酸を含まない実施例１の浴により得
られたと全く同じ光沢であつた。
実施例 ５
実施例１によるめつき浴中に、それぞれ0.06
c.c.／及び0.18c.c./のオクチルアルコールを添加
した。これらの浴を実施例１と同様に操作したと
ころ、すずを95重量％と鉛を５重量％含む極めて
明るいすず−鉛皮膜が生成した。
これらの浴のそれぞれ及び実施例１の浴から試
料を採取して瓶中に仕込み、蓋をほどこしたのち
振盪した。0.06c.c./のオクチルアルコールを含
む試料の泡の高さは実施例１の浴から採取した試
料を含む瓶中の高さよりも約20％ないし30％低か
つた。0.18c.c./のオクチルアルコール含有試料
瓶中の泡の高さは実施例１の浴から採取した試料
を含む瓶中の高さと殆んど同じであつた。前者に
おける泡の消失時間は後者のそれより約30％少な
かつた。
実施例 ６
次の諸成分を用いてめつき浴を調製した。
成 分 量
すず（フツ化ホウ素酸第１すずとして添加）
30ｇ/
鉛（フツ化ホウ素酸鉛として添加） ８ｇ/
フツ化ホウ素酸 172ｇ/
ｏ−クロルアニリン 0.56ｇ/
ホルマリン 20c.c./
ポリオキシエチレンラウリルエーテル2.5c.c./
１−ナフタアルデヒド 0.11c.c./
水 バランス
調製浴は安定であり、20℃、６A/Dm2にてか
くはん下で銅試験片をめつきした。生成したすず
−鉛皮膜は著しく光沢があり、60重量％のすずと
40重量％の鉛を含んでいた。
実施例 ７
この発明における必須の添加剤の効果を説明す
るために、次のような５種類のめつき浴を調製し
た。
Ａ−実施例１の浴
Ｂ−非イオン界面活性剤のない実施例１の浴
Ｃ−脂肪族アルデヒドのない実施例の浴
Ｄ−芳香族アミンのない実施例１の浴
Ｅ−芳香族アルデヒドのない実施例１の浴
これらの浴を実施例１と同じ条件にて操作した
ところ、次の結果が得られた。
浴Ａ 光沢性、平滑皮膜
浴Ｂ 樹枝状粒子のある黒色スポンジ皮膜
浴Ｃ 曇つた金属性白色皮膜
浴Ｄ 曇つた灰色又は黒色曇り
浴Ｅ 高電流密度部分にてスキツプめつきによ
る半光沢皮膜、低電流密度部分にて白色
曇り皮膜
実施例 ８
芳香族アミン対芳香族アルデヒドの比が1.25：
１ないし100：１の範囲以外の場合の浴を用いた
ときの効果を説明するために、次の諸成分を用い
て電気めつき浴を調製した。
成 分 量
すず（フツ化ホウ素酸第１すずとして添加）
30ｇ/
鉛（フツ化ホウ素酸鉛として添加） ４ｇ/
フツ化ホウ素酸 172ｇ/
ホルマリン 20c.c./
ポリオキシエチレンラウリルエーテル 2.5ｇ/
ｏ−クロルアニリン 変動
１−ナフタアルデヒド 変動
これらの実験では真鍮生地上に、浴温20℃、６
Ａ／Ｄm2、激しいかくはんの条件下ですず−鉛合
金めつきを施した。ｏ−クロルアニリン対１−ナ
フタアルデヒドのは、次のようになるように変え
た。
ノルマル−光沢剤の比率範囲内の濃度
ハイ−比率範囲の上限を越えた濃度
ロウ−比率範囲の下限以下の濃度
この方式では次のような結果が得られた。[Table] The PH of the bath at these concentrations is usually less than about 1, generally from about 1 to about 0.05, although it is possible to use PH of 1 or more. Bath temperature and current density are each about 10
℃ to 40℃ and about 0.5A/Dm 2 (5ASF) to 53
A/Dm 2 (500ASF), preferably 15°C or 25°C
℃ and 2.6A/Dm 2 (25ASF) to 21A/Dm 2
(200ASF). The plating bath and method according to the present invention allows for a wide variety of tin-lead alloy compositions. An alloy coating of about (99 wt.% tin and 1 wt.% lead) to about (99 wt.% lead and 1 wt.% tin salt) can be obtained. Of course, if it is desired to produce an alloy film of a different composition, the relative amounts of the bath components may be varied to provide the optimum gloss, ductility and other properties for the alloy of the desired composition. Should. From a practical point of view, tin-lead alloy coatings with a composition of about (95% by weight and 5% by weight lead) and about (60% by weight tin and 40% by weight
Particularly useful are solder films having a composition of lead), both of which can be easily produced by the baths and methods of this invention. Most plating operations involve agitation, often rapid agitation being preferred. Further, the anode:cathode ratio is about 1:1 to 10:1, with about 4:1 being preferred. The baths and methods of this invention are applicable to copper, copper alloys, steel, nickel, nickel alloys, and others. As previously mentioned, by using the bath of the present invention, copper and rhodium metals can be eutectoided into tin-lead alloys without the addition of additional additives or complexing agents. Metals such as nickel, iron and indium did not eutectoid under the same conditions. Generally, copper or rhodium is preferably added to the bath as a bath-soluble compound having the same anions as tin and lead. The amount added is approximately 5% in the tin-lead alloy.
The amount is sufficient to eutectoid the weight percent of copper or rhodium. The bath concentrations of copper and rhodium to obtain such eutectoid coatings are approximately 0.2 to 4 g/ and
0.2 to 2 g/. According to another proposal of the invention, in addition to the aliphatic aldehydes or up to 50% by weight of the aliphatic aldehydes can be replaced by the corresponding aliphatic acids, in this case forming the solder film. Does not adversely affect gloss or other film properties. For example, the basic tin-lead bath performance of the present invention can be maintained even if less than 50% by weight of formaldehyde is replaced by formic acid. For comparison, baths containing less than 50% by weight of formaldehyde as described above result in poor film appearance regardless of the amount of formic acid added. On the other hand, the amount of formic acid added does not have to correspond exactly to the amount of formaldehyde excluded, and it can also be added without formaldehyde exclusion. Furthermore, formic acid has little or no adverse effect on the baths of the invention, even without the addition of any formaldehyde. The advantage of replacing up to 50% by weight of formaldehyde with formic acid is that the amount of formaldehyde consumed during the plating operation is reduced, so that a relatively small amount of formaldehyde replenishment is sufficient. Under certain operating conditions it may be advantageous to add boric acid to the bath to prevent or reduce the formation of free hydrofluoric acid. The amount of boric acid added may be sufficient to substantially reduce the formation of free hydrofluoric acid. Usually about 60g/, preferably 30g/. Tin according to this invention
Lead plating baths contain surfactants, which can cause foaming when used in certain applications. This foaming problem can be solved with a suitable antifoaming agent of about 0.06
This can be solved by including the compound within the range of solubility in the bath. A particularly preferred antifoaming agent is octyl alcohol, which is chemically and electrochemically incompatible with other bath components but does not have any adverse effect on the tin-lead coating. This invention will become easier to understand by reading the following examples. Example 1 A plating bath was prepared from the following ingredients. Ingredients Quantity Tin salt (added as stannous fluoroborate)
30g/ Lead (added as lead fluoroborate) 4g/ Fluoroborate 172g/ o-chloranion 0.5g/ Formalin 20c.c./ Polyoxyethylene lauryl ether 2.5g/ 1-naphthaldehyde 0.05g/ Water balance The prepared bath is stable at 20℃ and 60ASF (6A/
Dm 2 ) on a copper specimen under agitation. The resulting tin-lead film consisted of 95% lead by weight and had a remarkable shine. Example 2 In the formulation of Example 1, 0.5 g/copper fluoroborate was added. 6A/Dm 2 using this bath
A bright tin-lead-copper alloy plating consisting of approximately 1% by weight copper, 89% tin and 5% lead was obtained. When iron and indium metals were used in place of copper in the above divalent tin-lead bath, no eutectoiding of these metals occurred. Example 3 A bath was prepared using the following ingredients. Ingredients Quantity Tin (added as stannous fluoroborate)
30g/ Lead (added as lead fluoroborate) 4g/ Fluoroboric acid 172g/ Boric acid 20g/ Formalin 20c.c./ o-Chloraniline 0.5g/ 1-Naphthalaldehyde 0.05g/ Polyoxyethylene lauryl ether 2.5 g/Formic acid (88% by weight) 2 c.c./ The bath was operated at room temperature, 6 A/Dm 2 with a tin-lead anode under rapid stirring. The formaldehyde concentration was exactly the same as in Example 1, but formic acid was added to eliminate the need for subsequent formaldehyde replenishment. The resulting tin-lead plating was extremely shiny and contained 95% by weight tin and 5% by weight lead. Example 4 A tin-lead plating bath was prepared using the following ingredients. Ingredients Quantity Tin (added as stannous fluoroborate)
30g/ Lead (added as lead fluoroborate) 4g/ Fluoroboric acid 172g/ Boric acid 20g/ Formalin 10c.c./ o-Chloraniline 0.5g/ 1-Naphthalaldehyde 0.05g/ Polyoxyethylene lauryl ether 2.5 g/Formic acid (88% by weight) 5 c.c./ This bath was operated under the conditions described in Example 3. Even though 50% by weight of the originally required amount of formaldehyde was replaced by formic acid, the gloss was exactly the same as that obtained with the bath of Example 1 containing 20 c.c./g of formalin and no formic acid. Example 5 In the plating bath according to Example 1, each 0.06
cc/ and 0.18 cc/ of octyl alcohol were added. When these baths were operated as in Example 1, very bright tin-lead films containing 95% by weight tin and 5% by weight lead were produced. Samples were taken from each of these baths and from the bath of Example 1, placed in bottles, capped and shaken. The foam height for the sample containing 0.06 cc/octyl alcohol was approximately 20% to 30% lower than the height in the bottle containing the sample taken from the bath of Example 1. The foam height in the sample bottle containing 0.18 cc/octyl alcohol was almost the same as the height in the bottle containing the sample taken from the bath of Example 1. The foam disappearance time in the former was about 30% less than that in the latter. Example 6 A plating bath was prepared using the following ingredients. Ingredients Quantity Tin (added as stannous fluoroborate)
30g/ Lead (added as lead fluoroborate) 8g/ Fluoroboric acid 172g/ o-chloroaniline 0.56g/ Formalin 20c.c./ Polyoxyethylene lauryl ether 2.5cc/ 1-naphthaldehyde 0.11cc/ Water balance The prepared bath was stable and copper specimens were plated at 20° C. and 6 A/Dm 2 with stirring. The resulting tin-lead film is extremely shiny and has a tin content of 60% by weight.
It contained 40% lead by weight. Example 7 In order to explain the effects of the essential additives in this invention, the following five types of plating baths were prepared. A - Bath of Example 1 B - Bath of Example 1 without nonionic surfactant C - Bath of Example 1 without aliphatic aldehyde D - Bath of Example 1 without aromatic amine E - Bath of example 1 without aromatic aldehyde When these baths were operated under the same conditions as in Example 1, the following results were obtained. Bath A Glossy, smooth film Bath B Black sponge film with dendritic particles Bath C Cloudy metallic white film Bath D Cloudy gray or black haze Bath E Semi-gloss film due to skip plating in high current density areas, low White cloudy film Example 8 in current density area Ratio of aromatic amine to aromatic aldehyde is 1.25:
An electroplating bath was prepared using the following components to illustrate the effect of using a bath outside the 1 to 100:1 range. Ingredients Quantity Tin (added as stannous fluoroborate)
30 g/ Lead (added as lead fluoroborate) 4 g/ Fluoroboric acid 172 g/ Formalin 20 c.c./ Polyoxyethylene lauryl ether 2.5 g/ o-Chloraniline variation 1 - Naphthaldehyde variation In these experiments, brass fabric Above, bath temperature 20℃, 6
A/Dm 2 , tin-lead alloy plating was applied under conditions of vigorous agitation. The ratio of o-chloroaniline to 1-naphthaldehyde was changed as follows. Normal - concentration within the ratio range of the brightener High - density above the upper limit of the ratio range Low - density below the lower limit of the ratio range The following results were obtained with this method.
【表】
ノルマル ノルマル 明るい平滑な皮膜
前記した実施例は単に説明の目的のためのもの
であり、この発明の範囲から逸脱することなく
種々の変更や修正がなされうることは自明であ
る。[Table] Normal Normal Bright Smooth Film It is obvious that the examples described above are for illustrative purposes only and that various changes and modifications can be made without departing from the scope of the invention.
Claims (1)
上に所望のすず−鉛合金めつきを折出せしめるの
に十分な量ないし浴への最高溶解量までの範囲の
浴可溶性２価すず塩及び２価鉛塩；該塩類と相容
する酸であつて浴に対し導電性を付与し浴中への
該塩類の溶解性を維持するのに十分な量の酸：め
つき粒子リフアイナーとして有効な量の非イオン
界面活性剤；ならびに芳香族アルデヒド、脂肪族
アルデヒド及び芳香族アミンから成る光沢剤組成
物であつて、該各成分がすず−鉛合金めつき膜に
光沢を付与するのに十分な量で存在し、かつ芳香
族アミン；芳香族アルデヒドの比が1.25；１ない
し100：１の範囲にある光沢剤組成物から成るめ
つき浴。 ２ すず塩および鉛塩が、それぞれフツ化ホウ素
酸第１すず塩及びフツ化ホウ素酸鉛である特許請
求の範囲第１項記載のめつき浴。 ３ 相容性の酸が、フツ化ホウ素酸である特許請
求の範囲第１項記載のめつき浴。 ４ 銅及びロジウムから成る群から選択された合
金化金属をさらに含有して成る特許請求の範囲第
１項記載のめつき浴。 ５ 浴中にホウ酸をさらに含有して成る特許請求
の範囲第１項記載のめつき浴。 ６ 浴中に消泡剤をさらに含有して成る特許請求
の範囲第１項記載のめつき浴。 ７ 消泡剤がオクチルアルコールである特許請求
の範囲第６項記載のめつき浴。 ８ 該脂肪族アルデヒドの50重量％までが対応す
る脂肪酸により置換されて成る特許請求の範囲第
１項記載のめつき浴。 ９ 各成分の次の量、 すず ５〜50ｇ/ 鉛 ３〜20ｇ/ 相容性の酸 100〜250ｇ/ 非イオン界面活性剤 0.1〜20ｇ/ 芳香族アミン 0.3〜15ｇ/ 芳香族アルデヒド 0.01〜0.5ｇ/ 脂肪族アルデヒド 0.5〜20ｇ/ にて含有されて成る特許請求の範囲第１項記載の
めつき浴。 １０ すず及び鉛がそれぞれフツ化ホウ素酸及び
フツ化ホウ素酸鉛として、相容性の酸がフツ化ホ
ウ素酸として、非イオン界面活性剤がポリオキシ
エチレンラウリルエーテルとして、芳香族アミン
がｏ−クロルアニリンとして、芳香族アルデヒド
が１−ナフタアルデヒドとして、脂肪族アルデヒ
ドがホルマリンとして添加されて成る特許請求の
範囲第９項記載のめつき浴。 １１ ホルムアルデヒドの50重量％までがギ酸に
より置換されて成る特許請求の範囲第１０項記載
のめつき浴。[Scope of Claims] 1. An electroplating bath for tin-lead alloys, which ranges from an amount sufficient to deposit a desired tin-lead alloy plating on fabrics to a maximum amount dissolved in the bath. bath-soluble divalent tin salts and divalent lead salts; an acid compatible with the salts in an amount sufficient to impart conductivity to the bath and maintain the solubility of the salts in the bath; : A brightener composition comprising an effective amount of a nonionic surfactant as a plating particle refiner; an aromatic aldehyde, an aliphatic aldehyde, and an aromatic amine, each of which is applied to a tin-lead alloy plating film. A plating bath comprising a brightener composition present in an amount sufficient to impart brightness and having an aromatic amine:aromatic aldehyde ratio in the range of 1.25:1 to 100:1. 2. The plating bath according to claim 1, wherein the tin salt and the lead salt are a stannous fluoroborate salt and a lead fluoroborate salt, respectively. 3. The plating bath according to claim 1, wherein the compatible acid is fluoroboric acid. 4. The plating bath according to claim 1, further comprising an alloying metal selected from the group consisting of copper and rhodium. 5. The plating bath according to claim 1, further comprising boric acid. 6. The plating bath according to claim 1, further comprising an antifoaming agent. 7. The plating bath according to claim 6, wherein the antifoaming agent is octyl alcohol. 8. A plating bath according to claim 1, wherein up to 50% by weight of the aliphatic aldehyde is replaced by the corresponding fatty acid. 9 The following amounts of each ingredient: Tin 5-50g/ Lead 3-20g/ Compatible acid 100-250g/ Nonionic surfactant 0.1-20g/ Aromatic amine 0.3-15g/ Aromatic aldehyde 0.01-0.5g. The plating bath according to claim 1, wherein the plating bath contains 0.5 to 20 g of aliphatic aldehyde/aliphatic aldehyde. 10 Tin and lead are used as fluoroboric acid and lead fluoroborate, respectively, a compatible acid is used as fluoroboric acid, a nonionic surfactant is used as polyoxyethylene lauryl ether, and an aromatic amine is used as o-chloride. 10. The plating bath according to claim 9, wherein aromatic aldehyde is added as aniline, aromatic aldehyde is added as 1-naphthaldehyde, and aliphatic aldehyde is added as formalin. 11. The plating bath according to claim 10, wherein up to 50% by weight of formaldehyde is replaced by formic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29976081A | 1981-09-08 | 1981-09-08 | |
| US299760 | 1981-09-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5842786A JPS5842786A (en) | 1983-03-12 |
| JPH0213036B2 true JPH0213036B2 (en) | 1990-04-03 |
Family
ID=23156175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57147498A Granted JPS5842786A (en) | 1981-09-08 | 1982-08-25 | Electrodeposition of tin-lead alloy |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5842786A (en) |
| BE (1) | BE894329A (en) |
| BR (1) | BR8205180A (en) |
| DE (1) | DE3228911A1 (en) |
| ES (1) | ES515543A0 (en) |
| FR (1) | FR2512466B1 (en) |
| GB (1) | GB2105370B (en) |
| IT (1) | IT1189337B (en) |
| NL (1) | NL8203230A (en) |
| SE (1) | SE8204505L (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617097A (en) * | 1983-12-22 | 1986-10-14 | Learonal, Inc. | Process and electrolyte for electroplating tin, lead or tin-lead alloys |
| ES2016313B3 (en) * | 1986-10-03 | 1990-11-01 | Asta Pharma Ag | COMPOUNDS OF DIAMINE-PLATINUM (II) COMPLEXES WITH A HYDROXYLATED PHENYL-INDOLL RING. |
| DE4440176C2 (en) * | 1994-02-05 | 1996-06-27 | Heraeus Gmbh W C | Bath for the electrodeposition of silver-tin alloys |
| GB0106131D0 (en) | 2001-03-13 | 2001-05-02 | Macdermid Plc | Electrolyte media for the deposition of tin alloys and methods for depositing tin alloys |
| ES2766775T3 (en) | 2013-09-05 | 2020-06-15 | Macdermid Enthone Inc | Aqueous electrolyte composition that has reduced air emission |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3785939A (en) * | 1970-10-22 | 1974-01-15 | Conversion Chem Corp | Tin/lead plating bath and method |
| US3905878A (en) * | 1970-11-16 | 1975-09-16 | Hyogo Prefectural Government | Electrolyte for and method of bright electroplating of tin-lead alloy |
| NL7104810A (en) * | 1971-04-08 | 1972-10-10 | ||
| US3730853A (en) * | 1971-06-18 | 1973-05-01 | Schloetter M | Electroplating bath for depositing tin-lead alloy plates |
| US3749649A (en) * | 1971-12-16 | 1973-07-31 | M & T Chemicals Inc | Bright tin-lead alloy plating |
| US3926749A (en) * | 1971-12-20 | 1975-12-16 | M & T Chemicals Inc | Tin-lead alloy plating |
| US4000047A (en) * | 1972-11-17 | 1976-12-28 | Lea-Ronal, Inc. | Electrodeposition of tin, lead and tin-lead alloys |
| JPS4993235A (en) * | 1973-01-10 | 1974-09-05 | ||
| US3850765A (en) * | 1973-05-21 | 1974-11-26 | Oxy Metal Finishing Corp | Bright solder plating |
| GB1469547A (en) * | 1973-06-28 | 1977-04-06 | Minnesota Mining & Mfg | Tin/lead electr-plating baths |
| SE390986B (en) * | 1973-10-18 | 1977-01-31 | Modo Kemi Ab | PROCEDURE FOR ELECTROPLETING AW COATINGS OF IGNITION OR IGNITION ALLOY UNIT OF AN ACID ELECTROLYTE BATH |
| US3875029A (en) * | 1974-02-19 | 1975-04-01 | R O Hull & Company Inc | Plating bath for electrodeposition of bright tin and tin-lead alloy |
| US3956123A (en) * | 1974-02-19 | 1976-05-11 | R. O. Hull & Company, Inc. | Additive for electrodeposition of bright tin and tin-lead alloy |
| US3977949A (en) * | 1975-07-07 | 1976-08-31 | Columbia Chemical Corporation | Acidic plating bath and additives for electrodeposition of bright tin |
| US4135991A (en) * | 1977-08-12 | 1979-01-23 | R. O. Hull & Company, Inc. | Bath and method for electroplating tin and/or lead |
| US4139425A (en) * | 1978-04-05 | 1979-02-13 | R. O. Hull & Company, Inc. | Composition, plating bath, and method for electroplating tin and/or lead |
| GB1567235A (en) * | 1978-05-15 | 1980-05-14 | Pmd Chemicals Ltd | Electrodeposition of tin or tin/lead alloys |
-
1982
- 1982-07-29 SE SE8204505A patent/SE8204505L/en not_active Application Discontinuation
- 1982-08-03 DE DE19823228911 patent/DE3228911A1/en active Granted
- 1982-08-17 NL NL8203230A patent/NL8203230A/en not_active Application Discontinuation
- 1982-08-18 IT IT49001/82A patent/IT1189337B/en active
- 1982-08-25 JP JP57147498A patent/JPS5842786A/en active Granted
- 1982-09-03 BR BR8205180A patent/BR8205180A/en not_active IP Right Cessation
- 1982-09-06 FR FR8215125A patent/FR2512466B1/en not_active Expired
- 1982-09-07 GB GB08225406A patent/GB2105370B/en not_active Expired
- 1982-09-07 ES ES515543A patent/ES515543A0/en active Granted
- 1982-09-07 BE BE0/208965A patent/BE894329A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5842786A (en) | 1983-03-12 |
| BE894329A (en) | 1983-03-07 |
| ES8308367A1 (en) | 1983-08-16 |
| FR2512466B1 (en) | 1987-06-26 |
| DE3228911A1 (en) | 1983-03-24 |
| IT8249001A0 (en) | 1982-08-18 |
| IT1189337B (en) | 1988-02-04 |
| SE8204505D0 (en) | 1982-07-29 |
| FR2512466A1 (en) | 1983-03-11 |
| NL8203230A (en) | 1983-04-05 |
| SE8204505L (en) | 1983-03-09 |
| GB2105370B (en) | 1985-05-01 |
| GB2105370A (en) | 1983-03-23 |
| BR8205180A (en) | 1983-09-06 |
| ES515543A0 (en) | 1983-08-16 |
| DE3228911C2 (en) | 1988-02-04 |
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