JPS63128194A - Tin-lead alloy plating bath - Google Patents
Tin-lead alloy plating bathInfo
- Publication number
- JPS63128194A JPS63128194A JP27595886A JP27595886A JPS63128194A JP S63128194 A JPS63128194 A JP S63128194A JP 27595886 A JP27595886 A JP 27595886A JP 27595886 A JP27595886 A JP 27595886A JP S63128194 A JPS63128194 A JP S63128194A
- Authority
- JP
- Japan
- Prior art keywords
- bath
- tin
- plating bath
- alloy plating
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 57
- 229910001174 tin-lead alloy Inorganic materials 0.000 title claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 150000003852 triazoles Chemical class 0.000 claims abstract description 7
- 150000003918 triazines Chemical class 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract 4
- 239000000956 alloy Substances 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000002932 luster Substances 0.000 abstract description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract 3
- 229910020816 Sn Pb Inorganic materials 0.000 abstract 3
- 229910020922 Sn-Pb Inorganic materials 0.000 abstract 3
- 229910008783 Sn—Pb Inorganic materials 0.000 abstract 3
- OWQPOVKKUWUEKE-UHFFFAOYSA-N 1,2,3-benzotriazine Chemical compound N1=NN=CC2=CC=CC=C21 OWQPOVKKUWUEKE-UHFFFAOYSA-N 0.000 abstract 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 abstract 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 20
- -1 aromatic amine compounds Chemical class 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 5
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- LEMQFBIYMVUIIG-UHFFFAOYSA-N trifluoroborane;hydrofluoride Chemical compound F.FB(F)F LEMQFBIYMVUIIG-UHFFFAOYSA-N 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 208000000474 Poliomyelitis Diseases 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 241000283690 Bos taurus Species 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229930008407 benzylideneacetone Natural products 0.000 description 3
- 229940046892 lead acetate Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 229940018563 3-aminophenol Drugs 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 2
- 229960002799 stannous fluoride Drugs 0.000 description 2
- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HOQPTLCRWVZIQZ-UHFFFAOYSA-H bis[[2-(5-hydroxy-4,7-dioxo-1,3,2$l^{2}-dioxaplumbepan-5-yl)acetyl]oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HOQPTLCRWVZIQZ-UHFFFAOYSA-H 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CRBREIOFEDVXGE-UHFFFAOYSA-N dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=CC=C1 CRBREIOFEDVXGE-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 1
- LZGUHMNOBNWABZ-UHFFFAOYSA-N n-nitro-n-phenylnitramide Chemical compound [O-][N+](=O)N([N+]([O-])=O)C1=CC=CC=C1 LZGUHMNOBNWABZ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】 本発明は錫−鉛合金めっき浴に関する。[Detailed description of the invention] The present invention relates to a tin-lead alloy plating bath.
近年、電気機器用部品に施すめっきとして、従来のカド
ミウムめっきに代えて、安価で安全性の高い錫−鉛合金
めっきの使用が検討されている。BACKGROUND ART In recent years, the use of tin-lead alloy plating, which is inexpensive and highly safe, has been considered as a plating for parts for electrical equipment in place of conventional cadmium plating.
この錫−鉛合金めっきを実用に供するためには、形成さ
れるめっき面が緻密で鏡面状の光沢を有することが必要
である。めっき面が粗雑で光沢がない場合には、外観が
悪いだけでなく、プリント配線などの材料とする場合に
、電気抵抗が大きくなシまた腐食に対しても゛弱いもの
となる。In order to put this tin-lead alloy plating into practical use, it is necessary that the formed plating surface be dense and have a mirror-like luster. If the plated surface is rough and lacks luster, it not only looks bad, but also has high electrical resistance and is susceptible to corrosion when used as a material for printed wiring.
錫−鉛合金めっきのめつき面に光沢を与えるためには、
めっき処理後ヒユージンク、研磨等の方法によってめっ
き表面を緻密にする方法と、錫−鉛合金めっき浴に光沢
剤を添加する方法とがある。In order to give gloss to the plated surface of tin-lead alloy plating,
There are two methods: one method is to make the plating surface denser by heating or polishing after plating treatment, and the other method is to add a brightener to the tin-lead alloy plating bath.
錫−鉛合金めっき用の光沢剤としては、芳香族アミン化
合物やアルダ七ド化合物とアミン化合物との反応生成物
等が知られている。しかしながらこれらの化合物は、め
っき浴中で分解変質し易く、このため、めっき浴の使用
時間が長くなると、光沢の良いめっき皮膜を形成できる
電流密度範囲が狭くなシ、また光沢の度合も低くなると
いう欠点がある。As brighteners for tin-lead alloy plating, aromatic amine compounds, reaction products of alda-7d compounds and amine compounds, and the like are known. However, these compounds tend to decompose and change in quality in the plating bath, and for this reason, as the plating bath is used for a long time, the current density range in which a high-gloss plating film can be formed becomes narrow, and the degree of gloss also decreases. There is a drawback.
従って、この様な光沢剤を用いる錫−鉛合金めっき浴で
は、電流密度分布の大きい複雑な形状の物品にめっきを
行なう場合には、光沢の良好な面と、灰色乃至灰褐色の
面とを有する均一性の悪い電着物が形成される。Therefore, in a tin-lead alloy plating bath using such a brightener, when plating an article with a complex shape with a large current density distribution, it is difficult to separate the high-gloss side and the gray or gray-brown side. An electrodeposit with poor uniformity is formed.
本発明者は、上述した如き問題点に＃１２みて、広い電
流密度範囲において光沢の良好なめつき皮膜を形成でき
、かつ長期間その効果を持続できる安定性の良い錫−鉛
合金めっき浴用光沢剤を得るべく鋭意研究を重ねてきた
。その結果、トリアソール類、トリアジン類及びこれら
の縮合環化合物の少なくとも１種を錫−鉛合金めっき浴
の光沢剤とする場合には、所期の目的が達成されること
を見出し、ここに本発明を完成するに至った。In view of the above-mentioned problem #12, the present inventor has developed a brightener for tin-lead alloy plating baths that is capable of forming a plating film with good gloss over a wide current density range and maintaining its effect for a long period of time. We have conducted extensive research to obtain the. As a result, it was found that the desired object can be achieved when at least one of triazoles, triazines, and their fused ring compounds is used as a brightener for a tin-lead alloy plating bath, and the present invention is hereby accomplished. I was able to complete it.
即ち、本発明は、２価の錫塩及び鉛塩を必須成分とする
錫−鉛合金めっき浴において、トリアシール類、トリア
ジン類及びこれらの縮合環化合物の少なくとも１種を含
有することを特徴とする錫−鉛合金めっき浴に係る。That is, the present invention is characterized in that a tin-lead alloy plating bath containing a divalent tin salt and a lead salt as essential components contains at least one of triacyls, triazines, and fused ring compounds thereof. This relates to a tin-lead alloy plating bath.
本発明錫−鉛合金めっき浴では、光沢剤として、トリア
ソール類、トリアジン類及びこれらの縮合環化合物の少
なくとも１種を用いる。これらの化合物の具体例として
は、１，２．８−）リアソール、１−フェニル−１／／
−１，２，８−トリアソール、２−フェニル−１／−１
，２，８−トリアソールＳ１，２゜８−ペンストリアシ
ール１メチルベンズトリアソール、１，２．８−）リア
ジン、１．２．４−）リアジン１１．１．５−トリアジ
ン、１．２．８−ベンズトリアジン等を示すことができ
る。これらの化合物の添加量は０．１〜５ ｆ／ｌ程度
が適当である。In the tin-lead alloy plating bath of the present invention, at least one of triazoles, triazines, and fused ring compounds thereof is used as a brightener. Specific examples of these compounds include 1,2,8-) riasol, 1-phenyl-1//
-1,2,8-triazole, 2-phenyl-1/-1
, 2,8-triazole S1,2°8-penstriazole 1 methylbenztriazole, 1,2.8-) riazine, 1.2.4-) riazine 11.1.5-triazine, 1.2. 8-benztriazine and the like can be shown. The appropriate amount of these compounds to be added is about 0.1 to 5 f/l.
本発明では、前記光沢剤を添加するめつき浴としては、
２価の錫塩及び鉛塩を必須成分とする公知の錫−鉛合金
めっき浴をいずれも使用できる。In the present invention, the plating bath to which the brightener is added includes:
Any known tin-lead alloy plating bath containing divalent tin salt and lead salt as essential components can be used.
この様なめつき浴としては、例えばホウフッ化第１＠、
ホウフッ化鉛及びホウフッ化水素酸を含有するめつき浴
、硝酸第１錫、塩化第１錫、酢酸第１錫等の水溶性第１
錫塩、及び硝酸鉛、酢酸鉛、クエン酸鉛等の水浴性鉛塩
に１スルフア三ン酸等の無機酸又はこれらの塩、クエン
酸、ジルコン酸等の有機酸又はこれらの塩等を加えため
つき浴等を基本浴とし、これらの基本浴に、必要に応じ
てホルマリン・アセトアルデヒド等の脂肪族アルデヒド
、ポリオ十ジエチレンノニルフェニルエーテル、ポリオ
十ジエチレンオクチルフェニルエーテル、ポリオ牛ジエ
チレンドデシルフェニルエーテル等のノ二オシ系界面活
性剤等を添加しためつき浴を示すことができる。この様
なめつき浴の組成例を以下に示す。As such a licking bath, for example, borofluoride #1@,
Plating baths containing lead borofluoride and fluoroboric acid;
Inorganic acids such as 1-sulfanoic acid or salts thereof, organic acids such as citric acid, zirconic acid, or salts thereof are added to tin salts and water-bathable lead salts such as lead nitrate, lead acetate, and lead citrate. A storage bath etc. is used as a basic bath, and in these basic baths, aliphatic aldehydes such as formalin/acetaldehyde, poly-deca-diethylene nonylphenyl ether, poly-deca-diethylene octylphenyl ether, poly-ox-diethylene dodecyl phenyl ether, etc. are added as necessary. It is possible to refer to a soaking bath to which a noniodine surfactant or the like is added. An example of the composition of such a plating bath is shown below.
（フッ化物浴） 範 囲ホウフッ化水素
酸 （４２％） ５０〜８００１７１ホウフツ化第
１スズ（４５％） ４０〜２５０ ｆ／１ホウフッ
化船 （４５％） １０〜１００ ｆ／Ｉｔポ
リオ士シエチレンノニルフエ １０〜５０１／にル
エーテル
（クエン酸浴）
硝酸第１スズ １０〜５０ ｆ／１硝酸鉛
５〜２５１７１
ク工ン酸アン℃ニウム ５０〜１００ ｆ／
１酢酸アンモニウム ８０〜８０ ｆｌ
／ＩＩポリオ士ジエチレジエチレンノニル１０〜５０
ｆ／１フェニルエーテル
（ジルコン酸浴）
塩化第１スズ ２０〜６０ ｆ／１
硝酸鉛 ５〜２０ ｆ／１
ジルコン酸ナトリウム ５０〜１５０ ｆ／
１ポリオ牛ジニジエチレンドデシル １０〜５０ｆ／／
１フエニルエーテル
また、本発明で用いる光沢剤は、芳香族アニン化合物と
併用することによって、更に広い電流密度範囲に亘って
、よシ一層良好な光沢めっき皮膜を形成でき、その効果
の持続性も優れたものとなる。この様な芳香族アミン化
合物として、アニリン、Ｎ−七ノメチルアニリン１ジメ
チルアニリン、トリメチルアニリン、ニドロアニリン、
ジニトロアニリン、トリニド０アニリン等のアニリン類
、アミノフェノール１アミノジフェニルアミン１トシイ
ジン１ニドＯトルイジン、フエニレシジアミン、戸−ニ
ドロー〇−フェニレンジアミン等を例示でき１特にアニ
リン類が好ましい。芳香族アミン類の使用量は通常０．
０１〜２．５１／ｌ程度、好ましくは０．１〜１．８ｆ
／ｌ程度である。(Fluoride Bath) Range Fluoroboric Acid (42%) 50-800171 Stannous Borofluoride (45%) 40-250 f/1 Fluoroborate (45%) 10-100 f/It Polyethylene Nonyl ether 10-501/1 ether (citric acid bath) Stannous nitrate 10-50 f/1 lead nitrate
5-25171 Ammonium citrate 50-100 f/
1 Ammonium acetate 80-80 fl
/II Polymer diethyl diethylene nonyl 10-50
f/1 phenyl ether (zirconate bath) stannous chloride 20-60 f/1
Lead nitrate 5-20 f/1 Sodium zirconate 50-150 f/1
1 Polio bovine diethylene dodecyl 10-50f//
Furthermore, by using the brightener used in the present invention in combination with an aromatic anine compound, it is possible to form an even better bright plating film over a wider current density range, and the durability of the effect can be improved. will also be excellent. Such aromatic amine compounds include aniline, N-7nomethylaniline, 1-dimethylaniline, trimethylaniline, nidroaniline,
Examples include anilines such as dinitroaniline and trinide aniline, aminophenol, aminodiphenylamine, tosidine, tosidine, phenylecidiamine, and nidro-phenylenediamine, with anilines being particularly preferred. The amount of aromatic amines used is usually 0.
01 to 2.51/l, preferably 0.1 to 1.8f
/l.
また・本発明めっき浴には、めっき皮膜の光沢をよシ向
上させるために、必要に応じて・ベンジリデンアセトン
を光沢助剤として添加することができる。ベンジリデン
アセトンの使用量は０．１〜ａ、ｏｆ／ｌ程度が適当で
ある。Additionally, benzylidene acetone can be added as a gloss aid to the plating bath of the present invention, if necessary, in order to further improve the gloss of the plating film. The appropriate amount of benzylidene acetone to be used is about 0.1 to a.of/l.
本発明めっき液では、芳香族アミン化合物、ベンジリデ
ンアセトン等の水に対する溶解度の低い化合物を用いる
場合には、メタノール１エタノール、プロパツール等の
低級アルコールに溶解して添加することができる。In the plating solution of the present invention, when using a compound with low solubility in water, such as an aromatic amine compound or benzylidene acetone, it can be added after being dissolved in a lower alcohol such as methanol, ethanol, propatool, etc.
本発明錫−鉛合金めっき浴では、浴温１５〜３０°Ｃ程
度、陰極電流密度１〜５ Ａ ／ ｄｍ２程度でめっき
を行なえばよい。In the tin-lead alloy plating bath of the present invention, plating may be carried out at a bath temperature of about 15 to 30°C and a cathode current density of about 1 to 5 A/dm2.
本発明めっき浴では、被めっき物の材質は特に限定され
ず、例えば銅、真鍮等の銅合金、ニッケル、鉄、鉄合金
等に好適にめっきを行なうことができる。In the plating bath of the present invention, the material to be plated is not particularly limited, and for example, copper, copper alloys such as brass, nickel, iron, iron alloys, etc. can be suitably plated.
本発明めっき浴によれば、長期間に亘って、広い電流密
度範囲において光沢の良好な錫−鉛合金めっき皮膜を形
成できる。According to the plating bath of the present invention, a tin-lead alloy plating film with good gloss can be formed over a wide current density range over a long period of time.
以下、実施例によυ本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
次に示す各組成のめつき浴を用いて、ハルセル試験によ
って銅板上にめっきを行ない、めっき状態の観察を行な
った。ハルセル条件は、浴温度２０°Ｃ１電流２Ａ、時
間５分、無攪拌とした。Example 1 Plating was performed on a copper plate by a Hull cell test using plating baths having the following compositions, and the state of the plating was observed. The Hull cell conditions were a bath temperature of 20° C., a current of 2 A, a time of 5 minutes, and no stirring.
０本発明浴１
ホウフッ化水素酸 （４２％） ２４０１／
Ｉｔホウフツ化第４スズ（４５％） １４０
１／１ホウフツ化船 （４５％） ６０１／１
ホルマリン （８７％） １０ｍ１／１メタ
ノール ５０ｍ１／１ポリオ士ジエチレ
ンノニル ａ Ｏｆ／１フェニルエーテル
ベンジリデンアセトン １ ｆｌ／１１
、２．８− ）リアリール １ ｆ／１
０比較浴１
ホウフッ化水素酸 （４２％） ２４０１／１ホウ
フツ化第１スズ（４５％） １４０ｆ／１ホウフツ
化鉛 （４５％） ６０１／１ホルマリン
（８７％） １０ｇ１／１メタノール
５０震１／Ｉｔポリオ士ジエチレンノニル
８０ ｆ／１１フェニルエーテル
ベンジリデンアセトン １１／１２．４
−ジメチルアニリン ０．５ｆ／ＩＩ上記２
種類のめつき浴について１建浴直後にハルセル試験を行
なったところ、いずれのめっき浴でも０．１〜１０Ａ／
ｄ＃Ｉ２の電流密度範囲において光沢のある錫−鉛合金
めっき皮膜（錫：鉛−６：４）が形成された。２４時間
経過後、ハルセル試験を行なったところ、本発明浴１で
は、０．２〜ｌ Ｑ Ａ ／ ４ｍ２の範囲で光沢のあ
るめっき皮膜が形成されたが、比較浴１では、光沢のあ
るめっき皮膜が得られる電流密度範囲は、０．５〜８Ａ
／ ４ｍ２と狭くなった。更に、この後、１０時間通
電してめっきを行なった後、ハルセル試験を行なったと
ころ、本発明浴１では、０．２〜ＬＯＡ／ｄｌｆｔ２（
Ｄ範囲で光沢のよいめっき皮膜が得られたのに対して、
比較浴１では、１〜ｇ Ａ ／ ４ｍ２の範囲でのみ光
沢のあるめっき皮膜が形成された。0 Inventive bath 1 Hydrofluoroboric acid (42%) 2401/
It 45% tin (45%) 140
1/1 Hofutsu ship (45%) 601/1
Formalin (87%) 10ml 1/1 methanol 50ml 1/1 polyethylene diethylene nonyl a Of/1 phenyl ether benzylidene acetone 1 fl/11
, 2.8-) Real reel 1 f/1
0 Comparison bath 1 Hydrofluoroboric acid (42%) 2401/1 Stannous borofluoride (45%) 140f/1 Lead borofluoride (45%) 601/1 Formalin
(87%) 10g1/1 methanol
50 earthquakes 1/It polyethylene diethylene nonyl
80 f/11 phenyl ether benzylidene acetone 11/12.4
-Dimethylaniline 0.5f/II above 2
When a Hull cell test was conducted on various types of plating baths immediately after the first bath was built, it was found that all plating baths had 0.1 to 10 A/
A shiny tin-lead alloy plating film (tin:lead-6:4) was formed in the current density range of d#I2. After 24 hours, a Hull cell test was conducted, and a shiny plating film was formed in the range of 0.2 to 1 QA/4 m2 in Bath 1 of the present invention, but a shiny plating film was formed in Comparative Bath 1. The current density range in which a film can be obtained is 0.5 to 8 A.
/ It became narrower at 4m2. Furthermore, after plating by applying electricity for 10 hours, a Hull cell test was conducted, and the results showed that bath 1 of the present invention had a value of 0.2 to LOA/dlft2 (
While a glossy plating film was obtained in the D range,
In comparative bath 1, a shiny plating film was formed only in the range of 1 to 4 m2.
実施例２
以下に示す組成のめつき浴を用いて、実施例１と同様に
してハルセル試験を行なった。光沢のある錫−鉛合金め
っき皮膜が得られた電流密度範囲を第１表に示す。Example 2 A Hull cell test was conducted in the same manner as in Example 1 using a plating bath having the composition shown below. Table 1 shows the current density range at which a shiny tin-lead alloy plating film was obtained.
０本発明浴２
ホウフッ化水素１！１２ （４２％） ２４０１
７１ホウフツ化第１スズ（４５％） １１０ｆ／
ｊホウフツ化船 （４５％） ２０ｆ／１ホル
マリン （８７％） ５ｄ／１メタノール
８０震ｔ／１ポリオ士ジエチレンノニル
フェニル ８０ ’ｌ／１工−テル
ベンシリダンアセトン １ ｆ／１０
−フェニレンジアミン Ｏ，Ｂｌ／１１．２
．８−）リアジン １１７ＩＱ比較浴
２
ホウフッ化水素酸 （４２％） ２４０１／１ホウ
フツ化第１スズ（４５％） １１０ｆ／ｌホウフツ
化船 （４５％） ２０１／１ホルマリン
（８７％） ５ｄ／１メタノール
８０ ｍｌ／ １ポリオ牛ジエチレンノニル
８０ ｆ／１フェニルエーテル
ベンシリダンアセトン １ ’ｌ／１
１０−フエニしンジア三ン ０．８ ｆ／
１０本発明浴８
ホウフッ化水素酸 （４２％） ２４０１／１ホ
ウフツ化第１スズ（４５％） １１０ｆ／ｊホウ
フツ化鉛 （４５％） ２０ｆ／１ア七トアル
デヒド ５＊ｌ／１イソプＯビル
アルコール ４０ｗ１／１ポリオ牛シエチ
レンオクチルフエ ａ ｏ ｙ７ｇニルエーテル
戸−アミノジフェニルアミン ０．２ｆ／１１．
２．８−）リアリール ０．５１／１０比
較浴８
ホウフッ化水素酸 （４２％） ２４０１／１ホウ
フツ化第１スズ（４５％） １１０ｊＦ／ｊホウフ
ツ化鉛 （４５％） ２０１／１アセトアルデ
ヒド ５ ｍｌ／ ｊイソプロビル
アルコール ４０ゴ／ｌポリオ十ジエチレン
オクチル ８０１／１フエニルエーテル
戸−アミノジフェニルアミン ０．２ｆ／１０本
発明浴４
ホウフッ化水素酸 （４２％） ２４０１／１ホ
ウフッ化第１ス、（（４５％＞ １４０１７１ホ
ウフツ化船 （４６％） ６０１／１りＯトン
アルデヒド ５冨ｔ／１イソプ０じ
ルアルコール ８０ ｍｌ／ １ポリオ士
シエチしジノニル ８０１／４フエニルエーテ
ル
Ｉｎ−７Ｅ）フエ）−Ｊｌ／ ０．５
１／１１、２．８− ）リアソール
１１／１０比較浴４
ホウフッ化水素酸 （４２％） ２４０１７１ホ
ウフツ化第１スズ（４５％） １４０ｆ／１ホウ
フツ化船 （４６％） ６０１／１りＯトン
アルデヒド ５＊ｌ／１イソプＯビ
ルアルコール ８０ｍ１／１ポリオ士ジエ
チレンノニル ８０１／１フエ＝ルエーテ
ル
ｍ−アミノフェノール ０．５ ｆ／
１０本発明浴５
酢酸第１スズ ８０ ｆ／１酢酸鉛
１５１／１
クエン酸アシ七ニウム ８０ ｆ／１
酢酸アンモニウム ５０ ｆ７１ホルマ
リン（８７％） ５ｍｌ／１メタノール
２０ｍ１／１ポリオ士ジエチレンノニ
ル ２０ ｆ／１フェニルエーテル
２、４．６− ）リメチルアニリン ０．８ｆ
／１１．２．８−）リアジン ０．４
（１／１０比較浴５
酢酸第１スズ ８０ ｆ／１酢酸鉛
１５ ｆ／１
クエン酸アシ七ニウム ８０１／ＩＩ
酢酸アンモニウム ５０ ｆ／１ホルマ
リン（３７％） ５ｍｌ／１メタノール
２０ ｍｌ／ １ポリオ士ジエチレン
ノニル ２０ ｆ／１フェニルエーテル
２、４．６− ）リメチルアニリン ０．８
ｆ／１０本発明本発
明化６１スズ ４０１／Ｉｔ硝酸鉛
１０ ｆ／１
ジルコン酸ナトリウム ８０１／１ホ
ルマリン（８７％） ５ａｌ／１メタノー
ル ２０ ｍｌ／ １ポリオ士ジエチ
レンドデシル ８０ ｆ／１フェニルエーテ
ル
ペンジリデンアｔトン ０．４１７１ｍ
−アミノフェノール ０．５ｆｌ／１
メチルベンツトリアソール ０．５１／１０
比較浴６
塩化第１スズ ４０ ｆ／１硝酸鉛
１０ ｆ／１
ジルコン酸ナトリウム ８０ ｆ／Ｉ
ｔホルマリン（８７％） ５ｙｔｔ／１メ
タノール ２０ ｍｌ／ １ポリオ牛
ジエチレンドデシル ８０ ｆ／１フエ＝ル
エーテル
ペンジリデンアｔトン ０．４ｆ／１
ｍ−アミノフェノール ０・５ ｆ／
１第 １ 表
実施例８
下記組成のめつき浴を基本浴とし光沢剤として１．２．
８−トリアソール１．１．２．８−）リアジン及びメチ
ルベンリドリアリールを各々単独で使用し、光沢剤の濃
度を変えて、実施例１と同様にハルセル試験を行なった
。めっき浴を建浴して、２４時間経過後に、光沢の良い
めっき皮膜が得られた電流密度範囲をｔＪ２表に示す。0 Inventive bath 2 Hydrogen borofluoride 1!12 (42%) 2401
71 stannous (45%) 110f/
j Hofutsu Chemical Ship (45%) 20f/1 formalin (87%) 5d/1 methanol
80 t/1 Polymer diethylene nonylphenyl 80 'l/1 Terbensylidene acetone 1 f/10
-Phenylenediamine O, Bl/11.2
．． 8-) Reazine 117IQ comparison bath 2 Hydrofluoroboric acid (42%) 2401/1 stannous fluoride (45%) 110 f/l fluoride (45%) 201/1 formalin
(87%) 5d/1 methanol
80 ml/1 Polio bovine diethylene nonyl
80 f/1 phenyl ether benzylidene acetone 1'l/1
10-Phenycin diazine 0.8 f/
10 Bath according to the present invention 8 Fluoroboric acid (42%) 2401/1 Stannous borofluoride (45%) 110f/j Lead borofluoride (45%) 20f/1 Acetataldehyde 5*l/1 Isop-Ovir Alcohol 40w1/1 poliocytheleneoctylphene ao y7g Nyl ether-aminodiphenylamine 0.2f/11.
2.8-) Realyl 0.51/10 comparative bath 8 Fluoroboric acid (42%) 2401/1 stannous borofluoride (45%) 110jF/j lead borofluoride (45%) 201/1 acetaldehyde 5 ml / j Isopropyl alcohol 40g/l polyolefin diethylene octyl 801/1 Phenyl ether aminodiphenylamine 0.2f/10 Inventive bath 4 Hydrofluoroboric acid (42%) 2401/1 1st borofluoride, ( (45%> 140171 fluoride (46%) 601/1 ton aldehyde 5 t/1 isopropyl alcohol 80 ml/1 poliomyelyl ether dinonyl 801/4 phenyl ether In-7E) -Jl/0.5
1/11, 2.8-) rear sole
11/10 Comparative Bath 4 Fluoroboric acid (42%) 240171 Stannous borofluoride (45%) 140f/1 borofluoride (46%) 601/1 Oton aldehyde 5*l/1 Isopropylene alcohol 80m1/1 Polymer diethylene nonyl 801/1 Phyl ether m-aminophenol 0.5 f/
10 Inventive bath 5 Stannous acetate 80 f/1 Lead acetate
151/1 Acinanium citrate 80 f/1
Ammonium acetate 50 f71 formalin (87%) 5ml/1 methanol
20m1/1 Polydiethylenenonyl 20 f/1 Phenyl ether 2,4.6-) Limethylaniline 0.8f
/11.2.8-) Reazine 0.4
(1/10 comparison bath 5 stannous acetate 80 f/1 lead acetate
15 f/1 acinanium citrate 801/II
Ammonium acetate 50 f/1 formalin (37%) 5ml/1 methanol
20 ml/1 poly(diethylenenonyl) 20 f/1 phenyl ether 2,4.6-)limethylaniline 0.8
f/10 Invention Invention 61 Tin 401/It Lead Nitrate
10 f/1 Sodium zirconate 801/1 Formalin (87%) 5al/1 Methanol 20 ml/1 Polydiethylenedodecyl 80 f/1 Phenyl ether penzylidene atton 0.4171m
-Aminophenol 0.5fl/1
Methylbenztriazole 0.51/10
Comparison bath 6 Stannous chloride 40 f/1 lead nitrate
10 f/1 Sodium zirconate 80 f/I
Formalin (87%) 5ytt/1 methanol 20 ml/1 Polio bovine diethylene dodecyl 80 f/1 Fe-L ether penzylidene atton 0.4 f/1
m-aminophenol 0.5 f/
1 Table 1 Example 8 A plating bath with the following composition was used as the basic bath and as a brightening agent 1.2.
8-Triazole 1.1.2.8-) A Hull cell test was conducted in the same manner as in Example 1, using each of riazine and methylbenlyrylyl alone and varying the brightener concentration. Table tJ2 shows the current density range in which a glossy plating film was obtained 24 hours after the plating bath was prepared.
ホウフッ化水素酸 く４２％） ２４０１／１ホ
ウフツ化第１スズ（４５％） Ｌ４０ｆ／１＊
’） ”７ ッ化鉛 （４５％＞ ６０ｆ／
１ホルマリン （８７％） ５ｍｌ／１メタ
ノール ５０ｍ１／１ポリオ牛ジエチ
レンオクチル ４０１／１フエニルエーテルHydrofluoroboric acid (42%) 2401/1 Stannous fluoride (45%) L40f/1*
') 7 Lead fluoride (45%>60f/
1 formalin (87%) 5 ml/1 methanol 50 ml 1/1 polio-bovine diethylene octyl 401/1 phenyl ether
Claims (1)
めっき浴において、トリアゾール類、トリアジン類及び
これらの縮合環化合物の少なくとも１種を含有すること
を特徴とする錫−鉛合金めっき浴。(1) A tin-lead alloy plating bath containing a divalent tin salt and a lead salt as essential components, which is characterized by containing at least one of triazoles, triazines, and fused ring compounds thereof. Alloy plating bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27595886A JPS63128194A (en) | 1986-11-18 | 1986-11-18 | Tin-lead alloy plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27595886A JPS63128194A (en) | 1986-11-18 | 1986-11-18 | Tin-lead alloy plating bath |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63128194A true JPS63128194A (en) | 1988-05-31 |
| JPH0450398B2 JPH0450398B2 (en) | 1992-08-14 |
Family
ID=17562793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27595886A Granted JPS63128194A (en) | 1986-11-18 | 1986-11-18 | Tin-lead alloy plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128194A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5412250A (en) * | 1977-06-29 | 1979-01-29 | Nippon Telegr & Teleph Corp <Ntt> | Synchronizing circuit for artificial random noise sequence |
| JPS5967387A (en) * | 1982-10-08 | 1984-04-17 | Hiyougoken | Tin, lead and tin-lead alloy plating bath |
| JPS6148589A (en) * | 1984-08-16 | 1986-03-10 | Keigo Obata | Tin-lead alloy plating bath |
-
1986
- 1986-11-18 JP JP27595886A patent/JPS63128194A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5412250A (en) * | 1977-06-29 | 1979-01-29 | Nippon Telegr & Teleph Corp <Ntt> | Synchronizing circuit for artificial random noise sequence |
| JPS5967387A (en) * | 1982-10-08 | 1984-04-17 | Hiyougoken | Tin, lead and tin-lead alloy plating bath |
| JPS6148589A (en) * | 1984-08-16 | 1986-03-10 | Keigo Obata | Tin-lead alloy plating bath |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0450398B2 (en) | 1992-08-14 |
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