JP2010265491A - Bath for tin or tin-alloy plating, and barrel-plating process using the plating bath - Google Patents
Bath for tin or tin-alloy plating, and barrel-plating process using the plating bath Download PDFInfo
- Publication number
- JP2010265491A JP2010265491A JP2009115600A JP2009115600A JP2010265491A JP 2010265491 A JP2010265491 A JP 2010265491A JP 2009115600 A JP2009115600 A JP 2009115600A JP 2009115600 A JP2009115600 A JP 2009115600A JP 2010265491 A JP2010265491 A JP 2010265491A
- Authority
- JP
- Japan
- Prior art keywords
- tin
- acid
- plating
- salt
- plating 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 233
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001128 Sn alloy Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 62
- -1 disulfide sulfonate compound Chemical class 0.000 claims abstract description 61
- 150000003839 salts Chemical class 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000009499 grossing Methods 0.000 claims description 6
- 238000005282 brightening Methods 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000006172 buffering agent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 43
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 abstract description 38
- 230000002776 aggregation Effects 0.000 abstract description 16
- 238000004220 aggregation Methods 0.000 abstract description 14
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005476 soldering Methods 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000012360 testing method Methods 0.000 description 22
- 229910000679 solder Inorganic materials 0.000 description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 18
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical group C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000009713 electroplating Methods 0.000 description 15
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 13
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 13
- 229910001316 Ag alloy Inorganic materials 0.000 description 12
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 12
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 11
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 238000007772 electroless plating Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 229960003975 potassium Drugs 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 7
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- JALQQBGHJJURDQ-UHFFFAOYSA-L bis(methylsulfonyloxy)tin Chemical compound [Sn+2].CS([O-])(=O)=O.CS([O-])(=O)=O JALQQBGHJJURDQ-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229940098779 methanesulfonic acid Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 5
- 229910001152 Bi alloy Inorganic materials 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 4
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 description 4
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 4
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910001245 Sb alloy Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000002140 antimony alloy Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- LJDVQYVDNYHZAV-UHFFFAOYSA-N ethanesulfonic acid;silver Chemical compound [Ag].CCS(O)(=O)=O LJDVQYVDNYHZAV-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 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 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- 229910000597 tin-copper alloy Inorganic materials 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
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- GBKGJMYPQZODMI-SNAWJCMRSA-N (e)-4-(furan-2-yl)but-3-en-2-one Chemical compound CC(=O)\C=C\C1=CC=CO1 GBKGJMYPQZODMI-SNAWJCMRSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- XHANCLXYCNTZMM-UHFFFAOYSA-N 2,5-dimethyl-1,3-benzothiazole Chemical compound CC1=CC=C2SC(C)=NC2=C1 XHANCLXYCNTZMM-UHFFFAOYSA-N 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 2
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 2
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 2
- BSQLQMLFTHJVKS-UHFFFAOYSA-N 2-chloro-1,3-benzothiazole Chemical compound C1=CC=C2SC(Cl)=NC2=C1 BSQLQMLFTHJVKS-UHFFFAOYSA-N 0.000 description 2
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 2
- LAKVUPMDDFICNR-UHFFFAOYSA-N 2-methyl-1,3-benzothiazol-5-ol Chemical compound OC1=CC=C2SC(C)=NC2=C1 LAKVUPMDDFICNR-UHFFFAOYSA-N 0.000 description 2
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical compound OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 2
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 2
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- JEHRBPXRCQRGBW-UHFFFAOYSA-L copper;2-hydroxyethanesulfonate Chemical compound [Cu+2].OCCS([O-])(=O)=O.OCCS([O-])(=O)=O JEHRBPXRCQRGBW-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ISDDBQLTUUCGCZ-UHFFFAOYSA-N dipotassium dicyanide Chemical compound [K+].[K+].N#[C-].N#[C-] ISDDBQLTUUCGCZ-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002333 glycines Chemical class 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 229910000337 indium(III) sulfate Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229940116298 l- malic acid Drugs 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229940099690 malic acid Drugs 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- BIHJEIFLAWVSQP-UHFFFAOYSA-N n-(anilinodisulfanyl)aniline Chemical compound C=1C=CC=CC=1NSSNC1=CC=CC=C1 BIHJEIFLAWVSQP-UHFFFAOYSA-N 0.000 description 1
- VOAJIZWMDUSXFK-UHFFFAOYSA-N n-(chloromethyl)aniline Chemical compound ClCNC1=CC=CC=C1 VOAJIZWMDUSXFK-UHFFFAOYSA-N 0.000 description 1
- BTWRPQHFJAFXJR-UHFFFAOYSA-N n-[2-(ethylaminooxy)ethoxy]ethanamine Chemical compound CCNOCCONCC BTWRPQHFJAFXJR-UHFFFAOYSA-N 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229940054441 o-phthalaldehyde Drugs 0.000 description 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- RJQRCOMHVBLQIH-UHFFFAOYSA-M pentane-1-sulfonate Chemical compound CCCCCS([O-])(=O)=O RJQRCOMHVBLQIH-UHFFFAOYSA-M 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- GQWFSUFTPBQRDY-UHFFFAOYSA-N propan-2-ol;silver Chemical compound [Ag].CC(C)O GQWFSUFTPBQRDY-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- HNDXKIMMSFCCFW-UHFFFAOYSA-N propane-2-sulphonic acid Chemical compound CC(C)S(O)(=O)=O HNDXKIMMSFCCFW-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- ULQFYBXXHIFWIQ-UHFFFAOYSA-M silver;2-hydroxyethanesulfonate Chemical compound [Ag+].OCCS([O-])(=O)=O ULQFYBXXHIFWIQ-UHFFFAOYSA-M 0.000 description 1
- FNRAFDRAOOKVOR-UHFFFAOYSA-M silver;2-hydroxypropane-1-sulfonate Chemical compound [Ag+].CC(O)CS([O-])(=O)=O FNRAFDRAOOKVOR-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- IAAKNVCARVEIFS-UHFFFAOYSA-M sodium;4-hydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(O)=CC=C(S([O-])(=O)=O)C2=C1 IAAKNVCARVEIFS-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- BATOPAZDIZEVQF-UHFFFAOYSA-N sorbic aldehyde Natural products CC=CC=CC=O BATOPAZDIZEVQF-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229940007163 stannous tartrate Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- ZPRVNEJJMJMSCN-UHFFFAOYSA-L tin(2+);disulfamate Chemical compound [Sn+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZPRVNEJJMJMSCN-UHFFFAOYSA-L 0.000 description 1
- 229910000969 tin-silver-copper Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- SNFLBFOWKDHQSB-UHFFFAOYSA-L zinc 2-hydroxypropane-1-sulfonate Chemical compound [Zn++].CC(O)CS([O-])(=O)=O.CC(O)CS([O-])(=O)=O SNFLBFOWKDHQSB-UHFFFAOYSA-L 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- MIPUHXODPDOHCI-UHFFFAOYSA-L zinc;2-hydroxyethanesulfonate Chemical compound [Zn+2].OCCS([O-])(=O)=O.OCCS([O-])(=O)=O MIPUHXODPDOHCI-UHFFFAOYSA-L 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
本発明はスズ又はスズ合金メッキ浴、並びに当該メッキ浴を用いたバレルメッキ方法に関して、広い電流密度範囲でのメッキ皮膜の均一性や平滑性を向上し、良好な皮膜外観やハンダ濡れ性を付与できるとともに、特に、バレルメッキに際して導電性媒体同士の凝集などを円滑に防止できるものを提供する。 The present invention relates to a tin or tin alloy plating bath and a barrel plating method using the plating bath, improving the uniformity and smoothness of the plating film in a wide current density range, and imparting good film appearance and solder wettability. In addition, it is possible to provide a material that can smoothly prevent aggregation of conductive media during barrel plating.
スズメッキ、或は、スズ−銀合金、スズ−ビスマス合金、スズ−鉛合金などのスズ合金メッキは、耐食性やハンダ濡れ性が良好であるため、弱電部品やリードフレーム等に代表される電子工業用部品等の工業用メッキとして広く利用されている。但し、最近では、環境保全の高まりから、スズ、スズ−銀合金、スズ−ビスマス合金などの鉛フリーメッキへの要望が増している。
しかしながら、スズメッキやスズ合金メッキでは、皮膜外観が良好でも適用可能な電流密度の範囲が狭かったり、皮膜外観が良好で適用可能な電流密度範囲が広くてもハンダ濡れ性が劣ったり、或は各メッキ作業で電着皮膜の膜厚を均一にできないなど種々の問題があるのが実情である。
Tin plating, or tin alloy plating such as tin-silver alloy, tin-bismuth alloy, tin-lead alloy, etc. has good corrosion resistance and solder wettability. Widely used as industrial plating for parts. However, recently, the demand for lead-free plating of tin, tin-silver alloy, tin-bismuth alloy and the like is increasing due to the increase in environmental conservation.
However, in tin plating and tin alloy plating, the applicable current density range is narrow even when the film appearance is good, or the solder wettability is inferior even when the film appearance is good and the applicable current density range is wide. The actual situation is that there are various problems such as inability to make the film thickness of the electrodeposition film uniform in the plating operation.
そこで、皮膜外観やハンダ濡れ性(又はハンダ付け性)の改善を主目的としたスズ又はスズ合金メッキ浴を挙げると、次の通りである。但し、特許文献1〜3は本出願人が開示したものである。
(1)特許文献1
スズ、スズ−鉛合金メッキ浴に2−メルカプトベンゾチアゾール(実施例10)などのベンゾチアゾール化合物を添加することで、広い電流密度範囲において良好なメッキ皮膜を均一な膜厚で得られることが記載される(第2頁左上欄、同頁右下欄)。
Accordingly, a tin or tin alloy plating bath whose main purpose is to improve the film appearance and solder wettability (or solderability) is as follows. However, Patent Documents 1 to 3 are disclosed by the present applicant.
(1) Patent Document 1
It is described that by adding a benzothiazole compound such as 2-mercaptobenzothiazole (Example 10) to a tin or tin-lead alloy plating bath, a good plating film can be obtained with a uniform film thickness in a wide current density range. (2nd page upper left column, same page lower right column).
(2)特許文献2
モノスルフィド結合の一方がベンゾアゾール環、他方がアルキレンスルホン酸(塩)基であるベンゾアゾール系スルホン酸化合物(2−メルカプトベンズイミダゾール−S−メタンスルホン酸塩、2−メルカプトベンゾチアゾール−S−プロパンスルホン酸塩など;段落17)をスズ又はスズ合金メッキ浴に添加することで、広い電流密度範囲にて優れた皮膜外観やハンダ付け性を付与できることが記載される(段落1、5、44)。
(2) Patent Document 2
A benzoazole sulfonic acid compound in which one of the monosulfide bonds is a benzoazole ring and the other is an alkylene sulfonic acid (salt) group (2-mercaptobenzimidazole-S-methanesulfonate, 2-mercaptobenzothiazole-S-propane It is described that by adding sulfonate, etc .; paragraph 17) to a tin or tin alloy plating bath, excellent film appearance and solderability can be imparted in a wide current density range (paragraphs 1, 5, 44). .
(3)特許文献3
モノ又はジスルフィド結合の両側或は片側に隣接して特定のアルキレンオキシド基などが単数又は繰り返し分子内に存在する直鎖状脂肪族炭化水素化合物と、特定のベンゾアゾール化合物(2−メルカプトベンゾチアゾールなど)とを、スズ又はスズ−鉛合金メッキ浴に併用添加することで、酸性からアルカリ性までの広いpH域で、皮膜外観やハンダ濡れ性を向上することが記載される。
(3) Patent Document 3
A linear aliphatic hydrocarbon compound in which a specific alkylene oxide group or the like is present in the molecule or adjacent to both sides or one side of a mono- or disulfide bond, and a specific benzoazole compound (such as 2-mercaptobenzothiazole) ) Is added to a tin or tin-lead alloy plating bath to improve the film appearance and solder wettability in a wide pH range from acidic to alkaline.
上記特許文献1では、皮膜外観やハンダ濡れ性(又はハンダ付け性)の改善を電流密度にそれほど拘束されずに実現できるが、同文献1の化合物は水に溶解しにくかったり、メルカプト基が酸化を受け易く、難溶性の化合物になって効果を発揮しなくなる恐れがあり、上記特許文献3も同様である。
また、特許文献2の化合物は分子内にスルホン酸基を導入することで、いわば同文献1の化合物が有する水に対する溶解性の難点を克服しようとするものである。
In the above-mentioned Patent Document 1, improvement of the film appearance and solder wettability (or solderability) can be realized without much restraint by the current density. However, the compound of Patent Document 1 is difficult to dissolve in water or the mercapto group is oxidized. It is easy to receive, there is a possibility that it becomes a poorly soluble compound and does not exhibit its effect, and the same applies to Patent Document 3.
In addition, the compound of Patent Document 2 attempts to overcome the water solubility of the compound of Patent Document 1 by introducing a sulfonic acid group into the molecule.
一般に、スズ又はスズ合金浴を用いた電気メッキにはラックメッキ、バレルメッキ、連続高速メッキなどの各種方法があるが、なかでも、バレルメッキは、チップ抵抗器、チップコンデンサ、水晶振動子のキャップなどの小物部品をラック掛けせずにバレルに入れてメッキする点で、メンテナンスが簡単で生産性が高いという利点がある。 In general, electroplating using a tin or tin alloy bath includes various methods such as rack plating, barrel plating, and continuous high-speed plating. Among these, barrel plating is a chip resistor, a chip capacitor, a crystal resonator cap. The advantage is that the maintenance is easy and the productivity is high in that the small parts such as are put in the barrel without being racked and plated.
通常、バレルメッキに際しては、被メッキ物を直径0.2〜1mm程度のスチール、銅、黄銅製などの球形の導電性媒体(通称:ダミー)に混ぜて、通電を改善しながら被メッキ物同士が円滑に混合する状態で電気メッキを行っているが、メッキ時に導電性媒体同士が凝集し、ひいては、これらが重畳的に集まってさらに大きな塊状物にまで成長することが多い。
導電性媒体が凝集して塊状物になると、小物部品の被メッキ物はこの中に取り込まれて給電不足からメッキ不良を起こしたり、或は、被メッキ物と導電性媒体をふるい分ける際に、塊状物がふるいを通過せず、被メッキ物を導電性媒体から選別する工程に時間を要するという問題が発生する。
また、導電性媒体を使用せずに被メッキ物だけでバレルメッキを行う場合にも、被メッキ物同士が凝集する恐れが少なくなく、やはりメッキ不良や生産性の低下を来す恐れがある。
Normally, in barrel plating, the objects to be plated are mixed with a spherical conductive medium (common name: dummy) made of steel, copper, brass or the like having a diameter of about 0.2 to 1 mm to improve the power supply. The electroplating is performed in a state where the particles are smoothly mixed. However, the conductive media are often aggregated during plating, and as a result, they are often gathered in a superimposed manner to grow into a larger lump.
When the conductive medium agglomerates into a lump, the object to be plated of small parts is taken into this, causing poor plating due to insufficient power supply, or when screening the object to be plated and the conductive medium, There is a problem that the lump does not pass through the sieve, and it takes time to sort the object to be plated from the conductive medium.
In addition, when barrel plating is performed only on an object to be plated without using a conductive medium, the objects to be plated are not likely to agglomerate with each other, which may result in poor plating and a decrease in productivity.
本出願人は、先に、特許文献4において、スズメッキ浴にビスマス、インジウム、亜鉛などの特定金属イオンを所定の微量濃度で添加することで、バレルメッキに際して、導電性媒体や被メッキ物同士の凝集を円滑に防止する技術を開示した。 The present applicant previously described in Patent Document 4 by adding specific metal ions such as bismuth, indium, and zinc to a tin plating bath at a predetermined trace concentration, so that the conductive medium and the objects to be plated are subjected to barrel plating. A technique for smoothly preventing aggregation has been disclosed.
しかしながら、上記特許文献4では、ダミーや被メッキ物同士の凝集を防止する見地から、ビスマス、インジウム等の異種金属をメッキ浴に添加するため、その金属が皮膜に共析して皮膜の機械特性が変わってしまう恐れがある。
また、前記特許文献1の化合物は広い電流密度範囲で良好なメッキ皮膜を均一な膜厚で得ることができるが、バレルメッキに際してダミーや被メッキ物同士の凝集を防止する機能には乏しく、特許文献2の化合物も、良好な水溶性の具備に加えて、広い電流密度範囲で良好な皮膜外観やハンダ付け性を付与できる反面、やはりバレルメッキに際してダミー同士などの凝集を防止する機能は不充分である。
However, in the above-mentioned Patent Document 4, since different metals such as bismuth and indium are added to the plating bath from the viewpoint of preventing agglomeration between the dummy and the object to be plated, the metal co-deposits on the film and the mechanical properties of the film are obtained. May change.
Further, the compound of Patent Document 1 can obtain a good plating film with a uniform film thickness in a wide current density range, but has a poor function of preventing aggregation of dummy and objects to be plated during barrel plating. In addition to having good water-solubility, the compound of Literature 2 can provide good film appearance and solderability in a wide current density range, but it also has an insufficient function to prevent aggregation of dummy and the like during barrel plating. It is.
本発明は、広い電流密度範囲でのメッキ皮膜の均一性、平滑性などの向上と、皮膜外観やハンダ濡れ性の改善を図るとともに、スズ又はスズ合金メッキ浴をバレルメッキに適用した場合に、ダミー同士の凝集などを防止して、バレルメッキを円滑に実施することを技術的課題とする。 The present invention improves the uniformity and smoothness of the plating film over a wide current density range, improves the film appearance and solder wettability, and applies a tin or tin alloy plating bath to barrel plating. A technical problem is to smoothly carry out barrel plating by preventing aggregation of the dummy.
本発明者らは、上記特許文献1〜2の化合物を参考にして、ベンゾアゾール環を有する化合物をスズ又はスズ合金メッキ浴に添加した場合において、得られるメッキ皮膜の均一性、皮膜外観或はハンダ濡れ性などに及ぼす影響、また、当該メッキ浴をバレルメッキに適用した場合に、ダミーや被メッキ物同士の凝集抑制の可否などを鋭意研究した。
その結果、ジスルフィド結合の両側に、スルホン酸基が結合したベンゾアゾール環を夫々有する、ジベンゾアゾールジスルフィドスルホン酸化合物は、水溶性が高くて酸化による変性もないため、スズ又はスズ合金メッキ浴に添加すると、広い電流密度範囲でメッキ皮膜の均一性、平滑性を向上でき、皮膜外観やハンダ濡れ性を良好にできること、特にこのメッキ浴をバレルメッキに適用すると、ダミー同士などの凝集を円滑に防止できることを見い出し、本発明を完成した。
The present inventors refer to the compounds of Patent Documents 1 and 2 above, and when a compound having a benzoazole ring is added to a tin or tin alloy plating bath, the uniformity of the obtained plating film, film appearance or We have intensively studied the effects on solder wettability, etc., and whether or not the dummy and the objects to be plated can be suppressed when the plating bath is applied to barrel plating.
As a result, dibenzoazole disulfide sulfonic acid compounds, each having a benzoazole ring with sulfonic acid groups bonded on both sides of the disulfide bond, are highly soluble in water and are not modified by oxidation, so they are added to tin or tin alloy plating baths. Then, the uniformity and smoothness of the plating film can be improved in a wide current density range, and the film appearance and solder wettability can be improved. Especially, when this plating bath is applied to barrel plating, aggregation of dummy etc. is prevented smoothly. We found what we could do and completed the present invention.
即ち、本発明1は、(A)第一スズ塩と、第一スズ塩及び銀、銅、ビスマス、インジウム、亜鉛、アンチモン、ニッケル、鉛からなる群より選ばれた金属の塩の混合物とのいずれかよりなる可溶性塩と、
(B)酸又はその塩と、
(C)下記の一般式(1)で表されるジベンゾアゾールジスルフィドスルホン酸化合物とを
含有することを特徴とするスズ又はスズ合金メッキ浴である。
That is, the present invention 1 includes (A) a stannous salt and a mixture of a stannous salt and a metal salt selected from the group consisting of silver, copper, bismuth, indium, zinc, antimony, nickel, and lead. A soluble salt comprising any of the following:
(B) an acid or a salt thereof;
(C) a dibenzoazole disulfide sulfonic acid compound represented by the following general formula (1):
A tin or tin alloy plating bath characterized by containing.
本発明2は、上記本発明1において、さらに、錯化剤、安定剤、酸化防止剤、界面活性剤、平滑剤、光沢剤、半光沢剤、導電性塩、pH調整剤、緩衝剤より選ばれた添加剤の少なくとも一種を含有することを特徴とするスズ又はスズ合金メッキ浴である。 The present invention 2 is the same as the present invention 1, further selected from a complexing agent, a stabilizer, an antioxidant, a surfactant, a smoothing agent, a brightening agent, a semi-glossing agent, a conductive salt, a pH adjusting agent, and a buffering agent. It is a tin or tin alloy plating bath characterized by containing at least one kind of additive.
本発明3は、上記本発明1又は2のスズ又はスズ合金メッキ浴を用いて被メッキ物にバレルメッキを施すことを特徴とするバレルメッキ方法である。 The present invention 3 is a barrel plating method characterized in that barrel plating is performed on an object to be plated using the tin or tin alloy plating bath of the first or second invention.
本発明4は、上記本発明3において、被メッキ物が、抵抗、可変抵抗、コンデンサ、フィルタ、インダクタ、サーミスタ、水晶振動子、スイッチ、リード線、プリント基板、半導体集積回路、モジュールより選ばれた電子部品であることを特徴とするバレルメッキ方法である。 In the present invention 4, in the present invention 3, the object to be plated is selected from a resistor, a variable resistor, a capacitor, a filter, an inductor, a thermistor, a crystal resonator, a switch, a lead wire, a printed circuit board, a semiconductor integrated circuit, and a module. It is a barrel plating method characterized by being an electronic component.
(1)本発明のメッキ浴を電気メッキに適用する場合、広い電気密度範囲でメッキ皮膜の均一性や平滑性を向上できる。
また、電気、無電解のメッキ方式を問わず、得られたメッキ皮膜は外観やハンダ濡れ性に優れる。
前記特許文献1の化合物では、水に溶解しにくかったり、メルカプト基が酸化を受け易く、難溶性の化合物になって効果を発揮しなくなる恐れがあるが、本発明の化合物ではスルホン酸(塩)基とジスルフィド結合を有するため、このような問題はない。
(1) When the plating bath of the present invention is applied to electroplating, the uniformity and smoothness of the plating film can be improved in a wide electric density range.
Regardless of the electroless or electroless plating method, the obtained plating film is excellent in appearance and solder wettability.
In the compound of Patent Document 1, it is difficult to dissolve in water, or the mercapto group is susceptible to oxidation and may become a poorly soluble compound and may not exhibit the effect. However, in the compound of the present invention, sulfonic acid (salt) There is no such problem because it has a disulfide bond with the group.
(2)本発明のメッキ浴をバレルメッキに適用すると、ダミーや被メッキ物同士の凝集を円滑に防止し、バレルメッキの生産性を向上できる。
前記特許文献4では、ダミーや被メッキ物同士の凝集防止のためにビスマス、インジウムなどの異種金属をメッキ浴に添加(ドープ)するため、その金属が皮膜に共析して皮膜の機械特性が変わってしまう恐れがあるが、本発明の化合物はベンゾアゾール環を有するジスルフィドジスルホン酸化合物であり、上記文献4のような異種金属の共析はないため、メッキ皮膜の機械的特性に悪影響を及ぼすこともない。
(2) When the plating bath of the present invention is applied to barrel plating, it is possible to smoothly prevent the dummy and the objects to be plated from agglomerating and improve the productivity of barrel plating.
In Patent Document 4, since different metals such as bismuth and indium are added (dope) to the plating bath in order to prevent agglomeration between the dummy and the object to be plated, the metal co-deposits on the film and the mechanical properties of the film are increased. The compound of the present invention is a disulfide disulfonic acid compound having a benzoazole ring, and there is no eutectoid of dissimilar metals as in the above-mentioned document 4, which adversely affects the mechanical properties of the plating film. There is nothing.
本発明は、第一に、ジスルフィド結合の両側にベンゾアゾール環を夫々有し、この両側のベンゾアゾール環の少なくともいずれかにスルホン酸基が1個以上結合したジベンゾアゾールジスルフィドスルホン酸化合物を含有するスズメッキ浴、又はスズ−銀合金やスズ−ビスマス合金などの所定のスズ合金メッキ浴であり、第二に、これらのメッキ浴をバレルメッキに適用するメッキ方法である。
但し、第一のメッキ浴は電気メッキ浴、無電解メッキ浴を問わない。
The present invention first includes a dibenzoazole disulfide sulfonic acid compound having a benzoazole ring on both sides of a disulfide bond and having at least one sulfonic acid group bonded to at least one of the benzoazole rings on both sides. A tin plating bath, or a predetermined tin alloy plating bath such as a tin-silver alloy or a tin-bismuth alloy, and second, a plating method in which these plating baths are applied to barrel plating.
However, the first plating bath may be an electroplating bath or an electroless plating bath.
上述の通り、本発明のジベンゾアゾールジスルフィドスルホン酸化合物は一般式(1)で表されるが、ベンゾアゾール環の3位に配置する原子Xはイオウ、窒素又は酸素であり、この中ではイオウが好ましい。即ち、Xがイオウ原子の場合にはベンゾアゾール環はベンゾチアゾール環になり、同じく、窒素ではベンズイミダゾール環、酸素ではベンゾオキサゾール環となり、ベンゾチアゾール環が好ましい。
このベンゾアゾール環に結合するスルホン酸(塩)基の個数m、nは夫々0〜2個であるが、mとnが共に0になることはない。つまり、水溶性などの観点から、左右両側のベンゾアゾール環には1個以上のスルホン酸(塩)基の結合が必要であり、一般にスルホン酸(塩)基が多いほど水溶性は増す。スルホン酸(塩)基(=SO3A)の原子Aは水素、ナトリウム又はカリウムであり、スルホン酸(遊離酸)の形態、或はスルホン酸のナトリウム塩やカリウム塩の形態のいずれかである。
また、ジスルフィド結合を間にして左右の各ベンゾアゾール環に結合する置換基Rは、C1〜C3アルキル、C1〜C3アルコキシ、ハロゲン、アミノ、ニトロ、カルボキシルよりなる群から選択でき、特に、C1〜C3アルキル、C1〜C3アルコキシ、ハロゲン、ニトロ、カルボキシルが好ましい。当該置換基Rは左右のベンゾアゾール環で同種になっても良いし、異種になっても良い。
この置換基Rの個数a及びbは0〜2個であり、無置換(a=b=0)でも良いし、各ベンゾアゾール環で1〜2個の置換基を有しても差し支えない。
As described above, the dibenzoazole disulfide sulfonic acid compound of the present invention is represented by the general formula (1), and the atom X arranged at the 3-position of the benzoazole ring is sulfur, nitrogen or oxygen, in which sulfur is preferable. That is, when X is a sulfur atom, the benzoazole ring is a benzothiazole ring, and similarly, when nitrogen is a benzimidazole ring, when oxygen is a benzoxazole ring, a benzothiazole ring is preferable.
The numbers m and n of the sulfonic acid (salt) groups bonded to the benzoazole ring are 0 to 2, respectively, but neither m nor n is 0. That is, from the viewpoint of water solubility, one or more sulfonic acid (salt) groups need to be bonded to the right and left benzoazole rings. Generally, the more sulfonic acid (salt) groups, the more water soluble. The atom A of the sulfonic acid (salt) group (= SO 3 A) is hydrogen, sodium or potassium, and is either in the form of sulfonic acid (free acid) or in the form of sodium salt or potassium salt of sulfonic acid. .
The substituent R bonded to each of the right and left benzoazole rings with a disulfide bond in between can be selected from the group consisting of C 1 -C 3 alkyl, C 1 -C 3 alkoxy, halogen, amino, nitro, carboxyl, In particular, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, halogen, nitro, carboxyl are preferred. The substituent R may be the same or different in the left and right benzoazole rings.
The numbers a and b of the substituents R are 0 to 2 and may be unsubstituted (a = b = 0), or each benzoazole ring may have 1 to 2 substituents.
本発明のジベンゾアゾールジスルフィドスルホン酸化合物としては、ジベンゾチアゾリルジスルフィドジスルホン酸、ジベンゾチアゾリルジスルフィドトリスルホン酸、ジベンゾチアゾリルジスルフィドモノスルホン酸、ジベンゾオキサゾリルジスルフィドジスルホン酸、ジベンズイミダゾリルジスルフィドジスルホン酸、又はこれらの塩、或はベンゾアゾール環に置換基を有するこれらの酸又はその塩などが挙げられる。
当該化合物のより具体的な例としては、ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム、ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム、ジベンゾチアゾリルジスルフィドモノスルホン酸カリウム、ジ(4−メチルベンゾチアゾリル)ジスルフィドジスルホン酸二ナトリウム、ジ(6−クロロベンゾチアゾリル)ジスルフィドジスルホン酸二ナトリウム、ジ(6−メトキシベンゾチアゾリル)ジスルフィドジスルホン酸二ナトリウム、ジ(6−ニトロベンゾチアゾリル)ジスルフィドジスルホン酸二ナトリウム、ジ(6−メチルベンゾチアゾリル)ジスルフィドトリスルホン酸、ジベンゾオキサゾリルジスルフィドジスルホン酸二ナトリウム、ジ(6−メチルベンゾオキサゾリル)ジスルフィドジスルホン酸二ナトリウム、ジベンズイミダゾリルジスルフィドジスルホン酸二ナトリウム、ジ(6−メトキシベンズイミダゾリル)ジスルフィドジスルホン酸二ナトリウムなどが好ましい。
Examples of the dibenzoazole disulfide sulfonic acid compound of the present invention include dibenzothiazolyl disulfide disulfonic acid, dibenzothiazolyl disulfide trisulfonic acid, dibenzothiazolyl disulfide monosulfonic acid, dibenzooxazolyl disulfide disulfonic acid, dibenzimidazolyl disulfide Examples thereof include disulfonic acid, or a salt thereof, or an acid or a salt thereof having a substituent on the benzoazole ring.
More specific examples of such compounds include disodium dibenzothiazolyl disulfide disulfonate, trisodium dibenzothiazolyl disulfide trisulfonate, potassium dibenzothiazolyl disulfide monosulfonate, di (4-methylbenzothiazoli D) Disodium disulfide disulfonate, disodium di (6-chlorobenzothiazolyl) disulfide disulfonate, disodium di (6-methoxybenzothiazolyl) disulfide disulfonate, di (6-nitrobenzothiazolyl) Disodium disulfide disulfonate, di (6-methylbenzothiazolyl) disulfide trisulfonic acid, dibenzoxazolyl disulfide disodium disulfonate, di (6-methylbenzoxazolyl) disulfide disulfonate dina Potassium, di-benzimidazolyl disulfide disulfonic acid disodium, and di (6-methoxy-benzimidazolyl) disulfide disulfonic acid disodium is preferred.
本発明のジベンゾアゾールジスルフィドスルホン酸化合物は単用又は併用でき、その含有量はメッキ浴全体に対して0.01〜10g/Lの少量が適しており、0.1〜3g/Lが好ましい。
含有量が0.01g/Lより少ないと、メッキ皮膜の平滑性や均一性、皮膜外観、ハンダ付け性の向上効果が発揮されず、また、バレルメッキに際して凝集防止効果が低下する。一方、含有量が10g/Lより多いと、電気メッキでは低電流密度部が無光沢メッキになる恐れがある。
The dibenzoazole disulfide sulfonic acid compound of the present invention can be used alone or in combination, and its content is suitably a small amount of 0.01 to 10 g / L, preferably 0.1 to 3 g / L with respect to the entire plating bath.
When the content is less than 0.01 g / L, the effect of improving the smoothness and uniformity of the plating film, the appearance of the film, and the solderability is not exhibited, and the effect of preventing aggregation is reduced during barrel plating. On the other hand, if the content is more than 10 g / L, the low current density part may become matte plating in electroplating.
また、本発明のジベンゾアゾールジスルフィドスルホン酸化合物は、ジベンゾアゾールジスルフィド化合物を濃硫酸又は発煙硫酸の存在下、70℃〜180℃、好ましくは100℃〜140℃にて5時間〜60時間反応させる方式を初めとして、常法により製造することができる。
ちなみに、上記ジベンゾアゾールジスルフィド化合物(例えば、ジベンゾチアゾールジスルフィド化合物)は市販されている。
The dibenzoazole disulfide sulfonic acid compound of the present invention is a method in which a dibenzoazole disulfide compound is reacted in the presence of concentrated sulfuric acid or fuming sulfuric acid at 70 to 180 ° C., preferably 100 to 140 ° C. for 5 to 60 hours. Can be produced by a conventional method.
Incidentally, the dibenzoazole disulfide compound (for example, dibenzothiazole disulfide compound) is commercially available.
本発明のスズ又はスズ合金メッキ浴において、可溶性第一スズ塩は、基本的に水中でSn2+を発生させる有機酸又は無機酸のスズ塩であり、具体的には、硫酸第一スズ、酢酸第一スズ、ホウフッ化第一スズ、スルファミン酸第一スズ、ピロリン酸第一スズ、塩化第一スズ、グルコン酸第一スズ、酒石酸第一スズ、酸化第一スズ、スズ酸ナトリウム、スズ酸カリウム、メタンスルホン酸第一スズ、エタンスルホン酸第一スズ、2−ヒドロキシエタンスルホン酸第一スズ、2−ヒドロキシプロパンスルホン酸第一スズ、スルホコハク酸第一スズなどが挙げられる。 In the tin or tin alloy plating bath of the present invention, the soluble stannous salt is basically a tin salt of an organic acid or an inorganic acid that generates Sn 2+ in water, specifically, stannous sulfate, Stannous acetate, stannous borofluoride, stannous sulfamate, stannous pyrophosphate, stannous chloride, stannous gluconate, stannous tartrate, stannous oxide, sodium stannate, stannic acid Examples include potassium, stannous methanesulfonate, stannous ethanesulfonate, stannous 2-hydroxyethanesulfonate, stannous 2-hydroxypropanesulfonate, and stannous sulfosuccinate.
本発明の所定のスズ合金メッキ浴において、スズ合金を形成するスズの相手方の金属の可溶性塩について述べれば、例えば、銀の可溶性塩としては、酢酸銀、硝酸銀、塩化銀、酸化銀、シアン化銀、シアン化銀カリウム、メタンスルホン酸銀、2−ヒドロキシエタンスルホン酸銀、2−ヒドロキシプロパンスルホン酸銀などが挙げられる。
銅の可溶性塩には、硫酸銅、硝酸銅、炭酸銅、ピロリン酸銅、塩化銅、シアン化銅、ホウフッ化銅、スルファミン酸銅、メタンスルホン酸銅、2−ヒドロキシエタンスルホン酸銅、2−ヒドロキシプロパンスルホン酸銅などがある。
ビスマスの可溶性塩には、硫酸ビスマス、グルコン酸ビスマス、硝酸ビスマス、酸化ビスマス、炭酸ビスマス、塩化ビスマス、メタンスルホン酸ビスマス、2−ヒドロキシプロパンスルホン酸ビスマスなどがある。
インジウムの可溶性塩には、スルファミン酸インジウム、硫酸インジウム、ホウフッ化インジウム、酸化インジウム、メタンスルホン酸インジウム、2−ヒドロキシプロパンスルホン酸インジウムなどがある。
亜鉛の可溶性塩には、硫酸亜鉛、硝酸亜鉛、塩化亜鉛、ピロリン酸亜鉛、シアン化亜鉛、メタンスルホン酸亜鉛、2−ヒドロキシエタンスルホン酸亜鉛、2−ヒドロキシプロパンスルホン酸亜鉛などがある。
アンチモンの可溶性塩には、ホウフッ化アンチモン、塩化アンチモン、酒石酸アンチモニルカリウム、ピロアンチモン酸カリウム、酒石酸アンチモン、メタンスルホン酸アンチモン、2−ヒドロキシプロパンスルホン酸アンチモンなどがある。
ニッケルの可溶性塩には、硫酸ニッケル、ギ酸ニッケル、塩化ニッケル、スルファミン酸ニッケル、ホウフッ化ニッケル、酢酸ニッケル、メタンスルホン酸ニッケル、2−ヒドロキシプロパンスルホン酸ニッケルなどがある。
鉛の可溶性塩には、酢酸鉛、硝酸鉛、炭酸鉛、ホウフッ化鉛、スルファミン酸鉛、メタンスルホン酸鉛、エタンスルホン酸鉛、2−ヒドロキシエタンスルホン酸鉛、2−ヒドロキシプロパンスルホン酸鉛などがある。
In the predetermined tin alloy plating bath of the present invention, the soluble salt of the tin counterpart metal that forms the tin alloy will be described. For example, the soluble salt of silver includes silver acetate, silver nitrate, silver chloride, silver oxide, cyanide. Examples include silver, potassium potassium cyanide, silver methanesulfonate, silver 2-hydroxyethanesulfonate, and silver 2-hydroxypropanesulfonate.
The soluble salts of copper include copper sulfate, copper nitrate, copper carbonate, copper pyrophosphate, copper chloride, copper cyanide, copper borofluoride, copper sulfamate, copper methanesulfonate, copper 2-hydroxyethanesulfonate, 2- Examples include copper hydroxypropane sulfonate.
Soluble salts of bismuth include bismuth sulfate, bismuth gluconate, bismuth nitrate, bismuth oxide, bismuth carbonate, bismuth chloride, bismuth methanesulfonate, and bismuth 2-hydroxypropanesulfonate.
Soluble salts of indium include indium sulfamate, indium sulfate, indium borofluoride, indium oxide, indium methanesulfonate, and indium 2-hydroxypropanesulfonate.
Soluble zinc salts include zinc sulfate, zinc nitrate, zinc chloride, zinc pyrophosphate, zinc cyanide, zinc methanesulfonate, zinc 2-hydroxyethanesulfonate, zinc 2-hydroxypropanesulfonate, and the like.
Soluble salts of antimony include antimony borofluoride, antimony chloride, potassium antimony tartrate, potassium pyroantimonate, antimony tartrate, antimony methanesulfonate, and antimony 2-hydroxypropanesulfonate.
Soluble nickel salts include nickel sulfate, nickel formate, nickel chloride, nickel sulfamate, nickel borofluoride, nickel acetate, nickel methanesulfonate, nickel 2-hydroxypropanesulfonate.
Soluble lead salts include lead acetate, lead nitrate, lead carbonate, lead borofluoride, lead sulfamate, lead methanesulfonate, lead ethanesulfonate, lead 2-hydroxyethanesulfonate, lead 2-hydroxypropanesulfonate, etc. There is.
上記金属の可溶性塩の浴中の総濃度は、一般に金属塩換算で1〜200g/L、好ましくは10〜100g/Lである。
また、スズとその他の金属の混合割合は、所望するスズ合金メッキ皮膜の組成比に応じて適宜調整すれば良い。
The total concentration of the metal soluble salt in the bath is generally 1 to 200 g / L, preferably 10 to 100 g / L in terms of metal salt.
Moreover, what is necessary is just to adjust suitably the mixing ratio of tin and another metal according to the composition ratio of the desired tin alloy plating film.
本発明のスズ合金はスズと、銀、銅、ビスマス、インジウム、亜鉛、アンチモン、ニッケル、鉛からなる群より選ばれた少なくとも一種の金属との合金であり、具体的には、スズ−銀、スズ−銅、スズ−ビスマス、スズ−インジウム、スズ−亜鉛、スズ−アンチモン、スズ−ニッケル、スズ−鉛の2成分系の合金を初め、スズ−銀−銅、スズ−ビスマス−銅、スズ−亜鉛−ニッケルなどの3成分系以上の合金を包含する。
浴管理の観点からは既述の2成分系のスズ合金が好ましい。
The tin alloy of the present invention is an alloy of tin and at least one metal selected from the group consisting of silver, copper, bismuth, indium, zinc, antimony, nickel, lead, specifically, tin-silver, Tin-copper, tin-bismuth, tin-indium, tin-zinc, tin-antimony, tin-nickel, tin-lead alloys, tin-silver-copper, tin-bismuth-copper, tin- Includes alloys of three or more components such as zinc-nickel.
From the viewpoint of bath management, the aforementioned two-component tin alloy is preferable.
本発明のスズ又はスズ合金メッキ浴において、浴ベースは有機酸、無機酸、或はそのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩などである。
上記有機酸としては、有機スルホン酸、脂肪族カルボン酸などが挙げられ、無機酸としては、硫酸、塩酸、ホウフッ化水素酸、ケイフッ化水素酸、スルファミン酸などが挙げられる。この中では、硫酸浴を初め、スズの溶解性、排水処理の容易性などの見地から有機スルホン酸又はその塩の浴が好ましい。
上記酸又はその塩は単用又は併用でき、その含有量は0.1〜10モル/L、好ましくは0.5〜5モル/Lである。
In the tin or tin alloy plating bath of the present invention, the bath base is an organic acid, an inorganic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt or amine salt thereof.
Examples of the organic acid include organic sulfonic acid and aliphatic carboxylic acid, and examples of the inorganic acid include sulfuric acid, hydrochloric acid, borohydrofluoric acid, hydrofluoric acid, and sulfamic acid. Among these, a bath of an organic sulfonic acid or a salt thereof is preferable from the standpoint of sulfuric acid bath, tin solubility, ease of wastewater treatment, and the like.
The acid or salt thereof can be used singly or in combination, and its content is 0.1 to 10 mol / L, preferably 0.5 to 5 mol / L.
上記有機スルホン酸は、アルカンスルホン酸、アルカノールスルホン酸、スルホコハク酸、芳香族スルホン酸などであり、アルカンスルホン酸としては、化学式CnH2n+1SO3H(例えば、n=1〜11)で示されるものが使用でき、具体的には、メタンスルホン酸、エタンスルホン酸、1―プロパンスルホン酸、2―プロパンスルホン酸、1―ブタンスルホン酸、2―ブタンスルホン酸、ペンタンスルホン酸などが挙げられる。 Examples of the organic sulfonic acid include alkane sulfonic acid, alkanol sulfonic acid, sulfosuccinic acid, and aromatic sulfonic acid. As the alkane sulfonic acid, chemical formula C n H 2n + 1 SO 3 H (for example, n = 1 to 11) In particular, methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, 2-propanesulfonic acid, 1-butanesulfonic acid, 2-butanesulfonic acid, pentanesulfonic acid and the like can be used. Can be mentioned.
上記アルカノールスルホン酸としては、化学式
CmH2m+1-CH(OH)-CpH2p-SO3H(例えば、m=0〜6、p=1〜5)
で示されるものが使用でき、具体的には、2―ヒドロキシエタン―1―スルホン酸(イセチオン酸)、2―ヒドロキシプロパン―1―スルホン酸(2−プロパノールスルホン酸)、3―ヒドロキシプロパン―1―スルホン酸、2―ヒドロキシブタン―1―スルホン酸、2―ヒドロキシペンタン―1―スルホン酸などの外、1―ヒドロキシプロパン―2―スルホン酸、4―ヒドロキシブタン―1―スルホン酸、2―ヒドロキシヘキサン―1―スルホン酸などが挙げられる。
Examples of the alkanol sulfonic acid include chemical formula C m H 2m + 1 —CH (OH) —C p H 2p —SO 3 H (for example, m = 0 to 6, p = 1 to 5).
In particular, 2-hydroxyethane-1-sulfonic acid (isethionic acid), 2-hydroxypropane-1-sulfonic acid (2-propanolsulfonic acid), 3-hydroxypropane-1 -Sulfonic acid, 2-hydroxybutane-1-sulfonic acid, 2-hydroxypentane-1-sulfonic acid and the like, 1-hydroxypropane-2-sulfonic acid, 4-hydroxybutane-1-sulfonic acid, 2-hydroxy Examples include hexane-1-sulfonic acid.
上記芳香族スルホン酸は、基本的にベンゼンスルホン酸、アルキルベンゼンスルホン酸、フェノールスルホン酸、ナフタレンスルホン酸、アルキルナフタレンスルホン酸、ナフトールスルホン酸などであり、具体的には、1−ナフタレンスルホン酸、2−ナフタレンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、p−フェノールスルホン酸、クレゾールスルホン酸、スルホサリチル酸、ニトロベンゼンスルホン酸、スルホ安息香酸、ジフェニルアミン−4−スルホン酸などが挙げられる。
上記有機スルホン酸では、メタンスルホン酸、エタンスルホン酸、2−プロパノールスルホン酸、2−ヒドロキシエタンスルホン酸などが好ましい。
The aromatic sulfonic acid is basically benzene sulfonic acid, alkyl benzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, naphthol sulfonic acid, etc., specifically, 1-naphthalene sulfonic acid, 2 -Naphthalenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, p-phenolsulfonic acid, cresolsulfonic acid, sulfosalicylic acid, nitrobenzenesulfonic acid, sulfobenzoic acid, diphenylamine-4-sulfonic acid and the like.
Among the organic sulfonic acids, methanesulfonic acid, ethanesulfonic acid, 2-propanolsulfonic acid, 2-hydroxyethanesulfonic acid, and the like are preferable.
本発明は酸性、中性(弱酸性を含む)などの任意のpH領域のスズ又はスズ合金メッキ浴に適用できる。
基本的に、第一スズイオンは酸性では安定であるが、中性付近では白色沈澱が生じ易い。このため、本発明を中性付近のスズメッキ浴に適用する場合には、スズイオンを安定化させる目的で、錯化剤を含有するのが好ましい。
上記錯化剤は、オキシカルボン酸、ポリカルボン酸、モノカルボン酸などであり、具体的には、グルコン酸、クエン酸、グルコヘプトン酸、グルコノラクトン、グルコヘプトラクトン、ギ酸、酢酸、プロピオン酸、酪酸、アスコルビン酸、シュウ酸、マロン酸、コハク酸、グリコール酸、リンゴ酸、酒石酸、ジグリコール酸、或はこれらの塩などが挙げられる。好ましくは、グルコン酸、クエン酸、グルコヘプトン酸、グルコノラクトン、グルコヘプトラクトン、或はこれらの塩などである。
また、エチレンジアミン、エチレンジアミン四酢酸(EDTA)、ジエチレントリアミン五酢酸(DTPA)、ニトリロ三酢酸(NTA)、イミノジ酢酸(IDA)、イミノジプロピオン酸(IDP)、ヒドロキシエチルエチレンジアミン三酢酸(HEDTA)、トリエチレンテトラミン六酢酸(TTHA)、エチレンジオキシビス(エチルアミン)−N,N,N′,N′−テトラ酢酸、グリシン類、ニトリロトリメチルホスホン酸、1−ヒドロキシエタン−1,1−ジホスホン酸、或はこれらの塩などのポリアミンやアミノカルボン酸類も錯化剤として有効である。
The present invention can be applied to tin or tin alloy plating baths in any pH range such as acidic and neutral (including weakly acidic).
Basically, stannous ions are stable when acidic, but white precipitates are likely to occur near neutrality. For this reason, when applying this invention to the tin plating bath near neutrality, it is preferable to contain a complexing agent for the purpose of stabilizing tin ions.
Examples of the complexing agent include oxycarboxylic acid, polycarboxylic acid, and monocarboxylic acid. Specifically, gluconic acid, citric acid, glucoheptonic acid, gluconolactone, glucoheptlactone, formic acid, acetic acid, propionic acid , Butyric acid, ascorbic acid, oxalic acid, malonic acid, succinic acid, glycolic acid, malic acid, tartaric acid, diglycolic acid, or salts thereof. Preferably, gluconic acid, citric acid, glucoheptonic acid, gluconolactone, glucoheptlactone, or a salt thereof.
In addition, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), iminodipropionic acid (IDP), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylene Tetramine hexaacetic acid (TTHA), ethylenedioxybis (ethylamine) -N, N, N ', N'-tetraacetic acid, glycines, nitrilotrimethylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, or these Polyamines such as these salts and aminocarboxylic acids are also effective as complexing agents.
また、本発明のスズ合金メッキ浴では、スズと合金を形成する相手方の銀、銅、ビスマスなどに電極電位が錫より貴な金属が多いため、これらの各種イオンを浴中で安定にしてスズと共析化させる見地から、安定剤を適宜添加するのが良い。
当該安定剤としては、チオ尿素、或はジメチルチオ尿素、トリメチルチオ尿素、ジエチルチオ尿素、アリルチオ尿素、アセチルチオ尿素、チオセミカルバジドなどのチオ尿素誘導体などのチオアミド類、チオグリコール(HS−CH2CH2OH)、チオグリコール酸(HSCH2COOH)、メルカプトプロピオン酸(CH3CH(SH)COOH)、メルカプトコハク酸などのメルカプタン類、チオジグリコール(HOCH2CH2−S−CH2CH2OH)、チオビス(ドデカエチレングリコール)(H−(OCH2CH2)12−S−(CH2CH2O)12−H)、チオジグリコール酸(HOOCCH2−S−CH2COOH)、ジチオジアニリン、ジピリジルジスルフィド、3,6−ジチオ−1,8−オクタンジオール、4,7−ジチオ−1,10−デカンジオールなどのスルフィド類、或は、亜硫酸塩等が挙げられる。
さらに、前記錯化剤として列挙したオキシカルボン酸、ポリカルボン酸又はこれらの塩、或はポリアミンやアミノカルボン酸類なども有効である。
Further, in the tin alloy plating bath of the present invention, there are more metals having a higher electrode potential than tin in the counterpart silver, copper, bismuth, etc. that form an alloy with tin. From the standpoint of co-deposition, it is preferable to add a stabilizer appropriately.
The stabilizer includes thiourea, or thioamides such as thiourea derivatives such as dimethylthiourea, trimethylthiourea, diethylthiourea, allylthiourea, acetylthiourea, thiosemicarbazide, thioglycol (HS-CH 2 CH 2 OH). , Thioglycolic acid (HSCH 2 COOH), mercaptopropionic acid (CH 3 CH (SH) COOH), mercaptans such as mercaptosuccinic acid, thiodiglycol (HOCH 2 CH 2 —S—CH 2 CH 2 OH), thiobis (Dodecaethylene glycol) (H— (OCH 2 CH 2 ) 12 —S— (CH 2 CH 2 O) 12 —H), thiodiglycolic acid (HOOCCH 2 —S—CH 2 COOH), dithiodianiline, dipyridyl Disulfide, 3,6-dithio-1,8-octanediol, 4,7-dithio-1, Examples thereof include sulfides such as 10-decanediol, and sulfites.
Furthermore, the oxycarboxylic acids, polycarboxylic acids or salts thereof listed as the complexing agent, polyamines, aminocarboxylic acids and the like are also effective.
また、本発明のスズメッキ浴には、上記錯化剤や安定剤の外にも、酸化防止剤、界面活性剤、平滑剤、光沢剤、半光沢剤、pH調整剤、導電性塩、防腐剤、消泡剤などの各種添加剤を含有できる。
上記酸化防止剤は浴中のSn2+の酸化防止を目的としたもので、アスコルビン酸又はその塩、ハイドロキノン、カテコール、レゾルシン、ヒドロキノン、フロログルシン、クレゾールスルホン酸又はその塩、フェノールスルホン酸又はその塩、カテコールスルホン酸又はその塩、ハイドロキノンスルホン酸又はその塩、ヒドロキシナフタレンスルホン酸又はその塩、ヒドラジンなどが挙げられる。例えば、中性浴ではアスコルビン酸又はその塩などが好ましい。
上記界面活性剤は、メッキ皮膜の外観、緻密性、平滑性、密着性などの改善を目的とし、通常のアニオン系、カチオン系、ノニオン系、或は両性などの各種界面活性剤が使用できる。
上記アニオン系界面活性剤としては、アルキル硫酸塩、ポリオキシエチレンアルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩などが挙げられる。カチオン系界面活性剤としては、モノ〜トリアルキルアミン塩、ジメチルジアルキルアンモニウム塩、トリメチルアルキルアンモニウム塩などが挙げられる。ノニオン系界面活性剤としては、C1〜C20アルカノール、フェノール、ナフトール、ビスフェノール類、C1〜C25アルキルフェノール、アリールアルキルフェノール、C1〜C25アルキルナフトール、C1〜C25アルコキシルリン酸(塩)、ソルビタンエステル、ポリアルキレングリコール、C1〜C22脂肪族アミドなどにエチレンオキシド(EO)及び/又はプロピレンオキシド(PO)を2〜300モル付加縮合させたものなどが挙げられる。両性界面活性剤としては、カルボキシベタイン、イミダゾリンベタイン、アミノカルボン酸などが挙げられる。
In addition to the above complexing agents and stabilizers, the tin plating bath of the present invention includes an antioxidant, a surfactant, a smoothing agent, a brightening agent, a semi-brightening agent, a pH adjusting agent, a conductive salt, a preservative. Various additives such as an antifoaming agent can be contained.
The above-mentioned antioxidant is for the purpose of preventing the oxidation of Sn 2+ in the bath. Ascorbic acid or a salt thereof, hydroquinone, catechol, resorcin, hydroquinone, phloroglucin, cresolsulfonic acid or a salt thereof, phenolsulfonic acid or a salt thereof Catecholsulfonic acid or a salt thereof, hydroquinonesulfonic acid or a salt thereof, hydroxynaphthalenesulfonic acid or a salt thereof, hydrazine and the like. For example, in a neutral bath, ascorbic acid or a salt thereof is preferable.
For the purpose of improving the appearance, denseness, smoothness, adhesion and the like of the plating film, various surfactants such as ordinary anionic, cationic, nonionic or amphoteric surfactants can be used.
Examples of the anionic surfactant include alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl benzene sulfonates, and alkyl naphthalene sulfonates. Examples of the cationic surfactant include mono-trialkylamine salts, dimethyldialkylammonium salts, and trimethylalkylammonium salts. Examples of the nonionic surfactant, C 1 -C 20 alkanols, phenol, naphthol, bisphenol, C 1 -C 25 alkyl phenols, aryl phenols, C 1 -C 25 alkyl naphthol, C 1 -C 25 alkoxyl phosphoric acid (salt ), Sorbitan esters, polyalkylene glycols, C 1 -C 22 aliphatic amides and the like, and 2-300 mol addition-condensation of ethylene oxide (EO) and / or propylene oxide (PO). Examples of amphoteric surfactants include carboxybetaine, imidazoline betaine, and aminocarboxylic acid.
上記平滑剤としては、β−ナフトール、β−ナフトール−6−スルホン酸、β−ナフタレンスルホン酸、m−クロロベンズアルデヒド、p−ニトロベンズアルデヒド、p−ヒドロキシベンズアルデヒド、(o−、p−)メトキシベンズアルデヒド、バニリン、(2,4−、2,6−)ジクロロベンズアルデヒド、(o−、p−)クロロベンズアルデヒド、1−ナフトアルデヒド、2−ナフトアルデヒド、2(4)−ヒドロキシ−1−ナフトアルデヒド、2(4)−クロロ−1−ナフトアルデヒド、2(3)−チオフェンカルボキシアルデヒド、2(3)−フルアルデヒド、3−インドールカルボキシアルデヒド、サリチルアルデヒド、o−フタルアルデヒド、ホルムアルデヒド、アセトアルデヒド、パラアルデヒド、ブチルアルデヒド、イソブチルアルデヒド、プロピオンアルデヒド、n−バレルアルデヒド、アクロレイン、クロトンアルデヒド、グリオキサール、アルドール、スクシンジアルデヒド、カプロンアルデヒド、イソバレルアルデヒド、アリルアルデヒド、グルタルアルデヒド、1−ベンジリデン−7−ヘプタナール、2,4−ヘキサジエナール、シンナムアルデヒド、ベンジルクロトンアルデヒド、アミン−アルデヒド縮合物、酸化メシチル、イソホロン、ジアセチル、ヘキサンジオン−3,4、アセチルアセトン、3−クロロベンジリデンアセトン、sub.ピリジリデンアセトン、sub.フルフリジンアセトン、sub.テニリデンアセトン、4−(1−ナフチル)−3−ブテン−2−オン、4−(2−フリル)−3−ブテン−2−オン、4−(2−チオフェニル)−3−ブテン−2−オン、クルクミン、ベンジリデンアセチルアセトン、ベンザルアセトン、アセトフェノン、(2,4−、3,4−)ジクロロアセトフェノン、ベンジリデンアセトフェノン、2−シンナミルチオフェン、2−(ω−ベンゾイル)ビニルフラン、ビニルフェニルケトン、アクリル酸、メタクリル酸、エタクリル酸、アクリル酸エチル、メタクリル酸メチル、メタクリル酸ブチル、クロトン酸、プロピレン−1,3−ジカルボン酸、ケイ皮酸、(o−、m−、p−)トルイジン、(o−、p−)アミノアニリン、アニリン、(o−、p−)クロロアニリン、(2,5−、3,4−)クロロメチルアニリン、N−モノメチルアニリン、4,4′−ジアミノジフェニルメタン、N−フェニル−(α−、β−)ナフチルアミン、メチルベンズトリアゾール、1,2,3−トリアジン、1,2,4−トリアジン、1,3,5−トリアジン、1,2,3−ベンズトリアジン、イミダゾール、2−ビニルピリジン、インドール、キノリン、モノエタノールアミンとo−バニリンの反応物、ポリビニルアルコール、カテコール、ハイドロキノン、レゾルシン、ポリエチレンイミン、エチレンジアミンテトラ酢酸二ナトリウム、ポリビニルピロリドンなどが挙げられる。
また、ゼラチン、ポリペプトン、N-(3-ヒドロキシブチリデン)-p-スルファニル酸、N-ブチリデンスルファニル酸、N-シンナモイリデンスルファニル酸、2,4-ジアミノ-6-(2'-メチルイミダゾリル(1'))エチル-1,3,5-トリアジン、2,4-ジアミノ-6-(2'-エチル-4-メチルイミダゾリル(1'))エチル-1,3,5-トリアジン、2,4-ジアミノ-6-(2'-ウンデシルイミダゾリル(1'))エチル-1,3,5-トリアジン、サリチル酸フェニル、或は、ベンゾチアゾール類も平滑剤として有効である。
上記ベンゾチアゾール類としては、ベンゾチアゾール、2-メチルベンゾチアゾール、2-メルカプトベンゾチアゾール、2-(メチルメルカプト)ベンゾチアゾール、2-アミノベンゾチアゾール、2-アミノ-6-メトキシベンゾチアゾール、2-メチル-5-クロロベンゾチアゾール、2-ヒドロキシベンゾチアゾール、2-アミノ-6-メチルベンゾチアゾール、2-クロロベンゾチアゾール、2,5-ジメチルベンゾチアゾール、6-ニトロ-2-メルカプトベンゾチアゾール、5-ヒドロキシ-2-メチルベンゾチアゾール、2-ベンゾチアゾールチオ酢酸などが挙げられる。
Examples of the smoothing agent include β-naphthol, β-naphthol-6-sulfonic acid, β-naphthalenesulfonic acid, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxybenzaldehyde, (o-, p-) methoxybenzaldehyde, Vanillin, (2,4-, 2,6-) dichlorobenzaldehyde, (o-, p-) chlorobenzaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 2 (4) -hydroxy-1-naphthaldehyde, 2 ( 4) -Chloro-1-naphthaldehyde, 2 (3) -thiophenecarboxaldehyde, 2 (3) -furaldehyde, 3-indolecarboxaldehyde, salicylaldehyde, o-phthalaldehyde, formaldehyde, acetaldehyde, paraaldehyde, butyraldehyde , Isobutyraldehyde, propi Onaldehyde, n-valeraldehyde, acrolein, crotonaldehyde, glyoxal, aldol, succindialdehyde, capronaldehyde, isovaleraldehyde, allylaldehyde, glutaraldehyde, 1-benzylidene-7-heptanal, 2,4-hexadienal, Cinnamaldehyde, benzylcrotonaldehyde, amine-aldehyde condensate, mesityl oxide, isophorone, diacetyl, hexanedione-3,4, acetylacetone, 3-chlorobenzylideneacetone, sub.pyridylideneacetone, sub.furfuridineacetone, sub. Tenylideneacetone, 4- (1-naphthyl) -3-buten-2-one, 4- (2-furyl) -3-buten-2-one, 4- (2-thiophenyl) -3-butene-2- On, Kurkumi Benzylideneacetylacetone, benzalacetone, acetophenone, (2,4-3,4-) dichloroacetophenone, benzylideneacetophenone, 2-cinnamylthiophene, 2- (ω-benzoyl) vinylfuran, vinylphenylketone, acrylic acid, Methacrylic acid, ethacrylic acid, ethyl acrylate, methyl methacrylate, butyl methacrylate, crotonic acid, propylene-1,3-dicarboxylic acid, cinnamic acid, (o-, m-, p-) toluidine, (o-, p-) aminoaniline, aniline, (o-, p-) chloroaniline, (2,5-3,4-) chloromethylaniline, N-monomethylaniline, 4,4'-diaminodiphenylmethane, N-phenyl- (α-, β-) naphthylamine, methylbenztriazole, 1,2,3-triazine, 1,2,4-triazine 1,3,5-triazine, 1,2,3-benztriazine, imidazole, 2-vinylpyridine, indole, quinoline, reaction product of monoethanolamine and o-vanillin, polyvinyl alcohol, catechol, hydroquinone, resorcin, polyethylene Examples include imine, disodium ethylenediaminetetraacetate, and polyvinylpyrrolidone.
Gelatin, polypeptone, N- (3-hydroxybutylidene) -p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino-6- (2'-methylimidazolyl) (1 ′)) Ethyl-1,3,5-triazine, 2,4-diamino-6- (2′-ethyl-4-methylimidazolyl (1 ′)) ethyl-1,3,5-triazine, 2, 4-Diamino-6- (2′-undecylimidazolyl (1 ′)) ethyl-1,3,5-triazine, phenyl salicylate, or benzothiazoles are also effective as a smoothing agent.
Examples of the benzothiazoles include benzothiazole, 2-methylbenzothiazole, 2-mercaptobenzothiazole, 2- (methylmercapto) benzothiazole, 2-aminobenzothiazole, 2-amino-6-methoxybenzothiazole, and 2-methyl. -5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylbenzothiazole, 2-chlorobenzothiazole, 2,5-dimethylbenzothiazole, 6-nitro-2-mercaptobenzothiazole, 5-hydroxy -2-methylbenzothiazole, 2-benzothiazolethioacetic acid and the like.
上記光沢剤、或は半光沢剤としては、上記平滑剤とも多少重複するが、ベンズアルデヒド、o−クロロベンズアルデヒド、2,4,6−トリクロロベンズアルデヒド、m−クロロベンズアルデヒド、p−ニトロベンズアルデヒド、p−ヒドロキシベンズアルデヒド、フルフラール、1−ナフトアルデヒド、2−ナフトアルデヒド、2−ヒドロキシ−1−ナフトアルデヒド、3−アセナフトアルデヒド、ベンジリデンアセトン、ピリジデンアセトン、フルフリリデンアセトン、シンナムアルデヒド、アニスアルデヒド、サリチルアルデヒド、クロトンアルデヒド、アクロレイン、グルタルアルデヒド、パラアルデヒド、バニリンなどの各種アルデヒド、トリアジン、イミダゾール、インドール、キノリン、2−ビニルピリジン、アニリン、フェナントロリン、ネオクプロイン、ピコリン酸、チオ尿素類、N―(3―ヒドロキシブチリデン)―p―スルファニル酸、N―ブチリデンスルファニル酸、N―シンナモイリデンスルファニル酸、2,4―ジアミノ―6―(2′―メチルイミダゾリル(1′))エチル―1,3,5―トリアジン、2,4―ジアミノ―6―(2′―エチル―4―メチルイミダゾリル(1′))エチル―1,3,5―トリアジン、2,4―ジアミノ―6―(2′―ウンデシルイミダゾリル(1′))エチル―1,3,5―トリアジン、サリチル酸フェニル、或は、ベンゾチアゾール、2―メチルベンゾチアゾール、2―アミノベンゾチアゾール、2―アミノ―6―メトキシベンゾチアゾール、2―メチル―5―クロロベンゾチアゾール、2―ヒドロキシベンゾチアゾール、2―アミノ―6―メチルベンゾチアゾール、2―クロロベンゾチアゾール、2,5―ジメチルベンゾチアゾール、5―ヒドロキシ―2―メチルベンゾチアゾール等のベンゾチアゾール類などが挙げられる。 As the brightener or semi-brightener, there are some overlaps with the smoothing agent, but benzaldehyde, o-chlorobenzaldehyde, 2,4,6-trichlorobenzaldehyde, m-chlorobenzaldehyde, p-nitrobenzaldehyde, p-hydroxy. Benzaldehyde, furfural, 1-naphthaldehyde, 2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 3-acenaphthaldehyde, benzylideneacetone, pyridideneacetone, furfurylideneacetone, cinnamaldehyde, anisaldehyde, salicylaldehyde, Various aldehydes such as crotonaldehyde, acrolein, glutaraldehyde, paraaldehyde, vanillin, triazine, imidazole, indole, quinoline, 2-vinylpyridine, aniline, phena Toroline, neocuproine, picolinic acid, thioureas, N- (3-hydroxybutylidene) -p-sulfanilic acid, N-butylidenesulfanilic acid, N-cinnamoylidenesulfanilic acid, 2,4-diamino-6- ( 2'-methylimidazolyl (1 ')) ethyl-1,3,5-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl (1')) ethyl-1,3,5 -Triazine, 2,4-diamino-6- (2'-undecylimidazolyl (1 ')) ethyl-1,3,5-triazine, phenyl salicylate, or benzothiazole, 2-methylbenzothiazole, 2- Aminobenzothiazole, 2-amino-6-methoxybenzothiazole, 2-methyl-5-chlorobenzothiazole, 2-hydroxybenzothiazole, 2-amino-6-methylben Thiazole, 2-chloro-benzothiazole, 2,5-dimethyl benzothiazole, benzothiazole such as 5-hydroxy-2-methyl-benzothiazole.
上記pH調整剤としては、塩酸、硫酸等の各種の酸、アンモニア水、水酸化カリウム、水酸化ナトリウム等の各種の塩基などが挙げられるが、ギ酸、酢酸、プロピオン酸などのモノカルボン酸類、ホウ酸類、リン酸類、シュウ酸、コハク酸などのジカルボン酸類、乳酸、酒石酸などのオキシカルボン酸類なども有効である。
上記導電性塩としては、硫酸、塩酸、リン酸、スルファミン酸、スルホン酸などのナトリウム塩、カリウム塩、マグネシウム塩、アンモニウム塩、アミン塩などが挙げられるが、上記pH調整剤で共用できる場合もある。
上記防腐剤としては、ホウ酸、5−クロロ−2−メチル−4−イソチアゾリン−3−オン、塩化ベンザルコニウム、フェノール、フェノールポリエトキシレート、チモール、レゾルシン、イソプロピルアミン、グアヤコールなどが挙げられる。
上記消泡剤としては、プルロニック界面活性剤、高級脂肪族アルコール、アセチレンアルコール及びそれらのポリアルコキシレートなどが挙げられる。
Examples of the pH adjuster include various acids such as hydrochloric acid and sulfuric acid, various bases such as aqueous ammonia, potassium hydroxide and sodium hydroxide, monocarboxylic acids such as formic acid, acetic acid and propionic acid, boron Dicarboxylic acids such as acids, phosphoric acids, oxalic acid and succinic acid, and oxycarboxylic acids such as lactic acid and tartaric acid are also effective.
Examples of the conductive salt include sodium salts such as sulfuric acid, hydrochloric acid, phosphoric acid, sulfamic acid, and sulfonic acid, potassium salts, magnesium salts, ammonium salts, and amine salts. is there.
Examples of the preservative include boric acid, 5-chloro-2-methyl-4-isothiazolin-3-one, benzalkonium chloride, phenol, phenol polyethoxylate, thymol, resorcin, isopropylamine, and guaiacol.
Examples of the antifoaming agent include pluronic surfactants, higher aliphatic alcohols, acetylene alcohols and polyalkoxylates thereof.
前述したように、本発明のスズ又はスズ合金メッキ浴は電気メッキ、無電解メッキを問わずに適用することができる。
電気メッキでは、バレルメッキ、ラックメッキ、高速連続メッキ、ラックレスメッキなどの各種メッキ方式が採用できる。
電気メッキの条件としては、浴温は0℃以上、好ましくは10〜50℃程度であり、陰極電流密度は0.001〜30A/dm2、好ましくは0.01〜10A/dm2である。
無電解メッキでの浴温は、上記電気メッキと同様に0〜50℃程度が一般的である。
As described above, the tin or tin alloy plating bath of the present invention can be applied regardless of electroplating or electroless plating.
In electroplating, various plating methods such as barrel plating, rack plating, high-speed continuous plating, and rackless plating can be employed.
As electroplating conditions, the bath temperature is 0 ° C. or higher, preferably about 10 to 50 ° C., and the cathode current density is 0.001 to 30 A / dm 2 , preferably 0.01 to 10 A / dm 2 .
The bath temperature in electroless plating is generally about 0 to 50 ° C. as in the above electroplating.
本発明3は、上記ジベンゾアゾールジスルフィドスルホン酸化合物を含有させたスズ又はスズ合金メッキ浴を用いて、被メッキ物にバレルメッキを施す方法である。
当該バレルメッキでは、バレルに被メッキ物と導電性媒体を収容し、上記スズメッキ浴にバレルを浸漬して、被メッキ物に電気メッキを行うことを基本とするが、導電性媒体を使用せず、被メッキ物だけをバレルに収容してメッキを行う方法であっても良い。
本発明のメッキ浴を電気メッキのうちの、特にバレルメッキに適用すると、導電性媒体同士の凝集を防止できる利点があり、小物の被メッキ物同士の凝集を防止する点でも有効である。
また、当該バレルメッキにおいては、水平型又は傾斜型回転バレル式、揺動バレル式、或は振動バレル式などの任意のバレルメッキ装置が使用できることはいうまでもない。
バレルメッキでの浴温や陰極電流密度の条件は、上記電気メッキでの一般条件と同程度で良い。
本発明4は、抵抗、可変抵抗、コンデンサ、フィルタ、インダクタ、サーミスタ、水晶振動子、スイッチ、コネクタ、リード線、フープ材、プリント基板、半導体集積回路(TABのフィルムキャリア、BGA基板などを含む)、モジュール等の電子部品などを被メッキ物とするバレルメッキ方法であり、特に、被メッキ物としては、チップ抵抗器、チップコンデンサー、水晶振動子のキャップなどの小物部品が好適である。
The present invention 3 is a method of barrel-plating an object to be plated using a tin or tin alloy plating bath containing the dibenzoazole disulfide sulfonic acid compound.
In the barrel plating, the object to be plated and the conductive medium are accommodated in the barrel, and the barrel is immersed in the tin plating bath to perform electroplating on the object to be plated, but the conductive medium is not used. Alternatively, a method may be used in which only the object to be plated is accommodated in the barrel for plating.
When the plating bath of the present invention is applied particularly to barrel plating among electroplating, there is an advantage that aggregation of conductive media can be prevented, which is also effective in preventing aggregation of small objects to be plated.
In the barrel plating, it is needless to say that any barrel plating apparatus such as a horizontal or inclined rotary barrel type, a swing barrel type, or a vibrating barrel type can be used.
The conditions of the bath temperature and cathode current density in barrel plating may be the same as the general conditions in the electroplating.
The present invention 4 is a resistor, variable resistor, capacitor, filter, inductor, thermistor, crystal resonator, switch, connector, lead wire, hoop material, printed circuit board, semiconductor integrated circuit (including TAB film carrier, BGA substrate, etc.) This is a barrel plating method in which electronic parts such as modules are to be plated. In particular, small parts such as a chip resistor, a chip capacitor, and a quartz resonator cap are suitable as the plated object.
以下、本発明のジベンゾアゾールジスルフィドジスルホン酸化合物の合成例、当該化合物を含有する本発明のスズ及びスズ合金メッキ浴の実施例、実施例で得られた各メッキ浴を用いて様々な電流密度でラックメッキを施した場合の電着皮膜の均一性、平滑性の評価試験例、前記実施例で得られた各メッキ浴を用いたハンダ濡れ性の評価試験例、本発明のスズ浴を用いた無電解メッキによるスズ皮膜の外観評価試験例、本発明のスズ又はスズ合金メッキ浴を用いてバレルメッキを施した場合の凝集抑制評価試験例を順次述べる。
尚、本発明は下記の合成例、実施例、試験例に拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。
Hereinafter, synthesis examples of the dibenzoazole disulfide disulfonic acid compound of the present invention, examples of the tin and tin alloy plating baths of the present invention containing the compound, and various current densities using the plating baths obtained in the examples. Evaluation test example of uniformity and smoothness of electrodeposited film when rack plating is applied, evaluation test example of solder wettability using each plating bath obtained in the above examples, and tin bath of the present invention were used A tin film appearance evaluation test example by electroless plating and an aggregation suppression evaluation test example when barrel plating is performed using the tin or tin alloy plating bath of the present invention will be sequentially described.
The present invention is not limited to the following synthesis examples, examples, and test examples, and it goes without saying that arbitrary modifications can be made within the scope of the technical idea of the present invention.
先ず、本発明のジベンゾアゾールジスルフィドジスルホン酸化合物の代表例として、ジベンゾチアゾールジスルフィドジスルホン酸塩の合成例を述べる。
《ジベンゾチアゾールジスルフィドジスルホン酸塩の合成例》
温度計、冷却管、撹拌機を取り付けた500mlの4つ口フラスコに30%発煙硫酸94mlを仕込んだ。その後、氷水で冷却し、撹拌下20℃でジベンゾチアゾリルジスルフィド100gを加えた。
次いで、急速に115℃に加熱して24時間反応させた。反応後、80℃に冷却し、水200mlを加えた後、30℃で水酸化ナトリウム145gを水300mlに溶解した水溶液を滴下した。さらに、48%水酸化ナトリウム水を加えてpH9.5にした。そして、一夜放置後、吸引濾過して析出した硫酸ナトリウムを濾別し、ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウムの水溶液1550mlを得た。
First, as a representative example of the dibenzoazole disulfide disulfonic acid compound of the present invention, a synthesis example of dibenzothiazole disulfide disulfonate will be described.
<< Synthesis Example of Dibenzothiazole Disulfide Disulfonate >>
A 500 ml four-necked flask equipped with a thermometer, condenser and stirrer was charged with 94 ml of 30% fuming sulfuric acid. Thereafter, the mixture was cooled with ice water, and 100 g of dibenzothiazolyl disulfide was added at 20 ° C. with stirring.
Subsequently, it was rapidly heated to 115 ° C. and reacted for 24 hours. After the reaction, the mixture was cooled to 80 ° C., 200 ml of water was added, and an aqueous solution in which 145 g of sodium hydroxide was dissolved in 300 ml of water was added dropwise at 30 ° C. Further, 48% aqueous sodium hydroxide was added to adjust the pH to 9.5. After standing overnight, the sodium sulfate precipitated by suction filtration was separated by filtration to obtain 1550 ml of an aqueous solution of disodium dibenzothiazolyl disulfide disulfonate.
《スズ及びスズ合金メッキ浴の実施例》
実施例1、10、12はスズメッキ浴の例、実施例2、11、13はスズ−銀合金メッキ浴の例、実施例3はスズ−銅合金メッキ浴の例、実施例4はスズ−ビスマス合金メッキ浴の例、実施例5はスズ−インジウム合金メッキ浴の例、実施例6はスズ−亜鉛合金メッキ浴の例、実施例7はスズ−アンチモン合金メッキ浴の例、実施例8はスズ−鉛合金メッキ浴の例、実施例9はスズ−ニッケル合金メッキ浴の例である。
実施例1〜9は本発明のジベンゾアゾールジスルフィドスルホン酸化合物がベンゾチアゾールジスルフィドスルホン酸化合物である例、同様に実施例10〜11はベンゾオキサゾールジスルフィドスルホン酸化合物の例、実施例12〜13はベンズイミダゾールジスルフィドスルホン酸化合物の例である。
<< Examples of tin and tin alloy plating bath >>
Examples 1, 10, and 12 are examples of tin plating baths, Examples 2, 11, and 13 are examples of tin-silver alloy plating baths, Example 3 is an example of tin-copper alloy plating baths, and Example 4 is tin-bismuth. Example of alloy plating bath, Example 5 is an example of tin-indium alloy plating bath, Example 6 is an example of tin-zinc alloy plating bath, Example 7 is an example of tin-antimony alloy plating bath, Example 8 is tin An example of a lead alloy plating bath, Example 9 is an example of a tin-nickel alloy plating bath.
Examples 1 to 9 are examples in which the dibenzoazole disulfide sulfonic acid compound of the present invention is a benzothiazole disulfide sulfonic acid compound, examples 10 to 11 are examples of benzoxazole disulfide sulfonic acid compounds, and examples 12 to 13 are benz It is an example of an imidazole disulfide sulfonic acid compound.
(1)実施例1
下記の組成でスズメッキ浴を建浴した。
イセチオン酸第一スズ(Sn2+として) 20g/L
硫酸(比重1.84) 100g/L
ドデシルアミンポリエトキシレート(EO20) 10g/L
カテコール 0.5g/L
ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム 1g/L
イオン交換水 残部
[メッキ温度]
浴温:30℃
(1) Example 1
A tin plating bath was constructed with the following composition.
Stannous isethionate (as Sn 2+ ) 20g / L
Sulfuric acid (specific gravity 1.84) 100g / L
Dodecylamine polyethoxylate (EO20) 10g / L
Catechol 0.5g / L
Dibenzothiazolyl disulfide disulphonate disodium salt 1g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 30 ° C
(2)実施例2
下記の組成でスズ−銀合金メッキ浴を建浴した。
エタンスルホン酸第一スズ(Sn2+として) 30g/L
エタンスルホン酸銀(Ag+として) 0.8g/L
エタンスルホン酸(遊離酸として) 100g/L
トリメチルチオ尿素 16g/L
ジスチレン化フェノールポリエトキシレート(EO20) 10g/L
ハイドロキノン 1g/L
ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム 0.4g/L
ジベンゾチアゾリルジスルフィドモノスルホン酸カリウム 0.8g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(2) Example 2
A tin-silver alloy plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn 2+ ) 30g / L
Ethanesulfonic acid silver (as Ag + ) 0.8g / L
Ethanesulfonic acid (as free acid) 100g / L
Trimethylthiourea 16g / L
Distyrenated phenol polyethoxylate (EO20) 10g / L
Hydroquinone 1g / L
Dibenzothiazolyl disulfide trisulfonate trisodium salt 0.4 g / L
Potassium dibenzothiazolyl disulfide monosulfonate 0.8 g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(3)実施例3
下記の組成でスズ−銅合金メッキ浴を建浴した。
メタンスルホン酸第一スズ(Sn2+として) 30g/L
メタンスルホン酸銀(Cu2+として) 3g/L
メタンスルホン酸(遊離酸として) 130g/L
1−ナフトールポリエトキシレート(EO10) 10g/L
ベンザルアセトン 0.2g/L
ジ(4−メチルベンゾチアゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.8g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(3) Example 3
A tin-copper alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 30g / L
Silver methanesulfonate (as Cu 2+ ) 3g / L
Methanesulfonic acid (as free acid) 130g / L
1-naphthol polyethoxylate (EO10) 10g / L
Benzalacetone 0.2g / L
Di (4-methylbenzothiazolyl) disulfide
-Disodium disulfonate 0.8g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(4)実施例4
下記の組成でスズ−ビスマス合金メッキ浴を建浴した。
メタンスルホン酸第一スズ(Sn2+として) 55g/L
メタンスルホン酸ビスマス(Bi3+として) 7g/L
メタンスルホン酸(遊離酸として) 130g/L
トリスチレン化フェノールポリエトキシレート(EO23) 10g/L
ジ(6−クロロベンゾチアゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.8g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(4) Example 4
A tin-bismuth alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 55g / L
Bismuth methanesulfonate (as Bi 3+ ) 7g / L
Methanesulfonic acid (as free acid) 130g / L
Tristyrenated phenol polyethoxylate (EO23) 10g / L
Di (6-chlorobenzothiazolyl) disulfide
-Disodium disulfonate 0.8g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(5)実施例5
下記の組成でスズ−インジウム合金メッキ浴を建浴した。
メタンスルホン酸第一スズ(Sn2+として) 10g/L
スルファミン酸インジウム(In3+として) 10g/L
スルファミン酸 130g/L
アミノカプロン酸 60g/L
グリシン 50g/L
ジメチルアルキルベタイン 5g/L
ハイドロキノン 0.2g/L
ジ(6−メトキシベンゾチアゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 1.2g/L
イオン交換水 残部
pH(アンモニアで調整) 2.0
[メッキ温度]
浴温:25℃
(5) Example 5
A tin-indium alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 10g / L
Indium sulfamate (as In 3+ ) 10g / L
Sulfamic acid 130g / L
Aminocaproic acid 60g / L
Glycine 50g / L
Dimethyl alkyl betaine 5g / L
Hydroquinone 0.2g / L
Di (6-methoxybenzothiazolyl) disulfide
-Disodium disulphonate 1.2g / L
Ion-exchanged water balance pH (adjusted with ammonia) 2.0
[Plating temperature]
Bath temperature: 25 ° C
(6)実施例6
下記の組成でスズ−亜鉛合金メッキ浴を建浴した。
スルホコハク酸第一スズ(Sn2+として) 56.4g/L
メタンスルホン酸亜鉛(Zn2+として) 3.6g/L
スルホコハク酸 100g/L
アスコルビン酸 2g/L
ビスフェノールFポリエトキシレート(EO12) 3g/L
ラウリルアミンポリエトキシレート(EO15) 1g/L
ジ(6−ニトロベンゾチアゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.5g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(6) Example 6
A tin-zinc alloy plating bath was constructed with the following composition.
Stannous sulfosuccinate (as Sn 2+ ) 56.4 g / L
Zinc methanesulfonate (as Zn 2+ ) 3.6g / L
Sulfosuccinic acid 100g / L
Ascorbic acid 2g / L
Bisphenol F polyethoxylate (EO12) 3g / L
Laurylamine polyethoxylate (EO15) 1g / L
Di (6-nitrobenzothiazolyl) disulfide
-Disodium disulphonate 0.5g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(7)実施例7
下記の組成でスズ−アンチモン合金メッキ浴を建浴した。
硫酸第一スズ(Sn2+として) 25g/L
塩化アンチモン(Sb3+として) 0.87g/L
硫酸 100g/L
フッ化アンチモン 5g/L
ゼラチン 0.5g/L
フェノール 5g/L
ジ(6−メチルベンゾチアゾリル)ジスルフィドトリスルホン酸 0.5g/L
イオン交換水 残部
[メッキ温度]
浴温:45℃
(7) Example 7
A tin-antimony alloy plating bath was constructed with the following composition.
Stannous sulfate (as Sn 2+ ) 25g / L
Antimony chloride (as Sb 3+ ) 0.87 g / L
Sulfuric acid 100g / L
Antimony fluoride 5g / L
Gelatin 0.5g / L
Phenol 5g / L
Di (6-methylbenzothiazolyl) disulfide trisulfonic acid 0.5 g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 45 ° C
(8)実施例8
下記の組成でスズ−鉛合金メッキ浴を建浴した。
メタンスルホン酸第一スズ(Sn2+として) 50g/L
メタンスルホン酸鉛(Pb2+として) 4.2g/L
メタンスルホン酸(遊離酸として) 110g/L
1−ナフトールポリエトキシレート(EO10) 7g/L
ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム 0.5g/L
ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム 0.3g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(8) Example 8
A tin-lead alloy plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 50g / L
Lead methanesulfonate (as Pb 2+ ) 4.2g / L
Methanesulfonic acid (as free acid) 110g / L
1-naphthol polyethoxylate (EO10) 7g / L
Dibenzothiazolyl disulfide disulphonate disodium salt 0.5 g / L
Dibenzothiazolyl disulfide trisulfonic acid trisodium salt 0.3 g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(9)実施例9
下記の組成でスズ−ニッケル合金メッキ浴を建浴した。
硫酸第一スズ(Sn2+として) 30g/L
硫酸ニッケル(Ni2+として) 0.75g/L
グルコン酸ナトリウム 220g/L
チオビス(ドデカエチレングリコール) 20g/L
硫酸ナトリウム 50g/L
ジ(6−クロロベンゾチアゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.3g/L
イオン交換水 残部
pH(水酸化ナトリウムで調整) 4.0
[メッキ温度]
浴温:25℃
(9) Example 9
A tin-nickel alloy plating bath was constructed with the following composition.
Stannous sulfate (as Sn 2+ ) 30g / L
Nickel sulfate (as Ni 2+ ) 0.75g / L
Sodium gluconate 220g / L
Thiobis (dodecaethylene glycol) 20g / L
Sodium sulfate 50g / L
Di (6-chlorobenzothiazolyl) disulfide
-Disodium disulphonate 0.3g / L
Ion-exchanged water balance pH (adjusted with sodium hydroxide) 4.0
[Plating temperature]
Bath temperature: 25 ° C
(10)実施例10
下記の組成でスズメッキ浴を建浴した。
イセチオン酸第一スズ(Sn2+として) 20g/L
硫酸(比重1.84) 100g/L
ドデシルアミンポリエトキシレート(EO20) 10g/L
カテコール 0.5g/L
ジベンゾオキサゾリルジスルフィドジスルホン酸二ナトリウム 1g/L
イオン交換水 残部
[メッキ温度]
浴温:30℃
(10) Example 10
A tin plating bath was constructed with the following composition.
Stannous isethionate (as Sn 2+ ) 20g / L
Sulfuric acid (specific gravity 1.84) 100g / L
Dodecylamine polyethoxylate (EO20) 10g / L
Catechol 0.5g / L
Dibenzoxazolyl disulfide disulphonate disodium salt 1g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 30 ° C
(11)実施例11
下記の組成でスズ−銀合金メッキ浴を建浴した。
エタンスルホン酸第一スズ(Sn2+として) 30g/L
エタンスルホン酸銀(Ag+として) 0.8g/L
エタンスルホン酸(遊離酸として) 100g/L
トリメチルチオ尿素 16g/L
ジスチレン化フェノールポリエトキシレート(EO20) 10g/L
ハイドロキノン 1g/L
ジ(6−メチルベンゾオキサゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.8g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(11) Example 11
A tin-silver alloy plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn 2+ ) 30g / L
Ethanesulfonic acid silver (as Ag + ) 0.8g / L
Ethanesulfonic acid (as free acid) 100g / L
Trimethylthiourea 16g / L
Distyrenated phenol polyethoxylate (EO20) 10g / L
Hydroquinone 1g / L
Di (6-methylbenzoxazolyl) disulfide
-Disodium disulfonate 0.8g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(12)実施例12
下記の組成でスズメッキ浴を建浴した。
イセチオン酸第一スズ(Sn2+として) 20g/L
硫酸(比重1.84) 100g/L
ドデシルアミンポリエトキシレート(EO20) 10g/L
カテコール 0.5g/L
ジベンズイミダゾリルジスルフィドジスルホン酸二ナトリウム 1g/L
イオン交換水 残部
[メッキ温度]
浴温:30℃
(12) Example 12
A tin plating bath was constructed with the following composition.
Stannous isethionate (as Sn 2+ ) 20g / L
Sulfuric acid (specific gravity 1.84) 100g / L
Dodecylamine polyethoxylate (EO20) 10g / L
Catechol 0.5g / L
Dibenzimidazolyl disulfide disulphonate disodium salt 1g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 30 ° C
(13)実施例13
下記の組成でスズ−銀合金メッキ浴を建浴した。
エタンスルホン酸第一スズ(Sn2+として) 30g/L
エタンスルホン酸銀(Ag+として) 0.8g/L
エタンスルホン酸(遊離酸として) 100g/L
トリメチルチオ尿素 16g/L
ジスチレン化フェノールポリエトキシレート(EO20) 10g/L
ハイドロキノン 1g/L
ジ(6−メトキシベンズイミダゾリル)ジスルフィド
−ジスルホン酸二ナトリウム 0.8g/L
イオン交換水 残部
[メッキ温度]
浴温:25℃
(13) Example 13
A tin-silver alloy plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn 2+ ) 30g / L
Ethanesulfonic acid silver (as Ag + ) 0.8g / L
Ethanesulfonic acid (as free acid) 100g / L
Trimethylthiourea 16g / L
Distyrenated phenol polyethoxylate (EO20) 10g / L
Hydroquinone 1g / L
Di (6-methoxybenzimidazolyl) disulfide
-Disodium disulfonate 0.8g / L
Ion exchange water balance
[Plating temperature]
Bath temperature: 25 ° C
(14)比較例1
前記実施例1のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例1と同様に建浴して、比較例1のスズメッキ浴とした。尚、浴温条件も実施例1と同じである(後述の比較例2〜13でも、浴温条件は相当する実施例と同じである)。
(14) Comparative Example 1
Based on the plating bath of Example 1, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 1 to obtain a tin plating bath of Comparative Example 1. In addition, bath temperature conditions are also the same as Example 1 (The bath temperature conditions are the same as the corresponding Example also in the comparative examples 2-13 mentioned later).
(15)比較例2
前記実施例2のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例2と同様に建浴して、比較例2のスズ−銀合金メッキ浴とした。
(15) Comparative example 2
Based on the plating bath of Example 2, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 2, and the tin-silver alloy plating bath of Comparative Example 2 was used. It was.
(16)比較例3
前記実施例3のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例3と同様に建浴して、比較例3のスズ−銅合金メッキ浴とした。
(16) Comparative Example 3
Based on the plating bath of Example 3, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 3, and the tin-copper alloy plating bath of Comparative Example 3 was used. It was.
(17)比較例4
前記実施例4のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例4と同様に建浴して、比較例4のスズ−ビスマス合金メッキ浴とした。
(17) Comparative example 4
Based on the plating bath of Example 4, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 4, and the tin-bismuth alloy plating bath of Comparative Example 4 was used. It was.
(18)比較例5
前記実施例5のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例5と同様に建浴して、比較例5のスズ−インジウム合金メッキ浴とした。
(18) Comparative Example 5
Based on the plating bath of Example 5, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 5, and the tin-indium alloy plating bath of Comparative Example 5 was used. It was.
(19)比較例6
前記実施例6のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例6と同様に建浴して、比較例6のスズ−亜鉛合金メッキ浴とした。
(19) Comparative Example 6
Based on the plating bath of Example 6, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 6, and the tin-zinc alloy plating bath of Comparative Example 6 was used. It was.
(20)比較例7
前記実施例7のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例7と同様に建浴して、比較例7のスズ−アンチモン合金メッキ浴とした。
(20) Comparative Example 7
Based on the plating bath of Example 7, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 7, and the tin-antimony alloy plating bath of Comparative Example 7 was used. It was.
(21)比較例8
前記実施例8のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例8と同様に建浴して、比較例8のスズ−鉛合金メッキ浴とした。
(21) Comparative Example 8
Based on the plating bath of Example 8, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 8, and the tin-lead alloy plating bath of Comparative Example 8 was used. It was.
(22)比較例9
前記実施例9のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例9と同様に建浴して、比較例9のスズ−ニッケル合金メッキ浴とした。
(22) Comparative Example 9
Based on the plating bath of Example 9, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 9, and the tin-nickel alloy plating bath of Comparative Example 9 was used. It was.
(23)比較例10
前記実施例10のメッキ浴を基本として、本発明のベンゾオキサゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例10と同様に建浴して、比較例10のスズメッキ浴とした。
(23) Comparative Example 10
Based on the plating bath of Example 10, the benzoxazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 10 to obtain a tin plating bath of Comparative Example 10.
(24)比較例11
前記実施例11のメッキ浴を基本として、本発明のベンゾオキサゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例11と同様に建浴して、比較例11のスズ−銀合金メッキ浴とした。
(24) Comparative Example 11
Based on the plating bath of Example 11, the benzoxazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 11, and the tin-silver alloy plating bath of Comparative Example 11 was used. It was.
(25)比較例12
前記実施例12のメッキ浴を基本として、本発明のベンズイミダゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例12と同様に建浴して、比較例12のスズメッキ浴とした。
(25) Comparative Example 12
Based on the plating bath of Example 12, the benzimidazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 12 to obtain a tin plating bath of Comparative Example 12.
(26)比較例13
前記実施例13のメッキ浴を基本として、本発明のベンズイミダゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例13と同様に建浴して、比較例13のスズ−銀合金メッキ浴とした。
(26) Comparative Example 13
Based on the plating bath of Example 13, the benzimidazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 13, and the tin-silver alloy plating bath of Comparative Example 13 was used. It was.
そこで、実施例1〜13及び比較例1〜13で得られた各スズ又はスズ合金メッキ浴を用いて、下記の電流密度範囲並びに条件でラックメッキを行い、各電流密度での電着皮膜の均一性及び平滑性の優劣を評価した。
《メッキ皮膜の均一性及び平滑性の評価試験例1》
即ち、上記各メッキ浴をスターラー撹拌しながら、白金被覆チタンを陽極とし、銅板を陰極として、実施例又は比較例で示した所定の浴温にて、電流密度、メッキ時間を種々に変化させながら、ラック方式により電気メッキを施して、各電流密度におけるメッキ皮膜の状態を目視観察した。評価基準は次の通りである。
◎:非常に平滑で均一な外観を示した。
○:皮膜外観に異常がなく、実用レベルの外観を示した。
△:皮膜粒子が粗く、均一性及び平滑性が実用レベルからやや劣る外観を示した。
×:平滑性に劣り、ムラがあり、均一性に欠ける外観を示した。
Therefore, rack plating is performed using the tin or tin alloy plating baths obtained in Examples 1 to 13 and Comparative Examples 1 to 13 under the following current density ranges and conditions, and the electrodeposition film at each current density is applied. The superiority and inferiority of uniformity and smoothness were evaluated.
<< Evaluation Test Example 1 for Uniformity and Smoothness of Plating Film >>
That is, while stirring each of the plating baths with a stirrer, using platinum-coated titanium as an anode and a copper plate as a cathode, while varying the current density and plating time at the predetermined bath temperatures shown in the examples or comparative examples, Then, electroplating was performed by a rack method, and the state of the plating film at each current density was visually observed. The evaluation criteria are as follows.
A: A very smooth and uniform appearance was exhibited.
○: The film appearance was normal and showed a practical level appearance.
(Triangle | delta): The film particle was coarse and the external appearance which the uniformity and smoothness were a little inferior from a practical use level was shown.
X: Inferior smoothness, unevenness, and poor appearance.
下表はその試験結果である。
No. ハルセルテストの電流密度範囲 実施例 比較例
1 0.5〜5A/dm2 ◎ △
2 1〜5A/dm2 ◎ △
3 1〜5A/dm2 ◎ ×
4 1〜5A/dm2 ◎ ×
5 5〜15A/dm2 ◎ ×
6 2〜10A/dm2 ◎ ×
7 1〜5A/dm2 ○ ×
8 1〜20A/dm2 ◎ △
9 0.1〜3A/dm2 ○ ×
10 0.5〜5A/dm2 ◎ △
11 1〜5A/dm2 ◎ △
12 0.5〜5A/dm2 ◎ △
13 1〜5A/dm2 ◎ △
The table below shows the test results.
No. Current density range of Hull cell test Example Comparative example 1 0.5 to 5 A / dm 2 ◎ △
2 1-5 A / dm 2 ◎ △
3 1-5A / dm 2 ◎ ×
4 1-5 A / dm 2 ◎ ×
5 5-15A / dm 2 ◎ ×
6 2-10 A / dm 2 ◎ ×
7 1-5A / dm 2 ○ ×
8 1-20 A / dm 2 ◎ △
9 0.1-3 A / dm 2 ○ ×
10 0.5-5 A / dm 2 ◎ △
11 1-5 A / dm 2 ◎ △
12 0.5-5 A / dm 2 ◎ △
13 1-5 A / dm 2 ◎ △
次いで、実施例1〜13及び比較例1〜13で得られた各スズ又はスズ合金メッキ浴を用いて、所定の銅板にメッキ皮膜を形成し、ハンダ濡れ性の優劣を評価した。
《メッキ皮膜のハンダ濡れ性の評価試験例2》
25mm×25mmの圧延銅板の試験片に実施例及び比較例の各メッキ浴を用いて、各例に示した所定の浴温並びに下表に示す電流密度でスズ又はスズ合金メッキを施した後、フラックス(ロジン25%含有イソプロパノール溶液)中に5秒間浸漬し、次いで250℃に保持した溶融はんだ槽に5秒間浸漬し、イソプロパノールで洗浄した後、その表面のハンダ濡れ性の具合を目視観察した。ハンダ濡れ性の評価基準は次の通りである。
◎:95%以上濡れていた。
○:90%以上濡れていた。
×:濡れが90%未満であった。
Subsequently, using each tin or tin alloy plating bath obtained in Examples 1 to 13 and Comparative Examples 1 to 13, a plating film was formed on a predetermined copper plate, and the superiority or inferiority of solder wettability was evaluated.
<< Evaluation test example 2 of solder wettability of plating film >>
Using each plating bath of Examples and Comparative Examples on a test piece of a rolled copper plate of 25 mm × 25 mm, after performing tin or tin alloy plating at the predetermined bath temperature shown in each example and the current density shown in the table below, After immersing in a flux (25% rosin-containing isopropanol solution) for 5 seconds, then immersed in a molten solder bath maintained at 250 ° C. for 5 seconds and washed with isopropanol, the surface of the solder wettability was visually observed. The evaluation criteria of solder wettability are as follows.
A: Wet 95% or more.
○: Wet by 90% or more.
X: Wetting was less than 90%.
下表はその試験結果である。
No. 陰極電流密度 実施例 比較例
1 2A/dm2 ◎ ×
2 3A/dm2 ◎ ×
3 3A/dm2 ◎ ×
4 3A/dm2 ◎ ×
5 7.5A/dm2 ◎ ×
6 5A/dm2 ○ ×
7 3A/dm2 ○ ×
8 10A/dm2 ◎ ×
9 0.25A/dm2 ○ ×
10 0.5〜5A/dm2 ◎ ×
11 1〜5A/dm2 ○ ×
12 0.5〜5A/dm2 ◎ ×
13 1〜5A/dm2 ○ ×
The table below shows the test results.
No. Cathode current density Example Comparative example 1 2 A / dm 2
2 3A / dm 2 ◎ ×
3 3A / dm 2 ◎ ×
4 3A / dm 2 ◎ ×
5 7.5A / dm 2 ◎ ×
6 5A / dm 2 ○ ×
7 3A / dm 2 ○ ×
8 10A / dm 2 ◎ ×
9 0.25 A / dm 2 ○ ×
10 0.5-5 A / dm 2 ◎ ×
11 1-5 A / dm 2 ○ ×
12 0.5-5A / dm 2 ◎ ×
13 1-5 A / dm 2 ○ ×
次いで、下記の通り、実施例14〜15及び比較例14〜15の各無電解スズメッキ浴を建浴して、TABのフィルムキャリアのインナリード上にスズメッキ皮膜を形成し、皮膜外観の析出状態の優劣を評価した。
《スズメッキ皮膜の外観評価試験例3》
先ず、無電解スズメッキ浴を次の通りに建浴した。
[メッキ浴の実施例]
(1)実施例14
下記の組成で無電解スズメッキ浴を建浴した。
3−ヒドロキシプロパン
−1−スルホン酸第一スズ(Sn2+として) 0.25モル/L
エタンスルホン酸 0.50モル/L
クエン酸 0.50モル/L
チオ尿素 2.00モル/L
次亜リン酸 0.50モル/L
1−ナフトールポリエトキシレート(EO10) 5.0g/L
ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム 0.4g/L
Next, as shown below, each of the electroless tin plating baths of Examples 14 to 15 and Comparative Examples 14 to 15 was constructed, and a tin plating film was formed on the inner lead of the TAB film carrier. Superiority or inferiority was evaluated.
<< External evaluation test example 3 of tin plating film >>
First, an electroless tin plating bath was constructed as follows.
[Example of plating bath]
(1) Example 14
An electroless tin plating bath was constructed with the following composition.
3-hydroxypropane
-1 stannous sulfonate (as Sn 2+ ) 0.25 mol / L
Ethanesulfonic acid 0.50 mol / L
Citric acid 0.50 mol / L
Thiourea 2.00 mol / L
Hypophosphorous acid 0.50 mol / L
1-naphthol polyethoxylate (EO10) 5.0 g / L
Dibenzothiazolyl disulfide disulphonate disodium salt 0.4 g / L
(2)実施例15
下記の組成で無電解スズメッキ浴を建浴した。
3−ヒドロキシプロパン
−1−スルホン酸第一スズ(Sn2+として) 0.35モル/L
3−ヒドロキシプロパン−1−プロパンスルホン酸 1.00モル/L
リンゴ酸 1.00モル/L
チオ尿素 1.50モル/L
次亜リン酸 0.10モル/L
ヤシ油脂肪酸アミドプロピルジメチルアミンオキシド 6.0g/L
ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム 0.6g/L
(2) Example 15
An electroless tin plating bath was constructed with the following composition.
3-hydroxypropane
-1 stannous sulfonate (as Sn 2+ ) 0.35 mol / L
3-hydroxypropane-1-propanesulfonic acid 1.00 mol / L
Malic acid 1.00 mol / L
Thiourea 1.50 mol / L
Hypophosphorous acid 0.10 mol / L
Palm oil fatty acid amidopropyldimethylamine oxide 6.0 g / L
Dibenzothiazolyl disulfide trisulfonate trisodium salt 0.6 g / L
(3)比較例14
前記実施例14のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例14と同様に建浴して、比較例14の無電解スズメッキ浴とした。
(3) Comparative Example 14
Based on the plating bath of Example 14, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 14 to obtain an electroless tin plating bath of Comparative Example 14. .
(4)比較例15
前記実施例15のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例15と同様に建浴して、比較例15の無電解スズメッキ浴とした。
(4) Comparative Example 15
Based on the plating bath of Example 15, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 15 to obtain an electroless tin plating bath of Comparative Example 15. .
[評価試験例]
次いで、SLP(電解銅箔の一種)でパターン形成したTABのフィルムキャリアを被メッキ物として、このフィルムキャリアのインナリード上に、上記実施例14〜15及び比較例14〜15の各スズメッキ浴を用いて、浴温65℃、メッキ時間5分の条件で無電解メッキを施して、得られたスズ皮膜の析出状態を微視観察し、皮膜外観を評価した。
当該評価基準は次の通りである。
○:異常粒子が認められなかった。
×:異常粒子が発生した。
[Evaluation test example]
Next, a TAB film carrier patterned with SLP (a kind of electrolytic copper foil) is used as an object to be plated, and the tin plating baths of Examples 14 to 15 and Comparative Examples 14 to 15 are placed on the inner leads of the film carrier. Then, electroless plating was performed under conditions of a bath temperature of 65 ° C. and a plating time of 5 minutes, and the deposited state of the obtained tin film was observed microscopically to evaluate the film appearance.
The evaluation criteria are as follows.
○: Abnormal particles were not recognized.
X: Abnormal particles were generated.
下表はその試験結果である。
スズメッキ皮膜の外観
実施例14 ○
実施例15 ○
比較例14 ×
比較例15 ×
The table below shows the test results.
Appearance of tin plating film Example 14 ○
Example 15
Comparative Example 14 ×
Comparative Example 15 ×
次いで、下記の通り、本発明の化合物を含有した実施例16〜18及び比較例16〜18の各スズ又はスズ合金メッキ浴を建浴し、当該各電気メッキ浴を用いてバレルメッキを施して、導電性媒体(ダミーボール)の凝集抑制度合の優劣を評価した。
《バレルメッキにおける凝集抑制評価試験例4》
先ず、スズ又はスズ合金メッキ浴を次の通りに建浴した。
[メッキ浴の実施例]
(1)実施例16
下記の組成でスズ−銀合金メッキ浴を建浴した。
エタンスルホン酸第一スズ(Sn2+として) 30g/L
2−プロパノールスルホン酸銀(Ag+として) 0.1g/L
イセチオン酸(遊離酸として) 200g/L
チオ尿素 3g/L
2−ナフトールポリエトキシレート(EO10) 10g/L
プルロニックTR−720 1g/L
ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム 0.3g/L
ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム 0.2g/L
ジベンゾチアゾリルジスルフィドモノスルホン酸カリウム 0.1g/L
イオン交換水 残部
尚、上記プルロニックTR−720は旭電化工業(株)製の市販品である。
Next, as described below, each tin or tin alloy plating bath of Examples 16 to 18 and Comparative Examples 16 to 18 containing the compound of the present invention was constructed, and barrel plating was performed using each of the electroplating baths. The superiority or inferiority of the degree of inhibition of aggregation of the conductive medium (dummy ball) was evaluated.
<< Aggregation suppression evaluation test example 4 in barrel plating >>
First, a tin or tin alloy plating bath was constructed as follows.
[Example of plating bath]
(1) Example 16
A tin-silver alloy plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn 2+ ) 30g / L
Silver 2-propanol sulfonate (as Ag + ) 0.1 g / L
Isethonic acid (as free acid) 200g / L
Thiourea 3g / L
2-Naphthol polyethoxylate (EO10) 10g / L
Pluronic TR-720 1g / L
Dibenzothiazolyl disulfide disulphonate disodium salt 0.3g / L
Dibenzothiazolyl disulfide trisulfonate trisodium 0.2 g / L
Potassium dibenzothiazolyl disulfide monosulfonate 0.1 g / L
Ion-exchanged water balance The above Pluronic TR-720 is a commercial product manufactured by Asahi Denka Kogyo Co., Ltd.
(2)実施例17
下記の組成でスズメッキ浴を建浴した。
エタンスルホン酸第一スズ(Sn2+として) 15g/L
イセチオン酸(遊離酸として) 35g/L
グルコン酸カリウム 120g/L
コハク酸 10g/L
オレイルアミンポリエトキシレート(EO15) 2g/L
ラウリルイソキノリニウムメタンスルホネート 0.5g/L
ヒドロキノン 0.3g/L
ジベンゾチアゾリルジスルフィドトリスルホン酸三ナトリウム 0.7g/L
イオン交換水 残部
(2) Example 17
A tin plating bath was constructed with the following composition.
Stannous ethanesulfonate (as Sn 2+ ) 15g / L
Isethonic acid (as free acid) 35g / L
Potassium gluconate 120g / L
Succinic acid 10g / L
Oleylamine polyethoxylate (EO15) 2g / L
Laurylisoquinolinium methanesulfonate 0.5g / L
Hydroquinone 0.3g / L
Dibenzothiazolyl disulfide trisulfonate trisodium 0.7 g / L
Ion exchange water balance
(3)実施例18
下記の組成でスズメッキ浴を建浴した。
メタンスルホン酸第一スズ(Sn2+として) 10g/L
メタンスルホン酸(遊離酸として) 30g/L
クミルフェノールポリエトキシレート(EO12) 3g/L
ポリオキシエチレンラウリルアンモニウム(EO15) 3g/L
グルコン酸ナトリウム 100g/L
クエン酸ナトリウム 50g/L
1−ヒドロキシ−4−ナフタレンスルホン酸ナトリウム 0.2g/L
ジベンゾチアゾリルジスルフィドジスルホン酸二ナトリウム 0.4g/L
ジベンゾチアゾリルジスルフィドモノスルホン酸カリウム 0.1g/L
イオン交換水 残部
pH(水酸化ナトリウムで調整) 5.0
(3) Example 18
A tin plating bath was constructed with the following composition.
Stannous methanesulfonate (as Sn 2+ ) 10g / L
Methanesulfonic acid (as free acid) 30g / L
Cumylphenol polyethoxylate (EO12) 3g / L
Polyoxyethylene lauryl ammonium (EO15) 3g / L
Sodium gluconate 100g / L
Sodium citrate 50g / L
Sodium 1-hydroxy-4-naphthalenesulfonate 0.2 g / L
Dibenzothiazolyl disulfide disulphonate disodium salt 0.4 g / L
Potassium dibenzothiazolyl disulfide monosulfonate 0.1 g / L
Ion-exchanged water balance pH (adjusted with sodium hydroxide) 5.0
(4)比較例16
前記実施例16のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例16と同様に建浴して、比較例16のスズ−銀合金メッキ浴とした。
(4) Comparative Example 16
Based on the plating bath of Example 16, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed similarly to Example 16, and the tin-silver alloy plating bath of Comparative Example 16 was used. It was.
(5)比較例17
前記実施例17のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例17と同様に建浴して、比較例17のスズメッキ浴とした。
(5) Comparative Example 17
Based on the plating bath of Example 17, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 17 to obtain a tin plating bath of Comparative Example 17.
(6)比較例18
前記実施例18のメッキ浴を基本として、本発明のベンゾチアゾールジスルフィドジスルホン酸化合物を添加せず、その他の組成は実施例18と同様に建浴して、比較例18のスズメッキ浴とした。
[評価試験例]
浸漬型水平回転バレルメッキ装置(コンドウ社製; 商品名ミニバレル)を用いて、サイズ500μmのスチールボールを被メッキ物とし、直径約10mmの鋼球を凝集粉砕用ダミーボール及び導電性媒体として、投入容量100mlの被メッキ物と投入量10個の導電性媒体を共にバレルに収容し、当該バレルを実施例16〜18及び比較例16〜18の各スズ又はスズ合金メッキ浴に浸漬して、下記の条件でバレルメッキ処理をした。
浴温:25℃
陰極電流密度:0.4A/dm2
メッキ時間:60分
次いで、メッキ終了後、被メッキ物から凝集粉砕用ダミーボールを取り除き、被メッキ物をメッシュ(0.85mm)の篩(ふるい)を用いて篩い分け操作して、下式で表される被メッキ物の残留率(%)により、各スズ又はスズ合金メッキ浴の凝集防止効果の優劣を評価した。
被メッキ物の残留率(%)=
篩に残った被メッキ物の数(重量)/バレルに収容した被メッキ物の総数(総重量)
(6) Comparative Example 18
Based on the plating bath of Example 18, the benzothiazole disulfide disulfonic acid compound of the present invention was not added, and the other compositions were constructed in the same manner as in Example 18 to obtain a tin plating bath of Comparative Example 18.
[Evaluation test example]
Using immersion type horizontal rotating barrel plating equipment (manufactured by Kondo Co., Ltd .; trade name: mini-barrel), steel balls with a size of 500 μm are used as objects to be plated, and steel balls with a diameter of about 10 mm are used as cohesive grinding dummy balls and conductive media. Both the object to be plated having a capacity of 100 ml and the conductive medium of 10 inputs are accommodated in a barrel, and the barrel is immersed in each of the tin or tin alloy plating baths of Examples 16 to 18 and Comparative Examples 16 to 18, and Barrel plating treatment was performed under the conditions described above.
Bath temperature: 25 ° C
Cathode current density: 0.4 A / dm 2
Plating time: 60 minutes Then, after finishing plating, remove the cohesive grinding dummy balls from the object to be plated, and screen the object to be plated using a mesh (0.85 mm) sieve. The superiority or inferiority of the anti-aggregation effect of each tin or tin alloy plating bath was evaluated based on the residual ratio (%) of the object to be plated.
Residual rate of plating object (%) =
Number of objects to be plated remaining on sieve (weight) / Total number of objects to be plated accommodated in barrel (total weight)
下表はその試験結果である。
被メッキ物の残留率(%)
実施例16 0.1
実施例17 0.3
実施例18 0.4
比較例16 18.5
比較例17 22.3
比較例18 20.7
The table below shows the test results.
Residual ratio of plating object (%)
Example 16 0.1
Example 17 0.3
Example 18 0.4
Comparative Example 16 18.5
Comparative Example 17 22.3
Comparative Example 18 20.7
《各種試験の総合評価》
本発明の化合物を添加しないブランク例である比較例1〜13のメッキ浴を用いて、陰極電流密度範囲を変化させてラックメッキを行った試験例1では、得られた電着皮膜の均一性や平滑性は劣り、或は実用レベルを下廻るのに対して、本発明の化合物を添加した実施例1〜13では、広い電流密度範囲において多くが平滑性や均一性に優れ、それ以外の実施例でも実用レベルを充分に具備していた。
また、ハンダ濡れ性の試験例2においても、比較例1〜13ではいずれの評価も×であったが、実施例1〜13では半分以上の例で◎の評価であり、それ以外の実施例も○の評価であった。
このように、上記実施例1〜13で得られたスズ又はスズ合金の電着皮膜では、平滑性や均一性、ハンダ濡れ性に優れることから、本発明の化合物を添加したメッキ浴を用いて無電解メッキを行ったところ、得られたスズ皮膜の外観は試験例3に見るように、異常粒子は認められず、皮膜外観についても優れていた。尚、本発明の化合物を添加しないブランク例である比較例14〜15では、得られたスズ皮膜に異常粒子が発生した。
従って、メッキ皮膜の広い電流密度範囲における平滑性や均一性、或は、皮膜外観やハンダ濡れ性については、本発明の化合物を添加したスズ又はスズ合金メッキ浴は、添加しないメッキ浴に対して顕著な優位性があり、しかも、電気メッキ又は無電解メッキを問わず、この優位性は確認された。
<< Comprehensive evaluation of various tests >>
In Test Example 1 in which rack plating was performed by changing the cathode current density range using the plating baths of Comparative Examples 1 to 13, which are blank examples to which the compound of the present invention was not added, the uniformity of the obtained electrodeposition film In Examples 1 to 13 to which the compound of the present invention was added, many of them were excellent in smoothness and uniformity over a wide current density range, whereas the smoothness was inferior or lower than the practical level. Even in the examples, a practical level was sufficiently provided.
Also, in the solder wettability test example 2, all evaluations were x in comparative examples 1 to 13, but in examples 1 to 13 the evaluation was ◎ in more than half of the examples, and other examples Was also rated as good.
Thus, in the electrodeposition film of tin or tin alloy obtained in the above Examples 1 to 13, since it is excellent in smoothness, uniformity and solder wettability, a plating bath to which the compound of the present invention is added is used. When electroless plating was performed, the appearance of the obtained tin film was excellent in the film appearance as no abnormal particles were observed as seen in Test Example 3. In Comparative Examples 14 to 15, which are blank examples to which the compound of the present invention was not added, abnormal particles were generated in the obtained tin coating.
Therefore, regarding the smoothness and uniformity of the plating film over a wide current density range, or the film appearance and solder wettability, the tin or tin alloy plating bath to which the compound of the present invention is added is different from the plating bath to which no plating is added. There was a significant advantage, and this advantage was confirmed regardless of electroplating or electroless plating.
本発明の化合物を添加したスズ又はスズ合金メッキ浴をバレルメッキに適用すると、試験例4に見るように、添加しないブランク例(比較例16〜18)では、いずれも被メッキ物の残留率が高くて、篩い分け作業が容易でないのに対して、添加した実施例16〜18では、いずれも残留率がきわめて低く、バレルメッキを円滑に実施できることが確認された。 When the tin or tin alloy plating bath to which the compound of the present invention is added is applied to barrel plating, as shown in Test Example 4, in all of the blank examples (Comparative Examples 16 to 18) that are not added, the residual rate of the object to be plated is Although it was high and the sieving operation was not easy, it was confirmed that all of the added Examples 16 to 18 had a very low residual rate and could smoothly perform barrel plating.
Claims (4)
(B)酸又はその塩と、
(C)下記の一般式(1)で表されるジベンゾアゾールジスルフィドスルホン酸化合物とを
含有することを特徴とするスズ又はスズ合金メッキ浴である。 (A) a soluble salt comprising any one of a stannous salt and a mixture of a salt of a metal selected from the group consisting of stannous salt and silver, copper, bismuth, indium, zinc, antimony, nickel, lead; ,
(B) an acid or a salt thereof;
(C) a dibenzoazole disulfide sulfonic acid compound represented by the following general formula (1):
A tin or tin alloy plating bath characterized by containing.
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