CN1802451A - 无电镀金液 - Google Patents
无电镀金液 Download PDFInfo
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- CN1802451A CN1802451A CNA2004800156936A CN200480015693A CN1802451A CN 1802451 A CN1802451 A CN 1802451A CN A2004800156936 A CNA2004800156936 A CN A2004800156936A CN 200480015693 A CN200480015693 A CN 200480015693A CN 1802451 A CN1802451 A CN 1802451A
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- gold
- plating solution
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- electroless
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- 238000007747 plating Methods 0.000 title claims abstract description 54
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000010931 gold Substances 0.000 title claims abstract description 37
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000002344 gold compounds Chemical class 0.000 claims abstract description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 24
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 15
- -1 sulfite compound Chemical class 0.000 abstract description 14
- 238000007772 electroless plating Methods 0.000 abstract description 12
- 229910000679 solder Inorganic materials 0.000 abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 150000003863 ammonium salts Chemical class 0.000 abstract description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-N disulfurous acid Chemical compound OS(=O)S(O)(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 229910052759 nickel Inorganic materials 0.000 description 16
- 238000007654 immersion Methods 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052728 basic metal Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JCDVTZPJEWWGHU-UHFFFAOYSA-N gold sulfurous acid Chemical compound [Au].S(O)(O)=O JCDVTZPJEWWGHU-UHFFFAOYSA-N 0.000 description 3
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 3
- 239000006174 pH buffer Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- AZMMUMQYPBKXHS-UHFFFAOYSA-N gold sodium Chemical compound [Na].[Au] AZMMUMQYPBKXHS-UHFFFAOYSA-N 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- TVGIYTJTDDLBJP-UHFFFAOYSA-N gold;thiocyanic acid Chemical compound [Au].SC#N TVGIYTJTDDLBJP-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- 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
- C23C18/42—Coating with noble metals
-
- 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
- C23C18/54—Contact plating, i.e. electroless electrochemical plating
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- 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)
- Electrochemistry (AREA)
- Chemically Coating (AREA)
Abstract
一种无电镀金液，特征在于其包含无氰的水溶性金化合物和焦亚硫酸化合物。该无电镀液还可以包含亚硫酸化合物或氨基羧酸化合物。作为焦亚硫酸化合物，可使用焦亚硫酸、其碱金属盐、碱土金属盐或铵盐等。该无电镀液毒性低，可在接近中性的pH下使用，且获得的金镀层在焊料和其上镀层之间具有良好的附着力。
Description
技术领域
本发明涉及镀覆技术，特别涉及无氰化物浸入型无电镀金液。
背景技术
浸入型无电镀金液已被用于形成中间层，以提高印刷电路板中电路、端点等的焊料附着力，并提高还原性镀金等的附着力。用于该目的的大多数镀金液含有有毒氰化物作为金化合物，但是出于对环境和工作场所的关心，需要不含有毒物质的无氰镀金液。
已经提出的无氰替代镀金液的专利申请包括：使用亚硫酸金化合物的申请(可见例如日本专利3030113号和日本专利公开2003-13249号)、使用亚硫酸金盐或氯金酸盐的申请(可见例如日本专利公开H8-291389号)和使用亚硫酸金、氯化金、硫代硫酸金或巯基羧酸金的申请(可见例如日本专利公开H10-317157号)。在这些专利中讨论的无电镀金液是无氰的，因此毒性低，并可在接近中性条件使用。但是，它们的问题是焊料附着力和镀膜附着力较低。“镀膜附着力”是指浸入型无电镀金膜与基底之间的附着力，和当浸入型无电镀金膜被用作中间层时，是指高于镀膜的层与低于镀膜的层之间的附着力。
发明内容
鉴于上述情况，本发明的目的是提供低毒、接近中性使用、可获得良好焊料附着力和镀膜附着力的无氰浸入型无电镀金液。
发明人研究了浸入型无电镀金膜的镀膜附着力和焊料附着力的不利影响因素，结果发现问题在于下面的金属镀膜(例如下面的镍膜)的非均匀取代。更具体地，当镀金膜剥离后在下面的镍膜上出现非均匀腐蚀痕迹(例如点状腐蚀)时，因为在浸入型无电镀金膜中还存在一些缺陷，焊料附着力和镀膜附着力就差。相反，只要不出现非均匀腐蚀痕迹，焊料附着力和镀膜附着力就好。
因此，发明人研究了在金剥离后不会在下面的镍膜产生非均匀腐蚀痕迹的镀液组成，结果发现加入焦亚硫酸化合物是有效的，它能够使镀金膜具有优良的焊料附着力和镀膜附着力。如上所述，关于无氰浸入型无电镀金液已经提出了许多专利申请，但是没有一个专利包含焦亚硫酸化合物。
本发明具体如下：
(1)一种无电镀金液，其含有无氰水溶性金化合物和焦亚硫酸化合物。
(2)根据上面(1)的无电镀金液，其进一步含有亚硫酸化合物。
(3)根据上面(1)或(2)的无电镀金液，其进一步包含氨基羧酸化合物。
(4)使用根据上面(1)至(3)任一项的无电镀金液制造的镀金制品。
用于本发明镀液中的无氰水溶性金化合物没有特殊限制，只要它是无氰和水溶的即可，但是其特征在于包含焦亚硫酸化合物作为添加剂。
附图的简单说明
图1是实施例1中镀金膜剥离后下面的镀镍膜的SEM显微图；
图2是实施例1中镀金膜剥离后下面的镀镍膜的SEM显微图；
图3是对比例1中镀金膜剥离后下面的镀镍膜的SEM显微图；和
图4是对比例2中镀金膜剥离后下面的镀镍膜的SEM显微图。
本发明的最佳实施方式
以下详细说明本发明的无电镀金液。
将无氰的水溶性金化合物和焦亚硫酸化合物溶解于水中，制得本发明的无电镀金液。只要是金化合物且是无氰的，对无氰水溶性金化合物就没有特殊的限制，但是优选使用亚硫酸金、硫代硫酸金、硫氰酸金、氯金酸或它们的盐。本发明无电镀金液优选以0.1至100g/L、更优选0.5至20g/L的量包含这些金化合物，作为镀液中金的浓度。如果金浓度小于0.1g/L，金的取代将变得非常慢，但是超过100g/L也没有其它好处。
焦亚硫酸化合物可以是焦亚硫酸或其碱金属、碱土金属、铵或其它这类的盐。焦亚硫酸化合物优选以0.1至200g/L、更优选1至100g/L的量包含在镀液中。如果焦亚硫酸的浓度小于0.1g/L时，则阻止下面的镍非均匀腐蚀的效果将变弱，但是超过200g/L也没有其它好处。
本发明的无电镀金液优选包含亚硫酸化合物作为稳定剂。这种亚硫酸化合物的例子包括亚硫酸及其碱金属、碱土金属、铵和其它这类的盐。镀液体中亚硫酸化合物的浓度优选为0.1至200g/L，更优选1至100g/L。如果浓度小于0.1g/L，该化合物就不具有稳定剂的作用，但是超过200g/L也没有其它好处。
本发明的镀液还可以包含氨基羧酸化合物作为络合剂。氨基羧酸化合物的例子包括乙二胺四乙酸、羟乙基乙二胺三乙酸、二羟乙基乙二胺二乙酸、丙二胺四乙酸、二亚乙基三胺五乙酸、三亚乙基四胺六乙酸、氨基乙酸、氨基乙酰基氨基乙酸、氨基乙酰基氨基乙酰基氨基乙酸、二羟乙基氨基乙酸、亚氨基二乙酸、羟乙基亚氨基二乙酸、氨三乙酸、氨三丙酸、及其碱金属、碱土金属、铵和其它这类的盐。镀液中氨基羧酸化合物的浓度优选为0.1至200g/L，更优选1至100g/L。如果氨基羧酸化合物的浓度小于0.1g/L，则作为络合剂的效果将变弱，但是超过200g/L也没有有其它好处。
当需要用作pH缓冲剂时，也可以在本发明的无电镀金液中加入磷酸化合物。
磷酸化合物的例子包括磷酸、焦磷酸或其碱金属、碱土金属和铵盐、碱金属磷酸二氢盐、碱土金属磷酸二氢盐、磷酸二氢铵、磷酸氢二碱金属盐、磷酸氢二碱土金属盐和磷酸氢二铵。镀液中磷酸化合物的浓度优选为0.1至200g/L、更优选1至100g/L。
优选使用上述化合物之一作为pH缓冲剂，将本发明镀液的pH调节到4至10之间，更优选将pH调节为5至9。
本发明的镀金液优选在10至95℃、更优选50至85℃的液体温度下使用。
如果镀液的pH或液体温度超过上面给出的范围，将出现镀覆速率慢或更易于发生镀液分解的问题。
在印刷电路板镀上镍作为下层以后，使用本发明的镀金液生产的镀金膜例如具有良好的焊料附着力和镀膜附着力，因为下面的镀镍膜没有被非均匀取代。镀金膜剥离后，下面的镀镍膜没有出现非均匀腐蚀的痕迹。
实施例
通过以下实施例和对比例描述本发明的优选实施方案。
实施例1和2以及对比例1和2
制备具有表1所示不同组成的镀液作为浸入型无电镀金液。待镀的材料是抗蚀剂开口直径为0.4mmΦ的印刷电路板，电镀以下列方法实施。
酸性脱脂(45℃，5分钟)
→软蚀刻(25℃，2分钟)
→酸洗(25℃，1分钟)
→催化剂(KG-522，Nikko Metal Plating制造)(25℃，pH＜1.0，5分钟)
→酸洗(25℃，1分钟)
→无电镀镍(镀液：KG-530，Nikko Metal Plating制造)(88℃，pH4.5，30分钟)
→浸入型无电镀金(使用表1所列镀液和镀覆条件)
→还原性无电镀金(镀液：KG-560，Nikko Metal Plating制造)(70℃，pH5.0，30分钟)
(除了酸洗→活化剂这一步骤，在所有步骤之间插入持续1分钟的水洗步骤。)
如下评价这样获得的电镀制品。
在用Nikko Metal Plating制造的金剥离器Aurum Strupper710剥离浸入型无电镀金膜(25℃，0.5分钟)之后，通过SEM放大2000倍观察下面的镀镍膜的腐蚀状态，并通过目测检查腐蚀痕迹(点状腐蚀)。图1至4分别显示在实施例1和2以及对比例1和2中剥离镀金膜之后下面的镀镍膜的SEM显微图。在实施例1和2中，剥离镀金膜后，在下面的镀镍膜中没有出现点状腐蚀或其它非均匀腐蚀痕迹，但是在对比例1和2中，剥离镀金膜后在下面的镀镍膜中出现了点状腐蚀。
如下测定焊料的附着强度：进行浸入型无电镀金；将直径为0.4mmΦ的锡-37铅焊料球置于其上，在回流炉中以240℃的峰温度加热和粘合；然后用Deiji制造的4000系列粘合检测器测定强度。
如下评价镀膜的附着力：完成浸入型无电镀金；进行还原性无电镀金；对镀层进行剥离试验，并目测镀层以检查是否有膜被剥离。该剥离试验包括将玻璃纸带(CellotapeTM，Nichiban制造)贴在镀膜上，然后剥离玻璃纸带并目测观察电镀膜是否粘在带上。
用Seiko Deshi Kogyo制造的SFT-3200荧光X-射线膜厚度计测量镀膜厚度。
评价结果列于表1。
表1
| 实施例 | 对比例 | ||||
| 1 | 2 | 1 | 2 | ||
| 镀液组成 | 金化合物 | 亚硫酸金钠：1g/L(金) | 氯金酸钠：1g/L(金) | 亚硫酸金钠：1g/L(金) | 氰化金钾：2g/L(金) |
| 添加剂 | 焦亚硫酸钠：5g/L | 焦亚硫酸钠：10g/L | —— | —— | |
| 稳定剂 | 亚硫酸钠：5g/L | 亚硫酸钠：10g/L | 亚硫酸钠：5g/L | 柠檬酸：30g/L | |
| 络合剂 | 乙二胺四乙酸：10g/L | 氨三乙酸：10g/L | 乙二胺四乙酸：10g/L | 乙二胺四乙酸：5g/L | |
| pH缓冲剂 | 磷酸二氢钠：30g/L | 磷酸二氢钠：30g/L | 磷酸二氢钠：30g/L | —— | |
| 镀覆条件 | pH | 7.5 | 7.5 | 7.5 | 5.0 |
| 镀覆温度(℃) | 80 | 80 | 80 | 90 | |
| 镀覆时间(分钟) | 10 | 10 | 10 | 5 | |
| 评价结果 | 膜厚度(μm) | 0.05 | 0.05 | 0.05 | 0.05 |
| 点状腐蚀 | 无 | 无 | 有 | 有 | |
| 焊料附着强度 | 1412 | 1395 | 1046 | 1014 | |
| 镀膜粘附 | 无剥离 | 无剥离 | 剥离 | 剥离 | |
焊料附着强度单位：gf(n＝20)
本发明提供了无氰浸入型无电镀金液，其毒性低，可接近中性使用，并获得了良好的焊料附着力和镀膜附着力。
Claims (4)
1、一种无电镀金液，其含有无氰水溶性金化合物和焦亚硫酸化合物。
2、根据权利要求1的无电镀金液，其进一步含有亚硫酸化合物。
3、根据权利要求1或2的无电镀金液，其进一步含有氨基羧酸化合物。
4、一种镀金制品，使用根据权利要求1至3任一项的无电镀金液制备。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP160974/2003 | 2003-06-05 | ||
| JP2003160974 | 2003-06-05 |
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| US (1) | US7419536B2 (zh) |
| EP (1) | EP1645658A4 (zh) |
| JP (1) | JP4299300B2 (zh) |
| KR (1) | KR100735259B1 (zh) |
| CN (1) | CN100549228C (zh) |
| HK (1) | HK1090097A1 (zh) |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275224B (zh) * | 2007-01-11 | 2011-05-18 | 上村工业株式会社 | 无电解镀金浴的镀敷能力维持控制方法 |
| WO2011150781A1 (zh) * | 2010-06-01 | 2011-12-08 | 无锡阿尔法电子科技有限公司 | 一种在电容式触摸屏表面进行化学镀金的方法 |
| CN103540973A (zh) * | 2013-09-24 | 2014-01-29 | 沈阳建筑大学 | 一种用于芯片和线路板热沉的电镀金液及使用方法 |
| CN112695306A (zh) * | 2020-12-16 | 2021-04-23 | 昆山成功环保科技有限公司 | 应用在印制线路板领域的无毒环保的化学沉金溶液 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006006367A1 (ja) * | 2004-07-09 | 2006-01-19 | Nippon Mining & Mrtals Co., Ltd. | 無電解金めっき液 |
| KR100832630B1 (ko) * | 2004-11-15 | 2008-05-27 | 닛코킨조쿠 가부시키가이샤 | 무전해금도금액 |
| CN108220934A (zh) * | 2018-01-22 | 2018-06-29 | 昆山成功环保科技有限公司 | 一种无氰化学浸金溶液 |
| JP7135384B2 (ja) * | 2018-03-30 | 2022-09-13 | 住友大阪セメント株式会社 | 光導波路素子 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3300328A (en) * | 1963-11-12 | 1967-01-24 | Clevite Corp | Electroless plating of gold |
| DE2803147C2 (de) * | 1978-01-25 | 1984-03-08 | W.C. Heraeus Gmbh, 6450 Hanau | Tauchgoldbad |
| CN1003524B (zh) * | 1985-10-14 | 1989-03-08 | 株式会社日立制作所 | 无电浸镀金溶液 |
| JP3030113B2 (ja) | 1991-04-12 | 2000-04-10 | エヌ・イーケムキャット株式会社 | 置換無電解金めつき液 |
| US5232492A (en) * | 1992-01-23 | 1993-08-03 | Applied Electroless Concepts Inc. | Electroless gold plating composition |
| DE630991T1 (de) * | 1992-11-25 | 1995-07-13 | Kanto Kagaku | Stromloses goldbeschichtungsbad. |
| JPH08291389A (ja) | 1995-04-18 | 1996-11-05 | Hitachi Chem Co Ltd | 非シアン置換金めっき液及びこの液を用いた金めっき方法 |
| JP3532046B2 (ja) | 1996-10-25 | 2004-05-31 | 株式会社大和化成研究所 | 非シアン置換銀めっき浴 |
| JP3566498B2 (ja) | 1997-05-14 | 2004-09-15 | 株式会社大和化成研究所 | 置換金めっき浴 |
| US5935306A (en) * | 1998-02-10 | 1999-08-10 | Technic Inc. | Electroless gold plating bath |
| GB9822822D0 (en) * | 1998-10-19 | 1998-12-16 | Dyno Particles As | Particles |
| JP3876634B2 (ja) | 2001-03-14 | 2007-02-07 | トヨタ自動車株式会社 | 合金触媒と排気ガス浄化用触媒の製造方法 |
| JP3482402B2 (ja) | 2001-06-29 | 2003-12-22 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | 置換金メッキ液 |
| WO2006006367A1 (ja) * | 2004-07-09 | 2006-01-19 | Nippon Mining & Mrtals Co., Ltd. | 無電解金めっき液 |
-
2004
- 2004-02-18 JP JP2005506727A patent/JP4299300B2/ja not_active Expired - Lifetime
- 2004-02-18 KR KR1020057023237A patent/KR100735259B1/ko active IP Right Grant
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- 2004-02-18 EP EP20040712169 patent/EP1645658A4/en not_active Withdrawn
- 2004-02-18 CN CNB2004800156936A patent/CN100549228C/zh not_active Expired - Lifetime
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275224B (zh) * | 2007-01-11 | 2011-05-18 | 上村工业株式会社 | 无电解镀金浴的镀敷能力维持控制方法 |
| WO2011150781A1 (zh) * | 2010-06-01 | 2011-12-08 | 无锡阿尔法电子科技有限公司 | 一种在电容式触摸屏表面进行化学镀金的方法 |
| CN103540973A (zh) * | 2013-09-24 | 2014-01-29 | 沈阳建筑大学 | 一种用于芯片和线路板热沉的电镀金液及使用方法 |
| CN112695306A (zh) * | 2020-12-16 | 2021-04-23 | 昆山成功环保科技有限公司 | 应用在印制线路板领域的无毒环保的化学沉金溶液 |
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| Publication number | Publication date |
|---|---|
| JP4299300B2 (ja) | 2009-07-22 |
| KR20060026035A (ko) | 2006-03-22 |
| CN100549228C (zh) | 2009-10-14 |
| US20060230979A1 (en) | 2006-10-19 |
| HK1090097A1 (en) | 2006-12-15 |
| WO2004108987A1 (ja) | 2004-12-16 |
| TW200427865A (en) | 2004-12-16 |
| TWI267564B (en) | 2006-12-01 |
| US7419536B2 (en) | 2008-09-02 |
| EP1645658A1 (en) | 2006-04-12 |
| KR100735259B1 (ko) | 2007-07-03 |
| EP1645658A4 (en) | 2011-08-03 |
| JPWO2004108987A1 (ja) | 2006-07-20 |
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