JP4430879B2 - Method for producing lead-containing copper alloy water supply device, casting deleading product of water supply device, and water supply device - Google Patents
Method for producing lead-containing copper alloy water supply device, casting deleading product of water supply device, and water supply device Download PDFInfo
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- JP4430879B2 JP4430879B2 JP2003069698A JP2003069698A JP4430879B2 JP 4430879 B2 JP4430879 B2 JP 4430879B2 JP 2003069698 A JP2003069698 A JP 2003069698A JP 2003069698 A JP2003069698 A JP 2003069698A JP 4430879 B2 JP4430879 B2 JP 4430879B2
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- Japan
- Prior art keywords
- lead
- peripheral surface
- water supply
- supply device
- product
- 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.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 178
- 238000004519 manufacturing process Methods 0.000 title claims description 49
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 36
- 238000005266 casting Methods 0.000 title claims description 25
- 230000002093 peripheral effect Effects 0.000 claims description 141
- 238000007747 plating Methods 0.000 claims description 69
- 238000005520 cutting process Methods 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 39
- 230000008569 process Effects 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 26
- 239000012670 alkaline solution Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 239000002585 base Substances 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- 238000010828 elution Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000004576 sand Substances 0.000 description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 14
- 238000005238 degreasing Methods 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 238000005422 blasting Methods 0.000 description 6
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 6
- 229910000165 zinc phosphate Inorganic materials 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007800 oxidant agent Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- -1 alkylbenzene sodium sulfate Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910000906 Bronze Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000010974 bronze Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- ZZGRDDIINJOLCK-UHFFFAOYSA-N 5-chloro-2-ethyl-4-hydroxy-1h-pyrimidin-6-one Chemical compound CCC1=NC(O)=C(Cl)C(=O)N1 ZZGRDDIINJOLCK-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910021569 Manganese fluoride Inorganic materials 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- ZYUIDCRSQBJHLB-UHFFFAOYSA-N [C-]#N.F Chemical compound [C-]#N.F ZYUIDCRSQBJHLB-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- JCMGUODNZMETBM-UHFFFAOYSA-N arsenic trifluoride Chemical compound F[As](F)F JCMGUODNZMETBM-UHFFFAOYSA-N 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- MZJUGRUTVANEDW-UHFFFAOYSA-N bromine fluoride Chemical compound BrF MZJUGRUTVANEDW-UHFFFAOYSA-N 0.000 description 1
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical group [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CTNMMTCXUUFYAP-UHFFFAOYSA-L difluoromanganese Chemical compound F[Mn]F CTNMMTCXUUFYAP-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- GGJOARIBACGTDV-UHFFFAOYSA-N germanium difluoride Chemical compound F[Ge]F GGJOARIBACGTDV-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- MLKFZZUUYQWFMO-UHFFFAOYSA-H osmium hexafluoride Chemical compound F[Os](F)(F)(F)(F)F MLKFZZUUYQWFMO-UHFFFAOYSA-H 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- YRGLXIVYESZPLQ-UHFFFAOYSA-I tantalum pentafluoride Chemical compound F[Ta](F)(F)(F)F YRGLXIVYESZPLQ-UHFFFAOYSA-I 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- CULOEOTWMUCRSJ-UHFFFAOYSA-M thallium(i) fluoride Chemical compound [Tl]F CULOEOTWMUCRSJ-UHFFFAOYSA-M 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- SANRKQGLYCLAFE-UHFFFAOYSA-H uranium hexafluoride Chemical compound F[U](F)(F)(F)(F)F SANRKQGLYCLAFE-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- C23F1/00—Etching metallic material by chemical means
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Description
【0001】
【発明の属する技術分野】
本発明は、鉛含有銅合金製水道用器具の製造方法と、水道用器具の鋳造脱鉛品と、水道用器具とに関する。
【0002】
【従来の技術】
水栓金具や水道管等の水道用器具には耐腐食性、切削性等の観点から鉛含有銅合金である青銅や黄銅等が用いられている。このような鉛含有銅合金製の水道用器具は過去においては以下のように製造されていた。すなわち、図12に示すように、まず、鋳造工程S90において、鉛含有銅合金からなり、水を通す通水路を有して水道用器具の粗形状をなす鋳造品を得る。次いで、切削工程S92において、その鋳造品の外周面を切削加工して切削品を得る。そして、めっき工程S94において、切削品の外周面に主に装飾性の観点からニッケル・クロムめっき等のめっき層を施してめっき品を得る。
【0003】
一般的なめっき工程S94は、切削品に前処理を行う前処理工程S95と、この前処理工程S95後に切削品の外周面にめっき層を施す本めっき工程S96とを備えている。より詳細には、前処理工程S95は、切削品をアルカリ液に浸漬して切削品の外周面及び通水路の内周面を脱脂する脱脂工程S95aを有している。ここで用いられるアルカリ液は、通常、水酸化ナトリウム等を水に溶解したアルカリ性の水溶液である。このアルカリ液に切削品を浸漬すれば、アルカリ液のpHに応じて脱脂が行われる。なお、アルカリ液のpHに応じて鉛のエッチングによる除去も行われている。また、前処理工程S95は、この脱脂工程S95aの他、アルカリ液中で切削品を陰極として切削品の外周面の脱脂をさらに行う陰極電解工程S95bと、切削品を酸性液で洗浄して切削品の外周面及び通水路の内周面を活性化する酸活性工程S95cと、これらの工程間に設けられる水洗工程とを有し得る。こうして得られた水道用器具は通水路内に水が通されて活用されることとなる。
【0004】
しかし、近年、水に含有されている鉛による健康阻害が危惧されつつあり、鉛含有銅合金製水道用器具の通水路の内周面からの水への鉛の溶出量を一層低減させたいという要望がある。
【0005】
このため、特許文献1には、本めっき工程S96の前、すなわち切削工程S92の後の前処理工程S95の脱脂工程S95aにおいて、pHの高いアルカリ液への浸漬を行う製造方法が提案されている。この製造方法によれば、通水路の内周面からの水への鉛の溶出量をある程度低減できるようである。
【0006】
また、特許文献2には、図13に示すように、めっき工程S94の後、めっき品を活性アルカリ液に浸漬してめっき品の通水路の内周面の脱鉛処理を行う脱鉛工程S98を行う製造方法が提案されている。また、脱鉛工程S98後、水にリン酸又はリン酸塩を主として添加した処理液により、通水路の内周面にリンを含む皮膜を形成する皮膜形成工程S99を行うことも提案されている。これらの製造方法によれば、通水路の内周面からの水への鉛の溶出量をより確実に低減できる。
【0007】
【特許文献1】
特開2000−96268号公報
【特許文献2】
WO02/36856A1
【0008】
【発明が解決しようとする課題】
しかし、社会的要請により水道用器具に関する鉛の溶出量を0.007(mg/l)未満とする基準値の見直しが行われようとしている。この点から言えば、上記特許文献1記載の製造方法により水道用器具を製造するとしても、通水路の内周面からの水への鉛の溶出量が未だ懸念される。また、上記特許文献2記載の製造方法により水道用器具を製造するとしても、通水路の内周面からの水への鉛の溶出量をより低減させることが好ましい。
【0009】
また、特許文献1記載の製造方法により、脱脂工程S95aでpHの高いアルカリ液への浸漬を行うこととすれば、図12に示す本めっき工程S96前において切削品の外周面及び通水路の内周面から鉛がエッチングにより除去され、切削品の外周面及び通水路の内周面に凹凸を生じやすい。このため、その後に本めっき工程S96を行うことにより、切削品の外周面にめっき層を施したとしても、凹凸が水道用器具の外周面に残り、水道用器具の外周面は悪い面性状となりやすい。このため、その水道用器具は美観を損なうこととなってしまう。この点、切削品の外周面にめっき層を厚く施すことにより、水道用器具の美観を保つこととすれば、製造コストの高騰化を招来してしまうこととなる。
【0010】
本発明は上記従来の実情に鑑みてなされたものであって、通水路の内周面からの水への鉛の溶出量を十分に少なくしつつ、優れた美観を奏する鉛含有銅合金製水道用器具を製造できるようにすることを解決すべき課題としている。
【0011】
【課題を解決するための手段】
本発明の鉛含有銅合金製水道用器具の製造方法は、鉛含有銅合金からなり、水を通す通水路を有して水道用器具の粗形状をなす鋳造品を得る鋳造工程と、該鋳造品の外周面を切削加工して切削品を得る切削工程と、該切削品の外周面にめっき層を施してめっき品を得るめっき工程とを備えた鉛含有銅合金製水道用器具の製造方法において、
前記切削工程前に前記鋳造品を脱鉛液に浸漬して該鋳造品の前記外周面及び前記通水路の内周面の脱鉛処理を行う脱鉛工程を行うことを特徴とする。
【0012】
本発明の製造方法では、脱鉛工程として、鋳造後の鋳造品を切削工程前に脱鉛液に浸漬し、鋳造品の外周面及び通水路の内周面の脱鉛処理を行う。この際、鉛含有銅合金からなる鋳造品は、水を通す通水路の内周面で脱鉛が行なわれるとともに、外周面においても脱鉛が行なわれることとなる。通水路の内周面は、脱鉛により凹凸を生じつつ、製品である水道用器具になった後における水への鉛の溶出量を十分に少なくする。他方、外周面は脱鉛により凹凸を生じることになるが、その凹凸は後の切削工程により平滑にされる。このため、その後のめっき工程において、厚くめっき層を施さなくても優れた外観を呈する。よって、さほどのコストアップも生じない。
【0013】
したがって、本発明の製造方法によれば、通水路の内周面からの水への鉛の溶出量を十分に少なくしつつ、優れた美観を奏する鉛含有銅合金製水道用器具を製造することができる。
【0014】
なお、特開平11−29887号には、鉛含有銅合金製の配管器材において、酸を含有する洗浄液により水と接する部分を洗浄する製造方法が開示されている。しかし、この製造方法はその洗浄を切削品に対して行なっていることから、製品である配管器材は外周面に凹凸が残りやすく、美観において劣るものとなる。また、この製造方法は必ずしも洗浄後にめっき工程を行なうとは限らないが、仮にめっき工程を行なう場合でも、通常の厚さのめっき層では凹凸が配管器材の外周面に残り、その配管器材の外周面は悪い面性状となりやすい。このため、その配管器材は、上記特許文献1開示の製造方法によるものと同様、美観を損なうこととなってしまう。また、洗浄後の切削品の外周面にめっき層を厚く施すこととすれば、やはり製造コストの高騰化を招来してしまうこととなる。
【0015】
脱鉛液としては、鉛が両性金属であるため、酸性液やアルカリ液を用いることが考えられる。発明者らの試験結果によれば、脱鉛液として、強酸水溶液を用いることが特に好ましい。強酸水溶液としては、塩酸水溶液、硫酸水溶液、酢酸水溶液等を採用することができる。脱鉛液が塩酸水溶液である場合、鉛は次の化1に示す化学反応により溶解することとなる。
【0016】
【化1】
Pb+2HCl→PbCl2+H2
【0017】
強酸水溶液であれば、鋳造品において、その外周面側及び通水路の内周面側に存在している鉛だけに限らず、外周面及び内周面から深い位置に存在している鉛までも除去することができる。
【0018】
また、鋳造品の外周面や通水路の内周面には鋳造時のいわゆる黒皮若しくは酸化スケールが付着している。また、鋳造品の外周面に残る鋳砂はショットブラスト等により落とされ得るものの、鋳造品の通水路の内周面に残る鋳砂はそのようなショットブラスト等によっては落とされ難い。
【0019】
かかる実情の下、一般的な製造方法により、鋳造品の外周面を直ぐに切削工程に供するとすれば、刃具は、少なくとも黒皮等を切削加工する必要があり、外周面に鋳砂が残存しているとすれば、たちまち摩耗してしまう。通水路の内周面の切削加工に至っては、黒皮等ばかりでなく、鋳砂が多く残存し、刃具の摩耗が著しい。このため、一般的な製造方法では、外周面の切削加工だけを行う場合においても、ショットブラスト等を入念に行わなければ、刃具の耐久性が極めて悪いものになってしまう。また、通水路の内周面の切削加工においても、可能な限り鋳砂を除去するようにショットブラスト等を工夫する必要が生じてしまう。
【0020】
これに対し、本発明に係る脱鉛工程の強酸水溶液は、外周面及び通水路の内周面に黒皮等とともに鋳砂が残存していたとしても、黒皮等を溶解し、これによって鋳砂も除去する。このため、外周面を切削加工する切削工程において、刃具は、黒皮等を切削加工する必要がなく、かつ鋳砂によって摩耗することもない。通水路の内周面の切削加工も同様である。なお、本発明に係る脱鉛工程の強酸水溶液は、黒皮等を溶解し、それによって鋳砂を除去した後、鉛含有銅合金からなる母材部の脱鉛処理を行う。こうして母材部の外周面側及び通水路の内周面側には、母材部と一体をなし、鉛濃度が母材部より低い低鉛含有層が形成されることとなる。この低鉛含有層は、鉛濃度が母材部より低いことから、切削性を低下させることとなるが、低鉛含有層による切削性の低下は、黒皮等、ひいては鋳砂による切削性の悪化に比べれば、ほとんど問題にならない。特に、切削工程においては、母材部まで切削工程を行うことがほとんどであるから、低鉛含有層による切削性の低下はほぼ確実に問題にならない。
【0021】
本発明の製造方法では、上記特許文献2と同様、めっき工程後にめっき品を第2脱鉛液に浸漬してめっき品の通水路の内周面の脱鉛処理を行う第2脱鉛工程を行うことが好ましい。これにより通水路の内周面から水への鉛の溶出量をさらに低減することができる。また、めっき工程後に第2脱鉛工程を行なえば、めっき品の外周面はめっき層に保護されて鉛の除去が行われず、めっき層のない通水路の内周面のみからさらに鉛が除去されることとなる。このため、めっき品の外周面には凹凸を生じず、めっき層も損なわれないことから、水道用器具の外周面は優れた面性状を保つこととなる。このため、その水道用器具は優れた美観を奏する。
【0022】
第2脱鉛液としても酸性液やアルカリ液を用いることが考えられる。しかし、銅は酸に反応するのに対し、両性金属である鉛は酸にもアルカリにも反応するので、第2脱鉛液としてはアルカリ液を用いることが好ましい。特に、活性アルカリ液を採用することが好ましい。その活性アルカリ液はpHが12〜14の範囲を示すようなアルカリ液をいう。pHがこの範囲の活性アルカリ液によれば、その活性アルカリ液は内周面の鉛と化学反応を起こしやすいので、その鉛を溶解して除去しやすい。このような活性アルカリ液は、主に炭酸ナトリウム、水酸化ナトリウム、リン酸ナトリウム、メタケイ酸ナトリウム、トリポリリン酸ナトリウム、オルケイ酸ナトリウム、水酸化カリウム等の水溶液である。
【0023】
このような第2脱鉛液は界面活性剤を含んでも良い。第2脱鉛液が界面活性剤を含めば、その第2脱鉛液の表面張力を低下させることができるので、通水路の内周面に対する第2脱鉛液の浸透性及び湿潤性を向上させることができる。このため、その内周面に含まれる鉛と第2脱鉛液との化学反応を起こしやすい。
【0024】
界面活性剤としては、アニオン界面活性剤やノニオン界面活性剤を用いることができる。アニオン界面活性剤としては、例えば、高級脂肪酸ナトリウム、硫酸化油、高級アルコール硫酸エステルナトリウム、アルキルベンゼン硫酸ナトリウム、高級アルキルエーテル硫酸エステルナトリウム、α−オレフィン硫酸ナトリウム等を採用することができる。また、ノニオン界面活性剤としては、例えば、アルキルポリオキシエチレンエーテル、アルキルフェニルポリオキシエチレンエーテル、脂肪酸エチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物等を採用することができる。
【0025】
また、第2脱鉛液にキレート剤を含ませることもできる。キレート剤が鉛と化学反応を起こして水溶性の錯体が形成されるので、通水路の内周面に含まれている鉛の除去を容易にすることができる。
【0026】
キレート剤としては、例えば、エチレンジアミン、チオ尿素、酒石酸、ロッシェル塩、EDTA、トリエタノールアミン等を採用することができる。
【0027】
さらに、第2脱鉛液に酸化剤を含ませることもできる。すなわち、活性アルカリ液である第2脱鉛液が水酸化ナトリウム水溶液である場合、水酸化ナトリウム水溶液だけで通水路の内周面に含まれている鉛を除去しようとすると、鉛は次の化2に示す化学反応により溶解することとなる。
【化2】
Pb+2NaOH→Na2PbO2+H2
【0028】
これに対し、活性アルカリ液である第2脱鉛液に酸化剤を含めば、まず酸化剤が鉛と以下の化3に示す化学反応を起こし、酸化鉛が形成される。
【0029】
【化3】
2Pb+O2→2PbO
【0030】
そして、酸化鉛は活性アルカリ液である第2脱鉛液に溶け、以下の化4に示す化学反応を起こし、酸化鉛塩が形成される。
【0031】
【化4】
PbO+2NaOH→Na2PbO2+H2O
【0032】
上記化2のみの反応よりも上記化3及び化4の反応の方が迅速に行われるため、こうして活性アルカリ液である第2脱鉛液に酸化剤を含ませた方が通水路の内周面に含まれている鉛の除去を容易にすることができる。
【0033】
酸化剤としては、例えば、メタニトロベンゼンズルホン酸ナトリウム、パラニトロ安息香酸ナトリウム、次亜塩素酸塩、さらし粉、過酸化水素、過マンガン酸カリウム、過硫酸塩、過塩素酸塩等を採用することができる。
【0034】
本発明の製造方法では、第2脱鉛工程後、水にリン酸又はリン酸塩を主として添加した処理液により、通水路の内周面にリンを含む皮膜を形成する皮膜形成工程を行うことが好ましい。皮膜形成工程で形成した皮膜が鉛の浸出をさらに防止する。この皮膜は、例えば、第一リン酸亜鉛(Zn(H2PO4)2)とリン酸(H3PO4)とを主成分とする処理液を用いた場合、以下のように生成されるものと考えられる。
【0035】
まず、鉛含有銅合金製のワークにそのような処理液を接触させると、化5に示すように、リン酸によって銅が処理液中に溶解して銅イオンを生じる。
【0036】
【化5】
Cu+2H+→Cu2++H2
【0037】
また、そのワークの表面に鉛が存在するのであれば、化6に示すように、リン酸によって鉛も処理液中に溶解して鉛イオンを生じ得る。
【0038】
【化6】
【0039】
Pb+2H+→Pb2++H2
【0040】
ここで、第一リン酸亜鉛は、化7に示すように、処理液中において一部が解離している。
【0041】
【化7】
【0042】
Zn(H2PO4)2→ZnPO4 -+H3PO4+H+
【0043】
このため、処理液中の銅イオン及び/又は鉛イオンは、以下の化8及び/又は化9に示す化学反応を起こし、ワークの表面にリンを含む皮膜を形成するものと考えられる。
【0044】
【化8】
Cu2++2ZnPO4 -→Zn2Cu(PO4)2
【0045】
【化9】
Pb2++2ZnPO4 -→Zn2Pb(PO4)2
【0046】
また、Zn2Cu(PO4)2、Zn2Pb(PO4)2以外にも、Zn3(PO4)2・4H2O又は/及びZn(H2PO4)2の不活性な結晶からなる皮膜が形成されているものとも考えられる。発明者らの実験結果によれば、こうして形成された皮膜により、鉛の浸出を防止することができる。
【0047】
また、この鉛浸出防止方法では、処理液として水にリン酸又はリン酸塩を主として添加したものを用いており、リン酸又はリン酸塩は、クロムめっき層を形成するための六価のクロムからなるクロム酸を含むクロムめっき浴や不動態化を行うためのクロム酸を含むクロメート液に比して毒性がほとんどない。このため、処理液を接触させた後のワークを洗浄した洗浄液や廃液に対して中和や希釈を行うだけでそれら洗浄液等を処分することができる。そのため、特開2000−96269号公報や特開2000−96270号公報に開示されるようなクロム酸を含むクロメート液の処分に比して、洗浄液等の管理も簡易となる。
【0048】
本発明に係るリン酸とは、五酸化リン(P2O5)が種々の程度に水化して生じる一連の酸(P2O5・nH2O)である。例えば、オルトリン酸(H3PO4(0.5P2O5・1.5H2O))、メタリン酸(HPO3(0.5P2O5・0.5H2O))等である。
【0049】
また、本発明に係るリン酸塩としては、リン酸亜鉛系、リン酸マンガン系、リン酸鉄系、リン酸亜鉛・カルシウム系等を採用することができる。リン酸亜鉛系としては、第1リン酸亜鉛(Zn(H2PO4)2)を主成分とするもの等がある。その他、リン酸ナトリウム(NaH2PO4、Na2HPO4等)、リン酸アルミニウム(Al(H2PO4)3等)、リン酸アンモニウム(NH4H2PO4等)等がある。
【0050】
本発明における処理液のリン酸又はリン酸塩の濃度は0.01〜10.0質量%であることが好ましい。発明者らの実験結果によれば、リン酸又はリン酸塩の濃度が0.01〜10.0質量%であれば、ワークの表面にリンを含む皮膜が形成し易いことがわかった。
【0051】
本発明で用いるクロムめっき浴にはフッ化物を含ませることが好ましい。クロムめっき浴中で形成されたクロム酸鉛はフッ化物によって溶解されることが考えられるからである。フッ化物としては、フッ化亜鉛、フッ化アルミニウム、フッ化アンチモン、フッ化アンモニウム、フッ化イオウ、フッ化ウラン、フッ化塩素、フッ化オスミウム、フッ化カドミウム、フッ化カリウム、フッ化カルシウム、フッ化キセノン、フッ化銀、フッ化クロム、フッ化珪素、フッ化ゲルマニウム、フッ化コバルト、フッ化酸素、フッ化シアン、フッ化臭素、フッ化ジルコニウム酸塩、フッ化スズ酸塩、フッ化ストロンチウム、フッ化タリウム、フッ化タンタル酸塩、フッ化窒素、フッ化鉄、フッ化銅、フッ化ナトリウム、フッ化ニオブ酸塩、フッ化ニッケル、フッ化バリウム、フッ化ヒ素、フッ化ホウ素、フッ化ホウ素酸、フッ化マグネシウム、フッ化マンガン、フッ化メチル、フッ化ヨウ素、フッ化ヨウ素酸塩、フッ化リチウム、フッ化リン、フッ化レリウム等を用いることができる。フッ化物としての例えばフッ化珪素は鉛と以下の化10に示す化学反応を起こし、ケイフッ化鉛を形成することも考えられる。こうして通水路の内周面に含まれる鉛を除去することができる。
【0052】
【化10】
PbCrO4+H2SiF6→PbSiF6+H2CrO4
【0053】
また、本発明の製造方法では、切削工程後に切削品を他の脱鉛液に浸漬して切削品の外周面及び通水路の内周面の脱鉛処理を行う他の脱鉛工程を行うことも可能である。つまり、他の脱鉛液としてpHの高いアルカリ液を採用する場合、上記特許文献1と同様、本めっき工程の前、すなわち切削工程の後の脱脂工程において、pHの高いアルカリ液への浸漬を行うことも可能である。切削工程後に他の脱鉛工程を行なえば、切削品の外周面及び通水路の内周面からさらに鉛が除去されることになると考えられる。但し、あまりにpHの高いアルカリ液への浸漬を行うこととすれば、水道用器具は美観を損なうこととなってしまうとともに、切削品の外周面にめっき層を厚く施す必要を生じ、製造コストの高騰化を招来してしまうこととなる。このため、pHの調整に留意を要する。
【0054】
本発明の製造方法において、水栓金具用の鋳造品に対して脱鉛工程、切削工程及びめっき工程を行なえば、本発明の水道用器具としての水栓金具が得られる。また、鋳造品を脱鉛工程に供すれば、本発明の水道用器具の鋳造脱鉛品が得られる。この鋳造脱鉛品は、鉛含有銅合金からなり、水を通す通水路を有して水道用器具の粗形状をなす母材部と、この母材部の外周面側及び通水路の内周面側で一体をなし、鉛濃度が該母材部より低い低鉛含有層とからなることを特徴とする。低鉛含有層は鉛を含まないことが好ましい。低鉛含有層に鉛を含まなければ、水道用器具の通水路を通る水に鉛がほとんど溶出しないからである。この鋳造脱鉛品の外周面が切削加工された後、めっき層が形成されることにより、本発明の水道用器具となる。この水道用器具は、水を通す通水路をもつ鉛含有銅合金からなる母材部と、通水路の外周面側に形成されためっき層と、通水路の内周面側で母材部と一体をなし、鉛濃度が母材部より低い低鉛含有層とからなる。また、皮膜形成工程を行った水道用器具は、通水路の内周面には低鉛含有層のより内周面側にリンを含む皮膜がある。
【0055】
【発明の実施の形態】
以下、本発明を具体化した実施形態、試験及び変形形態を図面を参照しつつ説明する。
【0056】
(実施形態)
実施形態の鉛含有銅合金製水道用器具の製造方法では、図1に示す工程S10〜S60を経て水道用器具を製造している。まず、鋳造工程S10において、図2に示すように、JISCAC406(青銅6種)からなり、水を通す通水路10aを有して水栓金具本体の粗形状をなす鋳造品10を得る。この鋳造品10における外周面や通水路10aの内周面には、図3に示すように、鋳造時のいわゆる黒皮等21aが付着している。また、鋳造品10の外周面に残る鋳砂21bはショットブラスト等により落とされ得るものの、鋳造品10の通水路10aの内周面に残る鋳砂21bはそのようなショットブラスト等によっては落とされ難い。
【0057】
次に、図1に示す脱鉛工程S20において、鋳造品10を脱鉛液に浸漬して鋳造品10の外周面及び通水路10aの内周面の脱鉛処理を行う。脱鉛液としては、濃度5〜7%、温度40〜60°Cの塩酸水溶液を強酸水溶液として使用し、この塩酸水溶液に鋳造品10を2〜4分浸漬する。この際、鋳造品10は、通水路10aの内周面で脱鉛が行なわれるとともに、外周面においても脱鉛が行なわれることとなる。特に、強酸水溶液を脱鉛液として採用しているため、鋳造品10は、その通水路10aの内周面及び外周面に存在している鉛だけに限らず、その外周面及び通水路10aの内周面から深い位置に存在している鉛までも除去することができる。また、脱鉛工程S20の塩酸水溶液は、外周面及び通水路10aの内周面に黒皮等21aとともに鋳砂21bが残存していたとしても、黒皮等21aを溶解し、これによって鋳砂21bも除去する。
【0058】
これにより、図4に示す鋳造脱鉛品20が得られる。この鋳造脱鉛品20は、図5にも示すように、鉛含有銅合金からなり、水を通す通水路10aを有して水栓金具本体の粗形状をなす母材部21と、この母材部21における通水路10aの内周面側で一体をなし、鉛濃度が母材部21より低い低鉛含有層22と、母材部21の外周面側で一体をなし、鉛濃度が母材部21より低い低鉛含有層23とからなる。通水路10aの内周面を形成する低鉛含有層22は、脱鉛により凹凸を生じつつ、製品である水栓金具になった後における水への鉛の溶出量を十分に少なくする。他方、外周面を形成する低鉛含有層23も脱鉛により凹凸を生じている。強酸水溶液の条件によって、低鉛含有層22、23が鉛を含まないようにすることも可能である。なお、脱鉛工程S20後、水洗工程を行なう。
【0059】
次いで、図1に示す切削工程S30において、鋳造脱鉛品20の外周面を約1mm切削加工し、図6に示す切削品30を得る。その際、弁座や吐水口等も寸法や形状が整えられる。これにより、図7にも示すように、凹凸を生じていた外周面側の低鉛含有層23は、完全に切削され、平滑にされる。また、鋳造工程S10で生じていた黒皮等21a及び鋳砂21bを脱鉛工程S20により除去しているため、切削工程S30が容易である。すなわち、外周面を切削加工する切削工程S30において、刃具は、黒皮等21aを切削加工する必要がなく、かつ鋳砂21bによって摩耗することもない。通水路10aの内周面を切削加工し、弁座等を整える場合も同様である。なお、外周面側の低鉛含有層23は、鉛濃度が母材部21より低いことから、切削性を低下させることとなるが、低鉛含有層23による切削性の低下は、黒皮等21a、ひいては鋳砂21bによる切削性の悪化に比べれば、ほとんど問題にならない。特に、切削工程S30において、母材部21まで切削工程S30を行うことから、低鉛含有層23による切削性の低下はほぼ確実に問題にならない。
【0060】
そして、図1に示すめっき工程S40において、切削品30の外周面にめっき層24を施し、図8に示すめっき品40を得る。このめっき工程S40は、図12に示す従来のめっき工程S94と同様、前処理工程S95と本めっき工程S96とからなる。
【0061】
前処理工程S95は、脱脂工程S95aと、陰極電解工程S95bと、酸活性工程S95cと、これらの工程間に設けられる水洗工程とを有している。ここで、脱脂工程S95aでは、切削品30をpH11のアルカリ液に5分間浸漬して切削品30の外周面及び通水路10aの内周面の脱脂を行う。このアルカリ液は、水酸化ナトリウムを数g/l含むとともに、界面活性剤とキレート剤とを含む水溶液であり、その温度は40°Cである。また、陰極電解工程S95bでは、同様のアルカリ液中において、脱脂工程S95a後の切削品30を陰極とすることによって、切削品30の外周面のさらなる脱脂を行う。さらに、酸活性工程S95cでは、陰極電解工程S95b後の切削品30を室温、pH2の硫酸水溶液で洗浄して切削品30の外周面及び通水路10aの内周面を活性化している。なお、これらの工程間では、水洗工程として切削品30の水洗を行う。
【0062】
本めっき工程S96も、ニッケルめっき工程と、クロムめっき工程とを有している。ニッケルめっき工程では、ニッケルめっき浴を用い、酸活性工程S95c後の切削品30の外周面にニッケルめっき層を施している。また、クロムめっき工程では、クロムめっき浴を用い、ニッケルめっき工程後の切削品30の外周面にクロムめっき層を施している。このクロムめっき浴中にはフッ化物としてのケイフッ化ナトリウムが5〜10g/l含まれている。このクロムめっき工程では、クロムめっき浴中のクロム酸により、クロム酸と鉛とが化学反応を起こし、通水路10aの内周面に含まれる鉛が除去される。この際、クロムめっき浴中で形成されたクロム酸鉛がフッ化物によって溶解されると考えられる。これらの工程間でも水洗工程を行っている。
【0063】
こうして、脱鉛工程S20によって外周面に生じていた凹凸がその後の切削工程S30により平滑にされているため、めっき工程S40において、厚くめっき層24を施さなくても優れた外観を呈することとなる。よって、さほどのコストアップも生じない。
【0064】
さらに、図1に示す第2脱鉛工程S50において、めっき品40を第2脱鉛液に10分間浸漬し、めっき品40の外周面及び通水路10aの内周面の脱鉛処理を行う。第2脱鉛液としては、pH14の強アルカリ水溶液として使用する。この第2脱鉛液は、水酸化ナトリウムを50g/l含む水溶液であり、その温度は50°Cである。これにより通水路10aの内周面から水への鉛の溶出量をさらに低減することができる。また、めっき工程S40後に第2脱鉛工程S50を行なえば、めっき品40の外周面はめっき層24に保護されて鉛の除去が行われず、めっき層24のない通水路10aの内周面のみからさらに鉛が除去されることとなる。このため、めっき品40の外周面には凹凸を生じず、めっき層24も損なわれない。また、第2脱鉛液が活性アルカリ液であるため、鉛含有銅合金の銅は反応せず、鉛だけが反応する。
【0065】
そして、図1に示す皮膜形成工程S60を行う。この皮膜形成工程S60では、第2脱鉛工程S50後のめっき品40を処理液に10分間浸漬している。この処理液は、リン酸(H3PO4)0.9質量%の水溶液であり、その温度は50°Cである。こうして、処理液が通水路10aの内周面の銅及び/又は鉛と反応を起こし、図9に示すように、通水路10aの内周面にリンを含む皮膜25を形成する。なお、この皮膜形成工程S60の前後にも水洗を行っている。こうして外周面が優れた面性状を保つ水栓金具本体50(図10参照)が得られる。
【0066】
この後、水栓金具本体50に同様に製造したハンドル51、図示しない弁体等を取付け、図10に示す水栓金具が得られる。この水栓金具は、図9に示すように、水を通す通水路10aをもつ鉛含有銅合金からなる母材部21と、母材部21の外周面側に形成されたニッケル・クロムめっき層24と、通水路10aの内周面側で母材部21と一体をなし、鉛濃度が母材部21より低い低鉛含有層22と、低鉛含有層22のより内周面側にあるリンを含む皮膜25とからなる。母材部21とニッケル・クロムめっき層24との間に鉛濃度が母材部21より低い低鉛含有層23(図5参照)を薄く残しても良い。この水栓金具は通水路10a内に水が通されて活用されることとなる。
【0067】
(試験)
JISS3200−7(1997年)「水道用器具−浸出性能試験方法」により、水栓金具から溶出される鉛の原液濃度(mg/l)を測定した。そして、鉛の溶出量(mg/l)を算出した。水栓金具における通水路10aの内容量は155mlと比較的大きく、基準値をクリアするために不利なものである。
【0068】
表1に示すように、試験例1では、上述した実施形態の製造方法によって製造した水栓金具を用いている。また、試験例2では、実施形態の製造方法において、第2脱鉛工程S50及び皮膜形成工程S60を連続して2回行うことによって製造した水栓金具を用いている。さらに、試験例3では、図11に示すように、実施形態の製造方法において、第2脱鉛工程S50及び皮膜形成工程S60を行わないで製造した水栓金具を用いている。
【0069】
他方、比較例1では、図12に示す一般的な製造方法によって製造した水栓金具を用いている。また、比較例2では、図13に示す特許文献2の製造方法2において、脱鉛工程S98を10分間行うことによって製造した水栓金具を用いている。その際、上記実施形態の製造方法における第2脱鉛液を用い、鉛の除去を行う。さらに、比較例3では、比較例2と同様、脱鉛工程S98を15分間行うことによって製造した水栓金具を用いている。また、比較例4では、比較例2と同様、10分間の脱鉛工程S98及び5分間の皮膜形成工程S99を連続して2回行うことによって製造した水栓金具を用いている。結果を表1に示す。
【0070】
【表1】
【0071】
表1に示すように、試験例1、2では、鉛の溶出量が基準値の0.007(mg/l)未満であった。よって、基準値をクリアするために不利な大きさの内容量をもつ水栓金具であっても、試験例1、2の製造方法によれば、通水路10aの内周面からの水への鉛の溶出量を十分に少なくしつつ、優れた美観を奏するものになることがわかる。なお、試験例3では、鉛の溶出量が0.007(mg/l)以上であり、脱鉛処理単独では、鉛の溶出量を0.007(mg/l)未満にすることが困難であると考えられる。
【0072】
他方、比較例2〜4に関しては、脱鉛工程S98を長時間行ったり、複数回行うことにより、鉛の溶出量が0.007(mg/l)に近づいたものの、未だ鉛の溶出量を十分に少なくし切れていないことがわかる。時間及び回数を増やすことによって鉛の溶出量を0.007(mg/l)未満にできる可能性はあるものの、工程の増加による製造コストの懸念がある。なお、比較例1では、鉛の溶出量が全く基準値に満たない。
【0073】
したがって、実施形態の鉛含有銅合金製水道用器具の製造方法では、通水路10aの内周面からの水への鉛の溶出量を基準値を満たすように十分に少なくしつつ、優れた美観を奏する鉛含有銅合金製水道用器具を製造できることがわかる。
【0074】
(変形形態)
図11に示すように、切削工程S30後のめっき工程S40の脱脂工程S95a(図11参照)において、他の脱鉛液としてのpHの高いアルカリ液への浸漬を行い、これにより切削品30の外周面及び通水路10aの内周面の脱鉛処理を行うことも可能である。切削工程S30後に他の脱鉛工程を行なえば、切削品30の外周面及び通水路10aの内周面からさらに鉛が除去されることになると考えられる。但し、あまりにpHの高いアルカリ液への浸漬を行うこととすれば、水道用器具は美観を損なうこととなってしまうとともに、切削品30の外周面にめっき層24を厚く施す必要を生じ、製造コストの高騰化を招来してしまうこととなる。このため、pHの調整に留意を要する。
【図面の簡単な説明】
【図1】実施形態に係り、鉛含有銅合金製水道用器具の製造方法の工程図である。
【図2】実施形態に係り、鋳造品の縦断面図である。
【図3】実施形態に係り、図2に示す鋳造品のA部の拡大断面図である。
【図4】実施形態に係り、鋳造脱鉛品の縦断面図である。
【図5】実施形態に係り、図4に示す鋳造脱鉛品のA部の拡大断面図である。
【図6】実施形態に係り、切削品の縦断面図である。
【図7】実施形態に係り、図6に示す切削品のA部の拡大断面図である。
【図8】実施形態に係り、めっき品の縦断面図である。
【図9】実施形態に係り、図8に示すめっき品のA部の拡大断面図である。
【図10】実施形態に係り、水栓金具の全体斜視図である。
【図11】変形形態に係り、鉛含有銅合金製水道用器具の製造方法の工程図である。
【図12】一般的な鉛含有銅合金製水道用器具の製造方法の工程図である。
【図13】特許文献2の鉛含有銅合金製水道用器具の製造方法の工程図である。
【符号の説明】
10a…通水路
10…鋳造品
S10…鋳造工程
30…切削品
S30…切削工程
24…めっき層
40…めっき品
S40…めっき工程(S95…前処理工程(S95a…脱脂工程、S95b…陰極電解工程、S95c…酸活性工程)、S96…本めっき工程)
S20…脱鉛工程
S50…第2脱鉛工程
S60…皮膜形成工程
21…母材部
22、23…低鉛含有層
20…鋳造脱鉛品
25…リンを含む皮膜[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a lead-containing copper alloy water supply device, a cast-free lead product of a water supply device, and a water supply device.
[0002]
[Prior art]
Bronze or brass, which is a lead-containing copper alloy, is used for water supply equipment such as faucet fittings and water pipes from the viewpoint of corrosion resistance, machinability and the like. In the past, such a water supply device made of lead-containing copper alloy has been manufactured as follows. That is, as shown in FIG. 12, first, in the casting step S90, a cast product made of a lead-containing copper alloy and having a water passage for passing water and having a rough shape of a water supply device is obtained. Next, in the cutting step S92, the outer peripheral surface of the cast product is cut to obtain a cut product. In the plating step S94, a plated product such as nickel / chrome plating is applied to the outer peripheral surface of the cut product mainly from the viewpoint of decorativeness to obtain a plated product.
[0003]
The general plating step S94 includes a pretreatment step S95 for preprocessing the cut product, and a main plating step S96 for applying a plating layer to the outer peripheral surface of the cut product after the pretreatment step S95. More specifically, the pretreatment step S95 includes a degreasing step S95a in which the cut product is immersed in an alkaline solution to degrease the outer peripheral surface of the cut product and the inner peripheral surface of the water passage. The alkaline solution used here is usually an alkaline aqueous solution in which sodium hydroxide or the like is dissolved in water. If the cut product is immersed in this alkaline liquid, degreasing is performed according to the pH of the alkaline liquid. Note that removal of lead by etching is also performed in accordance with the pH of the alkaline solution. In addition to the degreasing step S95a, the pretreatment step S95 includes a cathodic electrolysis step S95b for further degreasing the outer peripheral surface of the cut product using the cut product as a cathode in an alkaline liquid, and cutting the cut product with an acid solution for cutting. An acid activation step S95c for activating the outer peripheral surface of the product and the inner peripheral surface of the water passage, and a water washing step provided between these steps may be included. The water supply device obtained in this way is used by passing water through the water passage.
[0004]
However, in recent years, there is a concern about the health hindrance caused by lead contained in water, and it is said that we want to further reduce the amount of lead elution into the water from the inner surface of the water channel of lead-containing copper alloy water supply equipment. There is a request.
[0005]
For this reason, Patent Document 1 proposes a manufacturing method for immersing in an alkaline solution having a high pH in the degreasing step S95a of the pretreatment step S95 after the main plating step S96, that is, after the cutting step S92. . According to this manufacturing method, it seems that the elution amount of lead into the water from the inner peripheral surface of the water passage can be reduced to some extent.
[0006]
Further, in Patent Document 2, as shown in FIG. 13, after the plating step S94, a lead removal step S98 is performed in which the plated product is immersed in an active alkaline solution to perform a lead removal treatment on the inner peripheral surface of the water passage of the plated product. A manufacturing method has been proposed. It has also been proposed to perform a film formation step S99 for forming a film containing phosphorus on the inner peripheral surface of the water passage with a treatment liquid mainly containing phosphoric acid or phosphate added to water after the deleading step S98. . According to these manufacturing methods, the elution amount of lead into the water from the inner peripheral surface of the water passage can be more reliably reduced.
[0007]
[Patent Document 1]
JP 2000-96268 A
[Patent Document 2]
WO02 / 36856A1
[0008]
[Problems to be solved by the invention]
However, due to social demands, the standard value is being revised so that the amount of lead elution associated with water supply equipment is less than 0.007 (mg / l). Speaking from this point, even if a water supply device is manufactured by the manufacturing method described in Patent Document 1, the amount of lead eluted into water from the inner peripheral surface of the water passage is still a concern. Moreover, even if it manufactures the water supply apparatus with the manufacturing method of the said patent document 2, it is preferable to reduce more the elution amount of the lead to the water from the internal peripheral surface of a water channel.
[0009]
Moreover, if immersion in a high pH alkaline solution is performed in the degreasing step S95a by the manufacturing method described in Patent Document 1, before the main plating step S96 shown in FIG. Lead is removed from the peripheral surface by etching, and unevenness tends to occur on the outer peripheral surface of the cut product and the inner peripheral surface of the water passage. For this reason, by performing this plating process S96 after that, even if a plating layer is applied to the outer peripheral surface of the cut product, the unevenness remains on the outer peripheral surface of the water supply device, and the outer peripheral surface of the water supply device has poor surface properties. Cheap. For this reason, the device for water supply will spoil the beauty. In this regard, if the plating layer is thickly applied to the outer peripheral surface of the cut product to maintain the aesthetics of the water supply device, the manufacturing cost will increase.
[0010]
The present invention has been made in view of the above-described conventional situation, and is a lead-containing copper alloy tap water that provides an excellent aesthetic appearance while sufficiently reducing the amount of lead eluted into the water from the inner peripheral surface of the water passage. The problem to be solved is to make it possible to manufacture appliances.
[0011]
[Means for Solving the Problems]
The method for producing a lead-containing copper alloy water supply device of the present invention includes a casting step of obtaining a cast product comprising a lead-containing copper alloy and having a water passage through which water passes and having a rough shape of the water supply device, and the casting Method of manufacturing a lead-containing copper alloy water supply device comprising: a cutting step for cutting a peripheral surface of a product to obtain a cut product; and a plating step for obtaining a plated product by applying a plating layer to the peripheral surface of the cut product In
Before the cutting step, a deleading step is performed in which the cast product is immersed in a deleading solution to delead the outer peripheral surface of the cast product and the inner peripheral surface of the water passage.
[0012]
In the manufacturing method of the present invention, as a deleading step, the cast product after casting is immersed in a deleading solution before the cutting step, and a deleading process is performed on the outer peripheral surface of the cast product and the inner peripheral surface of the water passage. At this time, in the casting made of the lead-containing copper alloy, deleading is performed on the inner peripheral surface of the water passage through which water passes, and deleading is also performed on the outer peripheral surface. The inner peripheral surface of the water passage is uneven due to deleading, while sufficiently reducing the amount of lead elution into the water after becoming a water supply device as a product. On the other hand, the outer peripheral surface is uneven by lead removal, but the unevenness is smoothed by a subsequent cutting process. For this reason, in the subsequent plating process, an excellent appearance is exhibited even if a thick plating layer is not applied. Therefore, there is no significant cost increase.
[0013]
Therefore, according to the production method of the present invention, it is possible to produce a lead-containing copper alloy water supply device having an excellent aesthetic appearance while sufficiently reducing the amount of lead eluted into the water from the inner peripheral surface of the water passage. Can do.
[0014]
Japanese Patent Laid-Open No. 11-29887 discloses a manufacturing method for cleaning a portion in contact with water with a cleaning liquid containing acid in piping equipment made of lead-containing copper alloy. However, since this manufacturing method performs cleaning on a cut product, the product piping equipment tends to have unevenness on the outer peripheral surface, which is inferior in appearance. In addition, this manufacturing method does not necessarily perform the plating process after cleaning, but even when the plating process is performed, irregularities remain on the outer peripheral surface of the piping equipment even in the case of a normal thickness plating layer, and the outer circumference of the piping equipment The surface is prone to bad surface properties. For this reason, the plumbing equipment is detrimental to the aesthetics as in the manufacturing method disclosed in Patent Document 1. In addition, if the plating layer is thickly applied to the outer peripheral surface of the cut product after cleaning, the manufacturing cost is also increased.
[0015]
As the lead removal liquid, since lead is an amphoteric metal, it is conceivable to use an acidic liquid or an alkaline liquid. According to the test results of the inventors, it is particularly preferable to use a strong acid aqueous solution as the delead solution. As the strong acid aqueous solution, a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, an acetic acid aqueous solution or the like can be employed. When the delead solution is an aqueous hydrochloric acid solution, lead is dissolved by the chemical reaction shown in the following chemical formula 1.
[0016]
[Chemical 1]
Pb + 2HCl → PbCl2+ H2
[0017]
If it is a strong acid aqueous solution, in the cast product, not only the lead existing on the outer peripheral surface side and the inner peripheral surface side of the water passage, but also the lead existing deeply from the outer peripheral surface and the inner peripheral surface Can be removed.
[0018]
Further, so-called black skin or oxide scale at the time of casting adheres to the outer peripheral surface of the cast product and the inner peripheral surface of the water passage. Further, although the casting sand remaining on the outer peripheral surface of the cast product can be dropped by shot blasting or the like, the casting sand remaining on the inner peripheral surface of the water passage of the casting product is difficult to be dropped by such shot blasting or the like.
[0019]
Under such circumstances, if the outer peripheral surface of the cast product is immediately subjected to a cutting process by a general manufacturing method, it is necessary for the cutting tool to cut at least the black skin and the like, and the casting sand remains on the outer peripheral surface. If so, it will wear out quickly. When cutting the inner peripheral surface of the water passage, not only the black skin and the like, but also a lot of cast sand remains, and the wear of the cutting tool is remarkable. For this reason, in a general manufacturing method, even when only the outer peripheral surface is cut, unless the shot blasting or the like is performed carefully, the durability of the blade will be extremely poor. Moreover, also in the cutting process of the inner peripheral surface of the water passage, it is necessary to devise shot blasting or the like so as to remove the cast sand as much as possible.
[0020]
On the other hand, the strong acid aqueous solution in the deleading process according to the present invention dissolves the black skin and the like even if black sand and the like remain on the outer peripheral surface and the inner peripheral surface of the water passage. Also remove the sand. For this reason, in the cutting process which cuts an outer peripheral surface, a cutting tool does not need to cut a black skin etc. and is not worn by casting sand. The same applies to the cutting of the inner peripheral surface of the water passage. In addition, the strong acid aqueous solution of the deleading process which concerns on this invention melt | dissolves a black skin etc., and removes cast sand by it, Then, the deleading process of the base material part which consists of a lead-containing copper alloy is performed. Thus, on the outer peripheral surface side of the base material part and the inner peripheral surface side of the water passage, a low lead content layer that is integrated with the base material part and has a lower lead concentration than the base material part is formed. This low lead-containing layer has a lower lead concentration than the base metal part, so that the machinability is lowered. Compared to worsening, it is hardly a problem. In particular, in the cutting process, since the cutting process is mostly performed up to the base material portion, the deterioration of the machinability due to the low lead-containing layer is almost certainly not a problem.
[0021]
In the manufacturing method of the present invention, as in the above-mentioned Patent Document 2, the second deleading step is performed in which the plated product is immersed in the second deleading solution after the plating step to delead the inner circumferential surface of the water passage of the plated product. Preferably it is done. Thereby, the elution amount of lead into water from the inner peripheral surface of the water passage can be further reduced. In addition, if the second lead removal step is performed after the plating step, the outer peripheral surface of the plated product is protected by the plating layer and lead is not removed, and lead is further removed only from the inner peripheral surface of the water passage without the plating layer. The Rukoto. For this reason, since an unevenness | corrugation does not arise in the outer peripheral surface of a plating product, and a plating layer is not impaired, the outer peripheral surface of the water supply apparatus will maintain the outstanding surface property. For this reason, the water supply apparatus has an excellent aesthetic appearance.
[0022]
It is conceivable to use an acidic liquid or an alkaline liquid as the second deleading liquid. However, since copper reacts with an acid, while the amphoteric metal lead reacts with both an acid and an alkali, it is preferable to use an alkaline solution as the second deleading solution. In particular, it is preferable to employ an active alkali solution. The active alkaline solution refers to an alkaline solution having a pH ranging from 12 to 14. According to the activated alkaline solution having a pH in this range, the activated alkaline solution is likely to cause a chemical reaction with lead on the inner peripheral surface, so that the lead is easily dissolved and removed. Such an active alkaline solution is mainly an aqueous solution of sodium carbonate, sodium hydroxide, sodium phosphate, sodium metasilicate, sodium tripolyphosphate, sodium orthosilicate, potassium hydroxide or the like.
[0023]
Such a second delead solution may contain a surfactant. If the second deleading liquid contains a surfactant, the surface tension of the second deleading liquid can be lowered, so that the permeability and wettability of the second deleading liquid with respect to the inner peripheral surface of the water passage are improved. Can be made. For this reason, it is easy to raise | generate a chemical reaction with the lead contained in the internal peripheral surface, and a 2nd delead solution.
[0024]
As the surfactant, an anionic surfactant or a nonionic surfactant can be used. As the anionic surfactant, for example, higher fatty acid sodium, sulfated oil, higher alcohol sulfate sodium, alkylbenzene sodium sulfate, higher alkyl ether sulfate sodium, α-olefin sodium sulfate and the like can be employed. Examples of nonionic surfactants that can be used include alkyl polyoxyethylene ether, alkylphenyl polyoxyethylene ether, fatty acid ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, and the like.
[0025]
A chelating agent can also be included in the second delead solution. Since the chelating agent chemically reacts with lead to form a water-soluble complex, it is possible to easily remove lead contained in the inner peripheral surface of the water passage.
[0026]
As the chelating agent, for example, ethylenediamine, thiourea, tartaric acid, Rochelle salt, EDTA, triethanolamine and the like can be employed.
[0027]
Furthermore, an oxidizing agent can be included in the second deleading solution. That is, when the second deleading solution, which is an active alkaline solution, is an aqueous sodium hydroxide solution, if the lead contained in the inner peripheral surface of the water passage is removed only by the aqueous sodium hydroxide solution, the lead will be It will be dissolved by the chemical reaction shown in 2.
[Chemical 2]
Pb + 2NaOH → Na2PbO2+ H2
[0028]
On the other hand, if an oxidant is included in the second delead solution that is an active alkaline solution, the oxidant first causes a chemical reaction with lead as shown in the following chemical formula 3 to form lead oxide.
[0029]
[Chemical Formula 3]
2Pb + O2→ 2PbO
[0030]
And lead oxide melt | dissolves in the 2nd delead solution which is an active alkaline solution, raise | generates the chemical reaction shown to the following Chemical formula 4, and lead oxide salt is formed.
[0031]
[Formula 4]
PbO + 2NaOH → Na2PbO2+ H2O
[0032]
Since the reactions of Chemical Formula 3 and Chemical Formula 4 are performed more quickly than the reaction of Chemical Formula 2 alone, the inner circumference of the water passage is more preferably obtained by adding an oxidizing agent to the second deleading solution, which is an active alkaline solution. The removal of lead contained in the surface can be facilitated.
[0033]
As the oxidizing agent, for example, sodium metanitrobenzenesulfonate, sodium paranitrobenzoate, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate, perchlorate, etc. may be employed. it can.
[0034]
In the production method of the present invention, after the second deleading step, a film forming step of forming a film containing phosphorus on the inner peripheral surface of the water passage is performed by a treatment liquid mainly containing phosphoric acid or phosphate added to water. Is preferred. The coating formed in the coating formation process further prevents lead leaching. For example, this film is composed of zinc phosphate (Zn (H2POFour)2) And phosphoric acid (HThreePOFour) Is used as a main component, it is considered to be generated as follows.
[0035]
First, when such a processing liquid is brought into contact with a workpiece made of a lead-containing copper alloy, as shown in Chemical Formula 5, copper is dissolved in the processing liquid by phosphoric acid to generate copper ions.
[0036]
[Chemical formula 5]
Cu + 2H+→ Cu2++ H2
[0037]
Further, if lead is present on the surface of the workpiece, as shown in Chemical formula 6, lead can be dissolved in the treatment liquid by phosphoric acid to generate lead ions.
[0038]
[Chemical 6]
[0039]
Pb + 2H+→ Pb2++ H2
[0040]
Here, as shown in Chemical Formula 7, a part of the primary zinc phosphate is dissociated in the treatment liquid.
[0041]
[Chemical 7]
[0042]
Zn (H2POFour)2→ ZnPOFour -+ HThreePOFour+ H+
[0043]
For this reason, it is considered that the copper ions and / or lead ions in the treatment liquid cause a chemical reaction shown in the following chemical formula 8 and / or chemical formula 9 to form a film containing phosphorus on the surface of the workpiece.
[0044]
[Chemical 8]
Cu2++ 2ZnPOFour -→ Zn2Cu (POFour)2
[0045]
[Chemical 9]
Pb2++ 2ZnPOFour -→ Zn2Pb (POFour)2
[0046]
Zn2Cu (POFour)2, Zn2Pb (POFour)2Besides, ZnThree(POFour)2・ 4H2O or / and Zn (H2POFour)2It is also considered that a film made of an inert crystal is formed. According to the experiment results of the inventors, lead leaching can be prevented by the coating formed in this way.
[0047]
In this lead leaching prevention method, a treatment liquid in which phosphoric acid or phosphate is mainly added to water is used, and phosphoric acid or phosphate is hexavalent chromium for forming a chromium plating layer. Compared to a chromium plating bath containing chromic acid and a chromate solution containing chromic acid for passivating, there is almost no toxicity. For this reason, these washing | cleaning liquids etc. can be disposed only by neutralizing or diluting with respect to the washing | cleaning liquid and waste liquid which wash | cleaned the workpiece | work after making a processing liquid contact. Therefore, the management of the cleaning liquid and the like becomes easier as compared with the disposal of the chromate liquid containing chromic acid as disclosed in Japanese Unexamined Patent Publication Nos. 2000-96269 and 2000-96270.
[0048]
The phosphoric acid according to the present invention is phosphorus pentoxide (P2OFive) Is a series of acids (P2OFive・ NH2O). For example, orthophosphoric acid (HThreePOFour(0.5P2OFive・ 1.5H2O)), metaphosphoric acid (HPOThree(0.5P2OFive・ 0.5H2O)) and the like.
[0049]
Moreover, as the phosphate according to the present invention, zinc phosphate, manganese phosphate, iron phosphate, zinc phosphate / calcium, and the like can be employed. As the zinc phosphate system, primary zinc phosphate (Zn (H2POFour)2) As a main component. In addition, sodium phosphate (NaH2POFour, Na2HPOFourEtc.), aluminum phosphate (Al (H2POFour)ThreeEtc.), ammonium phosphate (NHFourH2POFourEtc.).
[0050]
The concentration of phosphoric acid or phosphate in the treatment liquid in the present invention is preferably 0.01 to 10.0% by mass. According to the experiment results of the inventors, it was found that when the concentration of phosphoric acid or phosphate is 0.01 to 10.0% by mass, a film containing phosphorus is easily formed on the surface of the workpiece.
[0051]
The chromium plating bath used in the present invention preferably contains fluoride. This is because it is considered that lead chromate formed in the chromium plating bath is dissolved by fluoride. Fluorides include zinc fluoride, aluminum fluoride, antimony fluoride, ammonium fluoride, sulfur fluoride, uranium fluoride, chlorine fluoride, osmium fluoride, cadmium fluoride, potassium fluoride, calcium fluoride, fluorine Xenon fluoride, silver fluoride, chromium fluoride, silicon fluoride, germanium fluoride, cobalt fluoride, oxygen fluoride, cyanide fluoride, bromine fluoride, zirconate fluoride, stannate fluoride, strontium fluoride , Thallium fluoride, tantalum fluoride, nitrogen fluoride, iron fluoride, copper fluoride, sodium fluoride, niobium fluoride, nickel fluoride, barium fluoride, arsenic fluoride, boron fluoride, fluorine Boron acid, magnesium fluoride, manganese fluoride, methyl fluoride, iodine fluoride, fluoroiodate, lithium fluoride, fluorine Phosphide can be used fluoride Reriumu like. For example, silicon fluoride as a fluoride may cause chemical reaction shown in the following
[0052]
[Chemical Formula 10]
PbCrOFour+ H2SiF6→ PbSiF6+ H2CrOFour
[0053]
Further, in the manufacturing method of the present invention, after the cutting process, another deleading process is performed in which the cutting product is immersed in another deleading liquid to perform a deleading process on the outer peripheral surface of the cutting product and the inner peripheral surface of the water passage. Is also possible. That is, when an alkaline solution having a high pH is employed as another deleading solution, the immersion in the alkaline solution having a high pH is performed in the degreasing process before the main plating process, that is, after the cutting process, as in Patent Document 1. It is also possible to do this. If another lead removal process is performed after the cutting process, it is considered that lead is further removed from the outer peripheral surface of the cut product and the inner peripheral surface of the water passage. However, if the immersion in an alkaline solution having an excessively high pH is performed, the water supply device will be detrimental to the appearance, and it will be necessary to apply a thick plating layer to the outer peripheral surface of the cut product, resulting in a reduction in production cost. It will lead to soaring. For this reason, attention must be paid to the adjustment of pH.
[0054]
In the production method of the present invention, if a lead removal process, a cutting process, and a plating process are performed on a cast product for a faucet fitting, a faucet fitting as a water supply device of the present invention is obtained. Moreover, if a cast product is used for a deleading process, the cast delead product of the water supply apparatus of this invention will be obtained. The cast lead-free product is made of a lead-containing copper alloy, has a water passage that allows water to pass therethrough, and forms a rough shape of a water supply device, an outer peripheral surface side of the base material portion, and an inner circumference of the water passage. It is formed of a low-lead-containing layer that is integrated on the surface side and has a lead concentration lower than that of the base material portion. The low lead-containing layer preferably does not contain lead. This is because if the low lead-containing layer does not contain lead, lead hardly elutes in the water passing through the water passage of the water supply device. After the outer peripheral surface of the cast lead-free product is cut, a plating layer is formed, whereby the water supply device of the present invention is obtained. The water supply device includes a base material portion made of a lead-containing copper alloy having a water passage for passing water, a plating layer formed on the outer peripheral surface side of the water passage, and a base material portion on the inner peripheral surface side of the water passage. It consists of a low-lead-containing layer that is integrated and has a lower lead concentration than the base material. Moreover, the water supply apparatus which performed the membrane | film | coat formation process has the membrane | film | coat containing phosphorus in the inner peripheral surface side of the low lead content layer in the inner peripheral surface of a water flow path.
[0055]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments, tests, and modifications embodying the present invention will be described with reference to the drawings.
[0056]
(Embodiment)
In the manufacturing method of the lead-containing copper alloy water supply device of the embodiment, the water supply device is manufactured through steps S10 to S60 shown in FIG. First, in the casting step S10, as shown in FIG. 2, a
[0057]
Next, in the deleading step S20 shown in FIG. 1, the casting
[0058]
Thereby, the cast lead-
[0059]
Next, in the cutting step S30 shown in FIG. 1, the outer peripheral surface of the cast lead-
[0060]
And in the plating process S40 shown in FIG. 1, the
[0061]
The pretreatment step S95 includes a degreasing step S95a, a cathode electrolysis step S95b, an acid activation step S95c, and a water washing step provided between these steps. Here, in the degreasing step S95a, the
[0062]
The main plating step S96 also includes a nickel plating step and a chromium plating step. In the nickel plating step, a nickel plating bath is used, and a nickel plating layer is applied to the outer peripheral surface of the
[0063]
In this way, since the unevenness generated on the outer peripheral surface by the deleading step S20 is smoothed by the subsequent cutting step S30, an excellent appearance is exhibited even if the
[0064]
Further, in the second deleading step S50 shown in FIG. 1, the plated
[0065]
Then, a film forming step S60 shown in FIG. 1 is performed. In this film forming step S60, the plated
[0066]
Thereafter, the
[0067]
(test)
The stock solution concentration (mg / l) of lead eluted from the faucet fitting was measured according to JIS 3200-7 (1997) “Equipment for water supply—Leaching performance test method”. And the elution amount (mg / l) of lead was computed. The internal capacity of the
[0068]
As shown in Table 1, in Test Example 1, a faucet fitting manufactured by the manufacturing method of the above-described embodiment is used. Moreover, in Test Example 2, the faucet fitting manufactured by continuously performing the second deleading step S50 and the film forming step S60 twice in the manufacturing method of the embodiment is used. Furthermore, in Test Example 3, as shown in FIG. 11, the faucet fitting manufactured without performing the second deleading step S50 and the film forming step S60 in the manufacturing method of the embodiment is used.
[0069]
On the other hand, in the comparative example 1, the faucet fitting manufactured by the general manufacturing method shown in FIG. 12 is used. Moreover, in the comparative example 2, the faucet metal fitting manufactured by performing the lead removal process S98 for 10 minutes in the manufacturing method 2 of patent document 2 shown in FIG. 13 is used. At that time, lead is removed by using the second delead solution in the manufacturing method of the embodiment. Furthermore, in Comparative Example 3, as in Comparative Example 2, a faucet fitting manufactured by performing the lead removal step S98 for 15 minutes is used. Further, in Comparative Example 4, as in Comparative Example 2, a faucet fitting manufactured by continuously performing the deleading step S98 for 10 minutes and the film forming step S99 for 5 minutes twice is used. The results are shown in Table 1.
[0070]
[Table 1]
[0071]
As shown in Table 1, in Test Examples 1 and 2, the elution amount of lead was less than the standard value of 0.007 (mg / l). Therefore, even with a faucet fitting having an unfavorable amount of capacity in order to clear the reference value, according to the manufacturing methods of Test Examples 1 and 2, the water from the inner peripheral surface of the
[0072]
On the other hand, for Comparative Examples 2 to 4, although the lead removal step S98 was performed for a long time or multiple times, the lead elution amount was close to 0.007 (mg / l), but the lead elution amount was still reduced. It turns out that it is not fully reduced. Although there is a possibility that the amount of lead elution can be reduced to less than 0.007 (mg / l) by increasing the time and number of times, there is a concern about manufacturing costs due to an increase in the number of processes. In Comparative Example 1, the amount of lead elution does not satisfy the reference value.
[0073]
Therefore, in the manufacturing method of the lead-containing copper alloy water supply device of the embodiment, excellent aesthetic appearance while sufficiently reducing the elution amount of lead into the water from the inner peripheral surface of the
[0074]
(Deformation)
As shown in FIG. 11, in the degreasing step S95a (see FIG. 11) of the plating step S40 after the cutting step S30, immersion in an alkaline solution having a high pH as another deleading solution is performed. It is also possible to perform a deleading process on the outer peripheral surface and the inner peripheral surface of the
[Brief description of the drawings]
FIG. 1 is a process diagram of a method for producing a lead-containing copper alloy water supply apparatus according to an embodiment.
FIG. 2 is a longitudinal sectional view of a cast product according to the embodiment.
FIG. 3 is an enlarged cross-sectional view of a portion A of the cast product shown in FIG. 2 according to the embodiment.
FIG. 4 is a longitudinal sectional view of a cast lead-free product according to the embodiment.
FIG. 5 is an enlarged cross-sectional view of a portion A of the cast lead-free product shown in FIG. 4 according to the embodiment.
FIG. 6 is a longitudinal sectional view of a cut product according to the embodiment.
7 is an enlarged cross-sectional view of a portion A of the cut product illustrated in FIG. 6 according to the embodiment.
FIG. 8 is a longitudinal sectional view of a plated product according to the embodiment.
FIG. 9 is an enlarged cross-sectional view of a portion A of the plated product shown in FIG. 8 according to the embodiment.
FIG. 10 is an overall perspective view of the faucet fitting according to the embodiment.
FIG. 11 is a process diagram of a method for producing a lead-containing copper alloy water supply apparatus according to a modified embodiment.
FIG. 12 is a process diagram of a method for producing a general lead-containing copper alloy water supply device.
13 is a process diagram of a method for producing a lead-containing copper alloy water supply device of Patent Document 2. FIG.
[Explanation of symbols]
10a ... Waterway
10 ... Cast product
S10 ... Casting process
30 ... Cutting product
S30: Cutting process
24 ... Plating layer
40 ... plated product
S40 ... Plating step (S95 ... Pretreatment step (S95a ... Degreasing step, S95b ... Cathodic electrolysis step, S95c ... Acid activation step), S96 ... Main plating step)
S20: Deleading process
S50 ... Second deleading step
S60 ... Film formation process
21 ... Base material part
22, 23 ... Low lead content layer
20 ... cast lead-free product
25 ... Film containing phosphorus
Claims (11)
前記切削工程前に前記鋳造品を脱鉛液に浸漬して該鋳造品の前記外周面及び前記通水路の内周面の脱鉛処理を行う脱鉛工程を行うことを特徴とする鉛含有銅合金製水道用器具の製造方法。A casting process comprising a lead-containing copper alloy, having a water passage for passing water and having a rough shape of a water supply device, and a cutting process for obtaining a cut product by cutting the outer peripheral surface of the cast product; In the method for producing a lead-containing copper alloy water supply device comprising a plating step of applying a plating layer to the outer peripheral surface of the cut product to obtain a plated product,
Lead-containing copper characterized by performing a deleading step of immersing the cast product in a deleading solution before the cutting step to delead the outer peripheral surface of the cast product and the inner peripheral surface of the water passage Manufacturing method of alloy water supply equipment.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069698A JP4430879B2 (en) | 2003-03-14 | 2003-03-14 | Method for producing lead-containing copper alloy water supply device, casting deleading product of water supply device, and water supply device |
| PCT/JP2004/002320 WO2004081257A1 (en) | 2003-03-14 | 2004-02-26 | Method for manufacturing utensil for drinking water system made from lead-containing copper alloy, cast and lead-removed utensil for drinking water system, and utensil for drinking water system |
| CNB2004800065636A CN100441744C (en) | 2003-03-14 | 2004-02-26 | Manufacturing method of plumbing utensils made of lead-containing copper alloy, casting and lead-free products of plumbing utensils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069698A JP4430879B2 (en) | 2003-03-14 | 2003-03-14 | Method for producing lead-containing copper alloy water supply device, casting deleading product of water supply device, and water supply device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004277793A JP2004277793A (en) | 2004-10-07 |
| JP4430879B2 true JP4430879B2 (en) | 2010-03-10 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003069698A Expired - Fee Related JP4430879B2 (en) | 2003-03-14 | 2003-03-14 | Method for producing lead-containing copper alloy water supply device, casting deleading product of water supply device, and water supply device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4430879B2 (en) |
| CN (1) | CN100441744C (en) |
| WO (1) | WO2004081257A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5473781B2 (en) * | 2009-06-01 | 2014-04-16 | 株式会社Lixil | Manufacturing method and processing method for lead-containing copper alloy water supply equipment |
| CN103143890A (en) * | 2013-03-04 | 2013-06-12 | 阮伟光 | Manufacturing method for low lead copper alloy bath utensil |
| JP2018165406A (en) * | 2018-04-20 | 2018-10-25 | 株式会社キッツ | Method for manufacturing water supply equipment made of copper alloy in faucet metal fitting or valve |
| CN114606503A (en) * | 2022-03-10 | 2022-06-10 | 杭州泛亚卫浴股份有限公司 | Tap inner cavity sticky sand removing liquid and sticky sand treatment method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9409811D0 (en) * | 1994-05-17 | 1994-07-06 | Imi Yorkshire Fittings | Improvements in copper alloy water fittings |
| DE69521064T2 (en) * | 1995-08-03 | 2002-01-03 | Europa Metalli S.P.A., Florenz/Firenze | COMPONENT MADE OF LEAD-CONTAINING COPPER ALLOYS WITH LOW LEAD LEAKING AND METHOD FOR THE PRODUCTION THEREOF |
| JP3182765B2 (en) * | 1997-12-03 | 2001-07-03 | 東陶機器株式会社 | Lead elution reduction treatment method for lead-containing copper alloy, lead elution reduction plating method for lead-containing copper alloy, and lead-containing copper alloy water supply device |
| JP3866198B2 (en) * | 2000-10-31 | 2007-01-10 | 株式会社Inax | Lead removal method and faucet fitting for plated products made of lead-containing copper alloy having a cylindrical part, and lead leaching prevention method and faucet fitting for lead-containing copper alloy products |
-
2003
- 2003-03-14 JP JP2003069698A patent/JP4430879B2/en not_active Expired - Fee Related
-
2004
- 2004-02-26 CN CNB2004800065636A patent/CN100441744C/en not_active Expired - Lifetime
- 2004-02-26 WO PCT/JP2004/002320 patent/WO2004081257A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004081257A1 (en) | 2004-09-23 |
| JP2004277793A (en) | 2004-10-07 |
| CN100441744C (en) | 2008-12-10 |
| CN1759205A (en) | 2006-04-12 |
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