WO2022186183A1 - Additive for acidic zinc alloy plating bath, acidic zinc alloy plating bath and zinc alloy plating film - Google Patents
Additive for acidic zinc alloy plating bath, acidic zinc alloy plating bath and zinc alloy plating film Download PDFInfo
- Publication number
- WO2022186183A1 WO2022186183A1 PCT/JP2022/008540 JP2022008540W WO2022186183A1 WO 2022186183 A1 WO2022186183 A1 WO 2022186183A1 JP 2022008540 W JP2022008540 W JP 2022008540W WO 2022186183 A1 WO2022186183 A1 WO 2022186183A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alloy plating
- zinc alloy
- nickel
- zinc
- plating bath
- Prior art date
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- 238000007747 plating Methods 0.000 title claims abstract description 392
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 229
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 46
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 150
- 239000000126 substance Substances 0.000 claims abstract description 109
- 239000004471 Glycine Substances 0.000 claims abstract description 73
- 229920000768 polyamine Polymers 0.000 claims abstract description 71
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 245
- 229910052759 nickel Inorganic materials 0.000 claims description 121
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 46
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 239000011701 zinc Substances 0.000 claims description 41
- 229910052725 zinc Inorganic materials 0.000 claims description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 23
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 17
- 238000005275 alloying Methods 0.000 claims description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 65
- 229910000990 Ni alloy Inorganic materials 0.000 description 64
- 229960002449 glycine Drugs 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 36
- 239000000203 mixture Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 230000008021 deposition Effects 0.000 description 12
- -1 glycinium ions Chemical class 0.000 description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000006172 buffering agent Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000000872 buffer Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 125000003118 aryl group Chemical class 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-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
- CJNRGSHEMCMUOE-UHFFFAOYSA-N 2-piperidin-1-ylethanamine Chemical compound NCCN1CCCCC1 CJNRGSHEMCMUOE-UHFFFAOYSA-N 0.000 description 2
- UVLSCMIEPPWCHZ-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-amine Chemical compound NCCCN1CCNCC1 UVLSCMIEPPWCHZ-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Natural products O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- ZRMOLCPODIMNPJ-UHFFFAOYSA-N 1-[4-(2-hydroxypropyl)piperazin-1-yl]propan-2-ol Chemical compound CC(O)CN1CCN(CC(C)O)CC1 ZRMOLCPODIMNPJ-UHFFFAOYSA-N 0.000 description 1
- NAHSJIQXYWGMJN-UHFFFAOYSA-N 1-cyclohexylpropane-1,3-diamine Chemical compound NCCC(N)C1CCCCC1 NAHSJIQXYWGMJN-UHFFFAOYSA-N 0.000 description 1
- ZYZXXEKBDWCGED-UHFFFAOYSA-N 1-n,2-n-diethylbutane-1,2-diamine Chemical compound CCNCC(CC)NCC ZYZXXEKBDWCGED-UHFFFAOYSA-N 0.000 description 1
- VECZPMZNUKYYOJ-UHFFFAOYSA-N 1-n,2-n-diethylpropane-1,2-diamine Chemical compound CCNCC(C)NCC VECZPMZNUKYYOJ-UHFFFAOYSA-N 0.000 description 1
- WLZRPMGWZLCLGV-UHFFFAOYSA-N 1-n,2-n-dimethylbutane-1,2-diamine Chemical compound CCC(NC)CNC WLZRPMGWZLCLGV-UHFFFAOYSA-N 0.000 description 1
- XCFLRKJSDRTWON-UHFFFAOYSA-N 1-n,3-n-diethylbutane-1,3-diamine Chemical compound CCNCCC(C)NCC XCFLRKJSDRTWON-UHFFFAOYSA-N 0.000 description 1
- DKZBLXUAJDHZQQ-UHFFFAOYSA-N 1-n,3-n-dimethylbutane-1,3-diamine Chemical compound CNCCC(C)NC DKZBLXUAJDHZQQ-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- POIVWEXWFKSJHL-UHFFFAOYSA-N 2-(dimethylamino)propan-2-ol Chemical compound CN(C)C(C)(C)O POIVWEXWFKSJHL-UHFFFAOYSA-N 0.000 description 1
- STMZGJLCKJFMLQ-UHFFFAOYSA-N 2-[3-(2-aminoethyl)cyclohexyl]ethanamine Chemical compound NCCC1CCCC(CCN)C1 STMZGJLCKJFMLQ-UHFFFAOYSA-N 0.000 description 1
- XUXZELZSNNYLRE-UHFFFAOYSA-N 2-[4-(2-aminoethyl)cyclohexyl]ethanamine Chemical compound NCCC1CCC(CCN)CC1 XUXZELZSNNYLRE-UHFFFAOYSA-N 0.000 description 1
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 1
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical class C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 241000080590 Niso Species 0.000 description 1
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- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
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- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
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- 229940043376 ammonium acetate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 150000004283 biguanides Chemical class 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- ULEAQRIQMIQDPJ-UHFFFAOYSA-N butane-1,2-diamine Chemical compound CCC(N)CN ULEAQRIQMIQDPJ-UHFFFAOYSA-N 0.000 description 1
- RGTXVXDNHPWPHH-UHFFFAOYSA-N butane-1,3-diamine Chemical compound CC(N)CCN RGTXVXDNHPWPHH-UHFFFAOYSA-N 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 235000004554 glutamine Nutrition 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 229960001269 glycine hydrochloride Drugs 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DTKANQSCBACEPK-UHFFFAOYSA-N n',n'-bis[3-(dimethylamino)propyl]-n,n-dimethylpropane-1,3-diamine Chemical compound CN(C)CCCN(CCCN(C)C)CCCN(C)C DTKANQSCBACEPK-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- WHDUKLPCKZTPFY-UHFFFAOYSA-N n,n'-diethylbutane-1,4-diamine Chemical compound CCNCCCCNCC WHDUKLPCKZTPFY-UHFFFAOYSA-N 0.000 description 1
- LDQWVRMGQLAWMN-UHFFFAOYSA-N n,n'-diethylhexane-1,6-diamine Chemical compound CCNCCCCCCNCC LDQWVRMGQLAWMN-UHFFFAOYSA-N 0.000 description 1
- BEPGHZIEOVULBU-UHFFFAOYSA-N n,n'-diethylpropane-1,3-diamine Chemical compound CCNCCCNCC BEPGHZIEOVULBU-UHFFFAOYSA-N 0.000 description 1
- CZPRYVBLOUZRGD-UHFFFAOYSA-N n,n'-dimethylbutane-1,4-diamine Chemical compound CNCCCCNC CZPRYVBLOUZRGD-UHFFFAOYSA-N 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- LFBJWQBNKOIOMJ-UHFFFAOYSA-N n,n'-dimethylheptane-1,7-diamine Chemical compound CNCCCCCCCNC LFBJWQBNKOIOMJ-UHFFFAOYSA-N 0.000 description 1
- MDKQJOKKKZNQDG-UHFFFAOYSA-N n,n'-dimethylhexane-1,6-diamine Chemical compound CNCCCCCCNC MDKQJOKKKZNQDG-UHFFFAOYSA-N 0.000 description 1
- BESLVGXJZXNIJE-UHFFFAOYSA-N n,n'-dimethylpentane-1,5-diamine Chemical compound CNCCCCCNC BESLVGXJZXNIJE-UHFFFAOYSA-N 0.000 description 1
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 1
- RWIVICVCHVMHMU-UHFFFAOYSA-N n-aminoethylmorpholine Chemical compound NCCN1CCOCC1 RWIVICVCHVMHMU-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- JAKNYTQAGPEFJB-UHFFFAOYSA-N piperidin-2-amine Chemical compound NC1CCCCN1 JAKNYTQAGPEFJB-UHFFFAOYSA-N 0.000 description 1
- RHPBLLCTOLJFPH-UHFFFAOYSA-N piperidin-2-ylmethanamine Chemical compound NCC1CCCCN1 RHPBLLCTOLJFPH-UHFFFAOYSA-N 0.000 description 1
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical compound NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 description 1
- LTEKQAPRXFBRNN-UHFFFAOYSA-N piperidin-4-ylmethanamine Chemical compound NCC1CCNCC1 LTEKQAPRXFBRNN-UHFFFAOYSA-N 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 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
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
An additive for acidic zinc alloy plating bath according to the present invention is used for obtaining acidic zinc alloy plating bath that can provide a zinc alloy plating film having satisfactory appearance, and contains active components that are a glycine-containing water-soluble substance and an aliphatic polyamine having 12 or less carbon atoms. The glycine/polyamine ratio which is a ratio of the molar concentration in terms of glycine of the glycine-containing water-soluble substance to the molar concentration of the aliphatic polyamine may be preferably 0.1-40 inclusive. The present invention also provides acidic zinc alloy plating bath comprising the additive and a zinc alloy plating film formed with the acidic zinc alloy plating bath.
Description
本発明は、酸性亜鉛合金めっき浴用添加剤、酸性亜鉛合金めっき浴、および亜鉛合金めっき皮膜に関する。
The present invention relates to an additive for an acidic zinc alloy plating bath, an acidic zinc alloy plating bath, and a zinc alloy plating film.
本明細書において、亜鉛合金めっきとは、亜鉛および合金成分ならびに不可避的な不純物からなるめっきをいう。亜鉛合金めっきはめっき中の亜鉛の濃度（質量％）が他の合金元素の濃度（質量％）のいずれよりも高くてもよいし、亜鉛の濃度（質量％）よりも濃度が高い合金元素が含まれていてもよい。
In this specification, zinc alloy plating refers to plating consisting of zinc, alloy components, and unavoidable impurities. In zinc alloy plating, the concentration (% by mass) of zinc in the plating may be higher than the concentration (% by mass) of any other alloying element, or the concentration (% by mass) of the alloying element is higher than the concentration (% by mass) of zinc. may be included.
亜鉛－ニッケル合金、亜鉛－鉄合金、すず－亜鉛合金など亜鉛合金のめっきからなる皮膜（本明細書において「亜鉛合金めっき皮膜」ともいう。）は、自動車用の鋼板やボルトやナットなどの鋼材からなる機械部品をはじめとして、我々の身の回りの部材に対して、耐食性、耐熱性などの機能性を向上させることを目的として広汎に用いられている。
Zinc-nickel alloy, zinc-iron alloy, tin-zinc alloy and other zinc alloy plating films (also referred to as "zinc alloy plating films" in this specification) are steel materials such as steel sheets for automobiles and bolts and nuts. It is widely used for the purpose of improving functionality such as corrosion resistance and heat resistance for members around us, including machine parts made of.
亜鉛合金めっき皮膜は、亜鉛合金めっき皮膜を形成するためのめっき浴（本明細書において「亜鉛合金めっき浴」ともいう。）に被めっき部材を浸漬した状態で電解を行う電気めっきにて形成される。この亜鉛合金めっき浴は、アルカリ浴（例えば特許文献１など）と酸性浴（例えば特許文献２など）とに大別され、アルカリ浴にはシアン化物浴やジンケート型亜鉛合金めっき浴、酸性浴には塩化亜鉛浴や硫酸亜鉛浴がある。求める亜鉛合金めっき皮膜の硬度や光沢性、被めっき部材の形状や大きさ、作業環境などの様々な条件を勘案して、これらの亜鉛合金めっき浴から適切な浴が選択されている。
The zinc alloy plating film is formed by electroplating in which electrolysis is performed while the member to be plated is immersed in a plating bath (also referred to as a “zinc alloy plating bath” in this specification) for forming the zinc alloy plating film. be. This zinc alloy plating bath is roughly divided into an alkaline bath (for example, Patent Document 1, etc.) and an acid bath (eg, Patent Document 2, etc.). There are zinc chloride baths and zinc sulfate baths. An appropriate bath is selected from these zinc alloy plating baths in consideration of various conditions such as the desired hardness and gloss of the zinc alloy plating film, the shape and size of the member to be plated, and the working environment.
特許文献３には、鉄または鋼の鋳造品からなる基材に、酢酸ナトリウム、酢酸カリウム、酢酸アンモニウム、およびこれらの混合体からなる群から選ばれる酢酸塩、亜鉛イオン源、ニッケルイオン源、およびアミノ酢酸を備える電解組成物を接触させること、および基板上に、ニッケル共析率が１０から１８質量％であって内部応力を実質的に有しない亜鉛ニッケル合金層を形成するために電流を印加することを備える亜鉛ニッケル合金層の基材上への堆積方法であって、酢酸塩およびアミノ酢酸はモル比で、酢酸塩：アミノ酢酸塩が約０．３５：１から約０．９１：１の範囲にある方法が開示されている。
In Patent Document 3, a substrate made of cast iron or steel is coated with an acetate selected from the group consisting of sodium acetate, potassium acetate, ammonium acetate, and mixtures thereof, a zinc ion source, a nickel ion source, and contacting an electrolytic composition comprising an aminoacetic acid and applying an electric current to form a zinc-nickel alloy layer on the substrate having a nickel codeposition rate of 10 to 18% by weight and substantially free of internal stress; wherein the acetate and aminoacetate are in a molar ratio of from about 0.35:1 to about 0.91:1 acetate:aminoacetate A method is disclosed that ranges from
これらの亜鉛合金めっき浴の中でも、酸性亜鉛合金めっき浴は、電流効率が高く生産性に優れるという利点がある。しかしながら、膜厚や外観の電流密度依存性が高くなりやすいため、被めっき部材が複雑な形状を有する場合には、付き周り性の低下や外観不良が生じやすくなる傾向がある。近年、生産性を高める観点から、バレルめっきにおいては投入量が増え、ラックでのめっきでは印加電圧を高める傾向がある。このような傾向は、局所的な電流密度の上昇をもたらしやすく、結果、局所的な外観不良が生じやすくなっている。
Among these zinc alloy plating baths, the acidic zinc alloy plating bath has the advantage of high current efficiency and excellent productivity. However, since the current density dependence of the film thickness and appearance tends to increase, when the member to be plated has a complicated shape, there is a tendency that the throwing power tends to decrease and appearance defects tend to occur. In recent years, from the viewpoint of improving productivity, there is a tendency to increase the input amount in barrel plating and increase the applied voltage in rack plating. Such a tendency tends to cause a local increase in current density, and as a result, local appearance defects tend to occur.
本発明は、外観が良好な亜鉛合金めっき皮膜を得ることが可能な酸性亜鉛合金めっき浴を得るために使用される添加剤を提供することを目的とする。また、本発明は、外観が良好な亜鉛合金めっき皮膜を得ることが可能な酸性亜鉛合金めっき浴、および上記の酸性亜鉛合金めっき浴を用いて形成される、外観が良好な亜鉛合金めっき皮膜を提供することを目的とする。
An object of the present invention is to provide an additive used to obtain an acidic zinc alloy plating bath capable of obtaining a zinc alloy plating film with a good appearance. The present invention also provides an acidic zinc alloy plating bath capable of obtaining a zinc alloy plating film with a good appearance, and a zinc alloy plating film with a good appearance formed using the above acidic zinc alloy plating bath. intended to provide
なお、亜鉛合金めっき部材とは、被めっき部材と、この被めっき部材の被めっき面上に形成された亜鉛合金めっき皮膜とを備えた部材をいう。また、亜鉛合金めっき皮膜に関する「外観が良好」とは、従来との対比において、亜鉛合金めっき皮膜に異常析出が生じやすくなる電流密度の下限値が高まること、およびある電流密度において無光沢であった亜鉛合金めっき皮膜が同じ電流密度であっても光沢または半光沢となることの少なくとも一方を満たすことをいう。
A zinc alloy-plated member refers to a member comprising a member to be plated and a zinc alloy plating film formed on the surface of the member to be plated. In addition, "good appearance" with respect to the zinc alloy plating film means that the lower limit of the current density at which abnormal deposition is likely to occur in the zinc alloy plating film is increased compared to the conventional one, and that the zinc alloy plating film is not glossy at a certain current density. It means that the zinc alloy plating film satisfies at least one of bright or semi-bright even at the same current density.
上記課題を解決するために提供される本発明の一態様は、グリシン含有水溶性物質および炭素数１２以下の脂肪族ポリアミンを有効成分として含有することを特徴とする酸性亜鉛合金めっき浴用添加剤である。
One aspect of the present invention provided for solving the above problems is an additive for an acidic zinc alloy plating bath, characterized by containing a glycine-containing water-soluble substance and an aliphatic polyamine having 12 or less carbon atoms as active ingredients. be.
上記の酸性亜鉛合金めっき浴用添加剤が含有する脂肪族ポリアミンは、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミンおよびテトラエチレンペンタミンからなる群から選ばれる１種または２種以上を含んでいてもよい。
The aliphatic polyamine contained in the acidic zinc alloy plating bath additive may contain one or more selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
上記の酸性亜鉛合金めっき浴用添加剤が含有するグリシン含有水溶性物質のグリシン換算モル濃度の脂肪族ポリアミンのモル濃度に対する比であるグリシン／ポリアミン比は、０．１以上４０以下であることが好ましい場合があり、１以上３５以下であることがより好ましい場合があり、４以上３４以下であることが特に好ましい場合がある。
The glycine/polyamine ratio, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance contained in the acidic zinc alloy plating bath additive to the molar concentration of the aliphatic polyamine, is preferably 0.1 or more and 40 or less. 1 or more and 35 or less may be more preferable, and 4 or more and 34 or less may be particularly preferable.
本発明の他の一態様は、浴可溶性亜鉛含有物質と、浴可溶性金属含有物質と、上記の添加剤の有効成分と、を含有することを特徴とする酸性亜鉛合金めっき浴である。
Another aspect of the present invention is an acidic zinc alloy plating bath characterized by containing a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, and the active ingredient of the above additive.
上記の酸性亜鉛合金めっき浴は、ｐＨが４以上６以下であってもよい。
The acidic zinc alloy plating bath may have a pH of 4 or more and 6 or less.
上記の酸性亜鉛合金めっき浴は、ホウ酸フリーであることが好ましい場合がある。
The above acidic zinc alloy plating bath may be preferably free of boric acid.
上記の酸性亜鉛合金めっき浴は、アンモニアフリーであることが好ましい場合がある。
The acidic zinc alloy plating bath described above may preferably be ammonia-free.
上記の酸性亜鉛合金めっき浴は、酢酸含有物質を含有することが好ましい場合がある。
The acidic zinc alloy plating bath described above may preferably contain an acetic acid-containing substance.
上記の酸性亜鉛合金めっき浴は、浴可溶性金属含有物質として、浴可溶性ニッケル含有物質を含んでいてもよく、この場合には、酸性亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜におけるニッケルの共析率が５質量％以上２０質量％以下であってもよい。
The above acidic zinc alloy plating bath may contain a bath-soluble nickel-containing substance as a bath-soluble metal-containing substance. The sedimentation rate may be 5% by mass or more and 20% by mass or less.
上記の酸性亜鉛合金めっき浴は、浴可溶性ニッケル含有物質を含み、グリシン含有水溶性物質のグリシン換算モル濃度の浴可溶性ニッケル含有物質のニッケル換算モル濃度に対する比であるグリシン／ニッケル比が０．１以上であることが好ましい場合がある。
The acidic zinc alloy plating bath contains a bath-soluble nickel-containing substance, and has a glycine/nickel ratio of 0.1, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance. There are cases where it is preferable to be equal to or greater than
上記の酸性亜鉛合金めっき浴は、一次光沢剤および二次光沢剤の少なくとも一種を含有してもよい。
The above acidic zinc alloy plating bath may contain at least one of a primary brightener and a secondary brightener.
本発明の別の一態様は、鉄系材料からなる被めっき部材に亜鉛合金めっき皮膜が形成された亜鉛合金めっき部材の深さプロファイルを測定したときに、亜鉛合金めっきにおける被めっき部材に近位な側に合金元素濃度が相対的に高い合金元素濃縮領域を有しないことを特徴とする亜鉛合金めっき皮膜である。
Another aspect of the present invention is that when measuring the depth profile of a zinc alloy plated member in which a zinc alloy plating film is formed on a member to be plated made of an iron-based material, The zinc alloy plating film is characterized in that it does not have an alloying element-concentrated region having a relatively high alloying element concentration on the other side.
上記の亜鉛合金めっき皮膜はニッケルを合金元素とする亜鉛合金めっき皮膜であって、グリシンおよび炭素数１２以下の脂肪族ポリアミンを含有するめっき浴から形成されたものであることが好ましい。
The zinc alloy plating film described above is a zinc alloy plating film containing nickel as an alloying element, and is preferably formed from a plating bath containing glycine and an aliphatic polyamine having 12 or less carbon atoms.
上記の亜鉛合金めっき皮膜の深さプロファイルにおいて、亜鉛濃度が６０質量％以上であって最表面に最も近い位置を亜鉛合金めっき皮膜の表面側端部、亜鉛濃度が被めっき部材に由来する鉄濃度に等しくなる位置を亜鉛合金めっき皮膜の被めっき部材側端部と定義し、表面側端部から被めっき部材側端部までの領域の長さを亜鉛合金めっき皮膜の厚さと定義したときに、表面側端部から亜鉛合金めっきの厚さの４０％から６０％の範囲からなる中間領域におけるニッケル濃度の平均値［Ｎｉ１］と、被めっき部材側端部から亜鉛合金めっきの厚さの３０％だけ表面側に移動した位置と被めっき部材側端部との範囲からなる初期領域におけるニッケル濃度の最大値［Ｎｉ２］と、間における、ニッケル濃度の最大値［Ｎｉ２］と、は、下記式（１）を満たすことが好ましい場合がある。
［Ｎｉ１］≧［Ｎｉ２］ （１） In the depth profile of the zinc alloy plating film, the zinc concentration is 60 mass% or more and the position closest to the outermost surface is the surface side end of the zinc alloy plating film, and the iron concentration derived from the member to be plated. is defined as the end of the zinc alloy plating film on the side of the member to be plated, and the length of the region from the end on the surface side to the end on the side of the member to be plated is defined as the thickness of the zinc alloy plating film, The average nickel concentration [Ni1] in the intermediate region from 40% to 60% of the zinc alloy plating thickness from the surface side end, and 30% of the zinc alloy plating thickness from the plated member side end The maximum value of nickel concentration [Ni2] in the initial region consisting of the position moved to the surface side and the end portion of the member to be plated, and the maximum value of nickel concentration [Ni2] in between are calculated by the following formula ( It may be preferable to satisfy 1).
[Ni1]≧[Ni2] (1)
［Ｎｉ１］≧［Ｎｉ２］ （１） In the depth profile of the zinc alloy plating film, the zinc concentration is 60 mass% or more and the position closest to the outermost surface is the surface side end of the zinc alloy plating film, and the iron concentration derived from the member to be plated. is defined as the end of the zinc alloy plating film on the side of the member to be plated, and the length of the region from the end on the surface side to the end on the side of the member to be plated is defined as the thickness of the zinc alloy plating film, The average nickel concentration [Ni1] in the intermediate region from 40% to 60% of the zinc alloy plating thickness from the surface side end, and 30% of the zinc alloy plating thickness from the plated member side end The maximum value of nickel concentration [Ni2] in the initial region consisting of the position moved to the surface side and the end portion of the member to be plated, and the maximum value of nickel concentration [Ni2] in between are calculated by the following formula ( It may be preferable to satisfy 1).
[Ni1]≧[Ni2] (1)
本発明に係る添加剤を含有する酸性亜鉛合金めっき浴を用いることにより、外観が良好な亜鉛合金めっき皮膜を得ることができる。また、本発明により、外観が良好な亜鉛合金めっき皮膜を備える亜鉛合金めっき部材を得ることができる。
By using an acidic zinc alloy plating bath containing the additive according to the present invention, a zinc alloy plating film with a good appearance can be obtained. Further, according to the present invention, a zinc alloy plated member having a zinc alloy plated film with a good appearance can be obtained.
以下、本発明について詳しく説明する。
The present invention will be described in detail below.
１．酸性亜鉛合金めっき浴用添加剤
本発明の一実施形態に係る酸性亜鉛合金めっき浴用添加剤（本添加剤）は、有効成分としてグリシン含有水溶性物質およびアミノ基を複数有し炭素数１２以下の脂肪族ポリアミン（本明細書において「ポリアミン（Ａ）」と略記する場合がある。）を含有する。 1. Additive for Acidic Zinc Alloy Plating Bath An additive for an acidic zinc alloy plating bath according to one embodiment of the present invention (this additive) comprises, as active ingredients, a glycine-containing water-soluble substance and a fat having 12 or less carbon atoms and having a plurality of amino groups. group polyamine (which may be abbreviated as "polyamine (A)" in this specification).
本発明の一実施形態に係る酸性亜鉛合金めっき浴用添加剤（本添加剤）は、有効成分としてグリシン含有水溶性物質およびアミノ基を複数有し炭素数１２以下の脂肪族ポリアミン（本明細書において「ポリアミン（Ａ）」と略記する場合がある。）を含有する。 1. Additive for Acidic Zinc Alloy Plating Bath An additive for an acidic zinc alloy plating bath according to one embodiment of the present invention (this additive) comprises, as active ingredients, a glycine-containing water-soluble substance and a fat having 12 or less carbon atoms and having a plurality of amino groups. group polyamine (which may be abbreviated as "polyamine (A)" in this specification).
本明細書において、グリシン含有水溶性物質とは、グリシン、グリシン塩酸塩などめっき浴中でグリシンを与えうる物質であるグリシン源からめっき浴中において生成した、グリシンに基づく水溶性物質である。本実施形態に係るめっき浴は酸性であるから、グリシニウムイオンがグリシン含有水溶性物質の具体例となる。グリシン源の具体例には、グリシンのメチルエステルなどのグリシン誘導体も含まれる。
As used herein, a glycine-containing water-soluble substance is a glycine-based water-soluble substance produced in a plating bath from a glycine source, which is a substance capable of giving glycine in the plating bath, such as glycine and glycine hydrochloride. Since the plating bath according to this embodiment is acidic, glycinium ions are a specific example of the glycine-containing water-soluble substance. Specific examples of glycine sources also include glycine derivatives such as the methyl ester of glycine.
ポリアミン（Ａ）は、炭素数１２以下の脂肪族であり、アミノ基を複数有する限り、他の構造は限定されない。ポリアミン（Ａ）は、１級アミン、２級アミンおよび３級アミンのいずれであってもよい。めっき液中では、ポリアミン（Ａ）は、１つ以上のプロトン（Ｈ+）が付与されてイオン化していてもよい。ポリアミン（Ａ）の具体例については後述する。
The polyamine (A) is aliphatic with 12 or less carbon atoms and has no other structure as long as it has a plurality of amino groups. Polyamine (A) may be any of primary amine, secondary amine and tertiary amine. In the plating solution, the polyamine (A) may be ionized by being given one or more protons (H + ). Specific examples of the polyamine (A) will be described later.
グリシン含有水溶性物質およびポリアミン（Ａ）を含有する酸性亜鉛合金めっき浴からは、光沢外観を有する亜鉛合金めっき皮膜が得られやすい。また、電流密度が高い条件、例えば１０Ａ／ｄｍ2を超える条件で電気めっきが行われた場合でも、得られた亜鉛合金めっき皮膜に異常析出に基づく外観不良が生じにくい。後述するように、外観不良が生じた亜鉛ニッケル合金めっき皮膜では、めっき皮膜のうち、被めっき部材側の端部に近位な領域のめっき、すなわち、めっき処理の初期（通電開始直後）の段階で形成されためっきのニッケル濃度が他の領域に比べて特異的に高くなる傾向がある。このようにニッケル濃度が高くなると、析出しためっき皮膜は黒色化し、銀白色の外観が得られにくくなる。すなわち、めっき皮膜の異常析出、特に外観不良は、めっき初期（通電開始直後）にニッケルが優先的に析出してニッケル濃縮領域（詳細は後述する。）が形成される現象と関連している。
A zinc alloy plating film having a glossy appearance can be easily obtained from an acidic zinc alloy plating bath containing a glycine-containing water-soluble substance and polyamine (A). In addition, even when electroplating is performed under high current density conditions, for example, exceeding 10 A/dm 2 , the resulting zinc alloy plated film is unlikely to have poor appearance due to abnormal deposition. As will be described later, in the zinc-nickel alloy plating film with a defective appearance, the plating of the region proximal to the end of the plated member side of the plating film, that is, the initial stage of the plating process (immediately after the start of energization) The nickel concentration of the plating formed in the area tends to be specifically higher than in other areas. When the nickel concentration increases in this way, the deposited plating film turns black, making it difficult to obtain a silvery white appearance. That is, the abnormal deposition of the plating film, particularly the poor appearance, is related to the phenomenon that nickel is preferentially deposited at the beginning of plating (immediately after the start of current application) to form a nickel-enriched region (details will be described later).
本実施形態に係る亜鉛合金めっき浴のようにグリシン含有水溶性物質およびポリアミン（Ａ）を含有することにより、亜鉛合金めっき皮膜においてニッケル濃縮領域の生成が抑制され、めっき皮膜の外観不良が生じにくくなる。グリシン含有水溶性物質およびポリアミン（Ａ）がニッケル濃縮領域の生成を抑制する理由は定かでない。なお、本添加剤はグリシン以外のアミノ酸を含有していてもよいが、本添加剤に他のアミノ酸（アラニン、グルタミン、グルタミン酸などが例示される。）を含有させても、グリシンと同様の効果は得られない。すなわち、他のアミノ酸は本添加剤の有効成分ではない。
By containing a glycine-containing water-soluble substance and polyamine (A) like the zinc alloy plating bath according to the present embodiment, the formation of a nickel-enriched region in the zinc alloy plating film is suppressed, and the appearance of the plating film is less likely to occur. Become. It is unclear why glycine-containing water-soluble substances and polyamine (A) suppress the formation of nickel-enriched regions. Although the present additive may contain amino acids other than glycine, even if the present additive contains other amino acids (eg, alanine, glutamine, glutamic acid, etc.), the same effect as glycine can be obtained. is not obtained. That is, other amino acids are not active ingredients of the additive.
グリシン含有水溶性物質およびポリアミン（Ａ）を有効成分として含有する本添加剤を含む酸性亜鉛合金めっき浴からは、ニッケル濃縮領域が形成されにくいため、光沢外観を有する亜鉛合金めっき皮膜が安定的に得られやすい。例えば、バレルめっきでは高電流密度のめっき処理が断続的に繰り返されるため、バレルめっきで形成された亜鉛合金めっき皮膜の外観は、めっき初期（通電開始直後）に形成されるめっきの影響を受けやすい。このため、ニッケル濃縮領域が形成されやすい従来技術に係るめっき浴を用いると、得られためっき皮膜の外観が不良となりやすい。これに対し、本実施形態に係るめっき浴はニッケル濃縮領域が形成されにくいため、バレルめっきにおいても外観不良が生じにくい。
From the acidic zinc alloy plating bath containing this additive containing a glycine-containing water-soluble substance and polyamine (A) as active ingredients, a nickel-enriched region is less likely to be formed, so that a zinc alloy plating film with a glossy appearance can be stably formed. easy to obtain. For example, in barrel plating, high current density plating is intermittently repeated, so the appearance of the zinc alloy plating film formed by barrel plating is easily affected by the plating that is formed at the beginning of plating (immediately after the start of energization). . For this reason, if the plating bath according to the prior art, in which the nickel-enriched region is likely to be formed, is used, the appearance of the obtained plating film is likely to be poor. On the other hand, since the nickel-enriched region is less likely to be formed in the plating bath according to the present embodiment, poor appearance is less likely to occur even in barrel plating.
また、本実施形態に係るめっき浴は、電流密度が高い条件で電気めっきが行われた場合でも、得られた亜鉛合金めっき皮膜に異常析出が生じにくい。ラックめっきでは生産性を高めるためにめっきの電流密度が高まる傾向にあるが、本実施形態に係るめっき浴であれば、電流密度を高めた場合であっても、得られた亜鉛合金めっき皮膜に外観不良が生じにくい。
In addition, in the plating bath according to the present embodiment, even when electroplating is performed under conditions of high current density, abnormal deposition is less likely to occur in the obtained zinc alloy plating film. In rack plating, the current density of plating tends to increase in order to increase productivity. Poor appearance is less likely to occur.
グリシン含有水溶性物質のグリシン酸換算のモル濃度の、ポリアミン（Ａ）のモル濃度に対する比であるグリシン／ポリアミン比は、亜鉛合金めっき皮膜にニッケル濃縮領域が生じにくくなることを安定的に実現させる観点から、０．１以上４０以下であることが好ましく、１以上３５以下であることがより好ましく、４以上３５以下であることが特に好ましい。
The glycine/polyamine ratio, which is the ratio of the molar concentration of the glycine-containing water-soluble substance in terms of glycic acid to the molar concentration of the polyamine (A), stably realizes that nickel-enriched regions are less likely to occur in the zinc alloy plating film. From the viewpoint, it is preferably 0.1 or more and 40 or less, more preferably 1 or more and 35 or less, and particularly preferably 4 or more and 35 or less.
このように、グリシン含有水溶性物質およびポリアミン（Ａ）は一次光沢剤としての機能を有することから、通常一次光沢剤として使用される界面活性剤の含有量を低減させることができる。めっき浴中の界面活性剤の含有量が低減されることにより、亜鉛合金めっきの作業性を低下させる発泡の問題を緩和することができる。
Thus, since the glycine-containing water-soluble substance and polyamine (A) function as primary brighteners, the content of surfactants normally used as primary brighteners can be reduced. By reducing the content of the surfactant in the plating bath, the problem of foaming that reduces the workability of zinc alloy plating can be alleviated.
亜鉛合金めっき浴が亜鉛ニッケル合金めっき浴である場合には、当該亜鉛合金めっき浴がグリシン含有水溶性物質およびポリアミン（Ａ）を含有することにより、ニッケル共析率が１０質量％以上２０質量％以下、好ましくは１２質量％以上１８質量％以下、より好ましくは１４質量％以上１６質量％以下の亜鉛ニッケル合金めっき皮膜が得られやすくなることもある。
When the zinc alloy plating bath is a zinc-nickel alloy plating bath, the zinc alloy plating bath contains the glycine-containing water-soluble substance and the polyamine (A), so that the nickel eutectoid ratio is 10% by mass or more and 20% by mass. A zinc-nickel alloy plating film having a content of preferably 12% by mass or more and 18% by mass or less, more preferably 14% by mass or more and 16% by mass or less may be easily obtained.
１級アミンのポリアミン（Ａ）の具体例として、エチレンジアミン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，２－ジアミノブタン、１，３－ジアミノブタン、１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、ビス－（３－アミノプロピル）エーテル、１，２－ビス－（３－アミノプロポキシ）エタン、１，３－ビス－（３－アミノプロポキシ）－２，２'－ジメチルプロパン、アミノエチルエタノールアミン、１，２－ビスアミノシクロヘキサン、１，３－ビスアミノシクロヘキサン、１，４－ビスアミノシクロヘキサン、１，３－ビスアミノメチルシクロヘキサン、１，４－ビスアミノメチルシクロヘキサン、１，３－ビスアミノエチルシクロヘキサン、１，４－ビスアミノエチルシクロヘキサン、１，３－ビスアミノプロピルシクロヘキサン、１，４－ビスアミノプロピルシクロヘキサン、水添４，４'－ジアミノジフェニルメタン、２－アミノピペリジン、４－アミノピペリジン、２－アミノメチルピペリジン、４－アミノメチルピペリジン、２－アミノエチルピペリジン、４－アミノエチルピペリジン、Ｎ－アミノエチルピペリジン、Ｎ－アミノプロピルピペリジン、Ｎ－アミノエチルモルホリン、Ｎ－アミノプロピルモルホリン、イソホロンジアミン、メンタンジアミン、１，４－ビスアミノプロピルピペラジン、ジエチレントリアミン、イミノビスプロピルアミン、メチルイミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、Ｎ－アミノエチルピペラジン、Ｎ－アミノプロピルピペラジン、１，４－ビス（アミノエチルピペラジン）、１，４－ビス（アミノプロピルピペラジン）などが挙げられる。
Specific examples of primary amine polyamine (A) include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis-(3-aminopropyl) ether, 1,2 -bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2'-dimethylpropane, aminoethylethanolamine, 1,2-bisaminocyclohexane, 1,3-bis Aminocyclohexane, 1,4-bisaminocyclohexane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3-bisaminoethylcyclohexane, 1,4-bisaminoethylcyclohexane, 1,3 -bisaminopropylcyclohexane, 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, 2-aminopiperidine, 4-aminopiperidine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 2-amino ethylpiperidine, 4-aminoethylpiperidine, N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis(amino ethylpiperazine), 1,4-bis(aminopropylpiperazine) and the like.
２級アミンのポリアミン（Ａ）の具体例として、Ｎ，Ｎ'－ジメチルエチレンジアミン、Ｎ，Ｎ'－ジメチル－１，２－ジアミノプロパン、Ｎ，Ｎ'－ジメチル－１，３－ジアミノプロパン、Ｎ，Ｎ'－ジメチル－１，２－ジアミノブタン、Ｎ，Ｎ'－ジメチル－１，３－ジアミノブタン、Ｎ，Ｎ'－ジメチル－１，４－ジアミノブタン、Ｎ，Ｎ'－ジメチル－１，５－ジアミノペンタン、Ｎ，Ｎ'－ジメチル－１，６－ジアミノヘキサン、Ｎ，Ｎ'－ジメチル－１，７－ジアミノヘプタン、Ｎ，Ｎ'－ジエチルエチレンジアミン、Ｎ，Ｎ'－ジエチル－１，２－ジアミノプロパン、Ｎ，Ｎ'－ジエチル－１，３－ジアミノプロパン、Ｎ，Ｎ'－ジエチル－１，２－ジアミノブタン、Ｎ，Ｎ'－ジエチル－１，３－ジアミノブタン、Ｎ，Ｎ'－ジエチル－１，４－ジアミノブタン、Ｎ，Ｎ'－ジエチル－１，６－ジアミノヘキサンなどが挙げられる。
Specific examples of secondary amine polyamine (A) include N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N , N′-dimethyl-1,2-diaminobutane, N,N′-dimethyl-1,3-diaminobutane, N,N′-dimethyl-1,4-diaminobutane, N,N′-dimethyl-1, 5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane, N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine, N,N'-diethyl-1, 2-diaminopropane, N,N'-diethyl-1,3-diaminopropane, N,N'-diethyl-1,2-diaminobutane, N,N'-diethyl-1,3-diaminobutane, N,N '-diethyl-1,4-diaminobutane, N,N'-diethyl-1,6-diaminohexane and the like.
３級アミンのポリアミン（Ａ）の具体例として、テトラメチルエチレンジアミン、Ｎ，Ｎ'－ジメチルピペラジン、Ｎ，Ｎ'－ビス（（２－ヒドロキシ）プロピル）ピペラジン、ヘキサメチレンテトラミン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラメチル－１，３－ブタンアミン、２－ジメチルアミノ－２－ヒドロキシプロパン、ジエチルアミノエタノール、Ｎ，Ｎ，Ｎ－トリス（３－ジメチルアミノプロピル）アミン、２，４，６－トリス（Ｎ，Ｎ－ジメチルアミノメチル）フェノール、ヘプタメチルイソビグアニドなどが挙げられる。
Specific examples of the tertiary amine polyamine (A) include tetramethylethylenediamine, N,N'-dimethylpiperazine, N,N'-bis((2-hydroxy)propyl)piperazine, hexamethylenetetramine, N,N,N ',N'-tetramethyl-1,3-butanamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N,N,N-tris(3-dimethylaminopropyl)amine, 2,4,6-tris (N,N-dimethylaminomethyl)phenol, heptamethylisobiguanide and the like.
ポリアミン（Ａ）は１級アミノ基、２級アミノ基および３級アミノ基の２種以上を有していてもよい。そのような化合物として、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ビグアニドが例示される。これらの中でも、効果の安定性の高さ、入手容易性の高さなどの観点から、ポリアミン（Ａ）は、ジエチレントリアミンを含むことが好ましく、ジエチレントリアミンから構成されていることがより好ましい。
The polyamine (A) may have two or more of primary amino groups, secondary amino groups and tertiary amino groups. Examples of such compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and biguanides. Among these, the polyamine (A) preferably contains diethylenetriamine, more preferably composed of diethylenetriamine, from the viewpoint of high stability of the effect, high availability, and the like.
ポリアミン（Ａ）は１種類の化合物から構成されていてもよいし、複数種類の化合物から構成されていてもよい。ポリアミン（Ａ）が複数種類の化合物から構成される場合において、それらの化合物の含有比率は限定されない。求める特性に応じて適宜設定される。
The polyamine (A) may be composed of one type of compound, or may be composed of multiple types of compounds. When the polyamine (A) is composed of multiple types of compounds, the content ratio of those compounds is not limited. It is appropriately set according to the desired characteristics.
ポリアミン（Ａ）の炭素数は、１０以下であることが好ましい場合があり、８以下であることがより好ましい場合があり、６以下であることが特に好ましい場合がある。
The number of carbon atoms in the polyamine (A) may be preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
好ましいポリアミン（Ａ）として、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミンおよびテトラエチレンペンタミンを例示することができ、これらの中でも、エチレンジアミン、ジエチレントリアミンおよびトリエチレンテトラミンがより好ましいポリアミン（Ａ）として例示される。
Examples of preferred polyamines (A) include ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, and among these, ethylenediamine, diethylenetriamine and triethylenetetramine are more preferred polyamines (A).
ポリアミン（Ａ）は、カルボニル基およびカルボニル基を含む基のいずれも有していないことが好ましい場合もある。
In some cases, the polyamine (A) preferably has neither a carbonyl group nor a group containing a carbonyl group.
本添加剤は、ポリアミン（Ａ）以外の成分を含有していてもよい。そのような成分として、一次光沢剤、二次光沢剤、酸化防止剤、消泡剤、金属封鎖剤などが例示される。なお、本発明の一実施形態に係る添加剤が含有するポリアミン（Ａ）は、一次光沢剤や二次光沢剤としての機能を有することから、本添加剤は一次光沢剤および二次光沢剤の少なくとも一方を含有していなくてもよい。
The additive may contain components other than polyamine (A). Examples of such components include primary brighteners, secondary brighteners, antioxidants, defoamers, sequestering agents, and the like. The polyamine (A) contained in the additive according to one embodiment of the present invention functions as a primary brightener and a secondary brightener. At least one may not be contained.
２．酸性亜鉛合金めっき浴
本発明の一実施形態に係る亜鉛合金めっき浴は酸性であるため、アルカリ性の亜鉛合金めっき浴に比べて電流効率が高く、生産性に優れる。本発明の一実施形態に係る亜鉛合金めっき浴は、浴可溶性亜鉛含有物質、浴可溶性金属含有物質、上記のグリシン含有水溶性物質およびポリアミン（Ａ）を含有する。このため、本実施形態に係る亜鉛合金めっき浴から形成された白銀色の亜鉛合金めっき皮膜の外観は良好となりやすい。 2. Acidic Zinc Alloy Plating Bath Since the zinc alloy plating bath according to one embodiment of the present invention is acidic, it has high current efficiency and excellent productivity compared to alkaline zinc alloy plating baths. A zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, the above water-soluble glycine-containing substance, and polyamine (A). Therefore, the silver-white zinc alloy plating film formed from the zinc alloy plating bath according to the present embodiment tends to have a good appearance.
本発明の一実施形態に係る亜鉛合金めっき浴は酸性であるため、アルカリ性の亜鉛合金めっき浴に比べて電流効率が高く、生産性に優れる。本発明の一実施形態に係る亜鉛合金めっき浴は、浴可溶性亜鉛含有物質、浴可溶性金属含有物質、上記のグリシン含有水溶性物質およびポリアミン（Ａ）を含有する。このため、本実施形態に係る亜鉛合金めっき浴から形成された白銀色の亜鉛合金めっき皮膜の外観は良好となりやすい。 2. Acidic Zinc Alloy Plating Bath Since the zinc alloy plating bath according to one embodiment of the present invention is acidic, it has high current efficiency and excellent productivity compared to alkaline zinc alloy plating baths. A zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, the above water-soluble glycine-containing substance, and polyamine (A). Therefore, the silver-white zinc alloy plating film formed from the zinc alloy plating bath according to the present embodiment tends to have a good appearance.
（１）金属成分
（１－１）浴可溶性亜鉛含有物質
本実施形態に係る亜鉛合金めっき浴は、浴可溶性亜鉛含有物質を含有する。本明細書において浴可溶性亜鉛含有物質とは、亜鉛合金めっき皮膜として析出する亜鉛の供給源であって、亜鉛の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる１種または２種以上の成分をいう。本実施形態に係る亜鉛合金めっき浴は酸性であるから、浴可溶性亜鉛含有物質の一例は亜鉛イオン（Ｚｎ2+）である。浴可溶性亜鉛含有物質をめっき浴に供給する原料物質（本発明において、「亜鉛源」ともいう。）として、塩化亜鉛、硫酸亜鉛、酸化亜鉛などが例示される。 (1) Metal Components (1-1) Bath-Soluble Zinc-Containing Substance The zinc alloy plating bath according to the present embodiment contains a bath-soluble zinc-containing substance. In the present specification, the bath-soluble zinc-containing substance is a source of zinc deposited as a zinc alloy plating film, and is one or two selected from the group consisting of zinc cations and bath-soluble substances containing the same. The above ingredients. Since the zinc alloy plating bath according to this embodiment is acidic, an example of bath-soluble zinc-containing substances is zinc ions (Zn 2+ ). Zinc chloride, zinc sulfate, zinc oxide and the like are exemplified as raw materials for supplying bath-soluble zinc-containing substances to the plating bath (also referred to as "zinc source" in the present invention).
（１－１）浴可溶性亜鉛含有物質
本実施形態に係る亜鉛合金めっき浴は、浴可溶性亜鉛含有物質を含有する。本明細書において浴可溶性亜鉛含有物質とは、亜鉛合金めっき皮膜として析出する亜鉛の供給源であって、亜鉛の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる１種または２種以上の成分をいう。本実施形態に係る亜鉛合金めっき浴は酸性であるから、浴可溶性亜鉛含有物質の一例は亜鉛イオン（Ｚｎ2+）である。浴可溶性亜鉛含有物質をめっき浴に供給する原料物質（本発明において、「亜鉛源」ともいう。）として、塩化亜鉛、硫酸亜鉛、酸化亜鉛などが例示される。 (1) Metal Components (1-1) Bath-Soluble Zinc-Containing Substance The zinc alloy plating bath according to the present embodiment contains a bath-soluble zinc-containing substance. In the present specification, the bath-soluble zinc-containing substance is a source of zinc deposited as a zinc alloy plating film, and is one or two selected from the group consisting of zinc cations and bath-soluble substances containing the same. The above ingredients. Since the zinc alloy plating bath according to this embodiment is acidic, an example of bath-soluble zinc-containing substances is zinc ions (Zn 2+ ). Zinc chloride, zinc sulfate, zinc oxide and the like are exemplified as raw materials for supplying bath-soluble zinc-containing substances to the plating bath (also referred to as "zinc source" in the present invention).
本実施形態に係る亜鉛合金めっき浴における可溶性亜鉛含有物質の亜鉛換算含有量（可溶性亜鉛含有物質の亜鉛換算の浴中含有量）は限定されない。この含有量が過度に少ない場合には亜鉛合金めっき皮膜が析出しにくくなることもあるため、上記の亜鉛換算含有量は５ｇ／Ｌ以上であることが好ましく、１０ｇ／Ｌ以上であることがより好ましく、１５ｇ／Ｌ以上であることが特に好ましい。可溶性亜鉛含有物質の亜鉛換算含有量が過度に多い場合には外観不良やつきまわり性の低下が生じやすくなることもあるため、上記の亜鉛換算含有量は１００ｇ／Ｌ以下であることが好ましく、８０ｇ／Ｌ以下であることがより好ましく、６０ｇ／Ｌ以下であることが特に好ましい。
The content of the soluble zinc-containing substance in terms of zinc (the content of the soluble zinc-containing substance in the bath in terms of zinc) in the zinc alloy plating bath according to the present embodiment is not limited. If the content is excessively small, the zinc alloy plating film may be difficult to deposit, so the content in terms of zinc is preferably 5 g / L or more, more preferably 10 g / L or more. It is preferably 15 g/L or more, and particularly preferably 15 g/L or more. If the zinc conversion content of the soluble zinc-containing substance is excessively large, poor appearance and decreased throwing power may occur, so the above zinc conversion content is preferably 100 g / L or less. It is more preferably 80 g/L or less, particularly preferably 60 g/L or less.
（１－２）浴可溶性金属含有物質
本発明の一実施形態に係る亜鉛合金めっき浴は、浴可溶性金属含有物質を含有する。本明細書において浴可溶性金属含有物質とは、亜鉛合金めっき皮膜に含有される亜鉛以外の金属の供給源であって、金属元素の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる一種または二種以上の成分をいう。浴可溶性金属含有物質に含有される金属元素として、鉄、ニッケル、およびスズが例示される。好ましい一例において、金属含有物質に含まれる金属元素は鉄、ニッケル、およびスズからなる群から選ばれる。 (1-2) Bath-Soluble Metal-Containing Substance The zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble metal-containing substance. In the present specification, the bath-soluble metal-containing substance is a source of metal other than zinc contained in the zinc alloy plating film, and is selected from the group consisting of cations of metal elements and bath-soluble substances containing the same. Refers to one or more components. Examples of metal elements contained in the bath-soluble metal-containing substance include iron, nickel, and tin. In one preferred example, the metal element contained in the metal-containing substance is selected from the group consisting of iron, nickel, and tin.
本発明の一実施形態に係る亜鉛合金めっき浴は、浴可溶性金属含有物質を含有する。本明細書において浴可溶性金属含有物質とは、亜鉛合金めっき皮膜に含有される亜鉛以外の金属の供給源であって、金属元素の陽イオンおよびこれを含有する浴可溶性物質からなる群から選ばれる一種または二種以上の成分をいう。浴可溶性金属含有物質に含有される金属元素として、鉄、ニッケル、およびスズが例示される。好ましい一例において、金属含有物質に含まれる金属元素は鉄、ニッケル、およびスズからなる群から選ばれる。 (1-2) Bath-Soluble Metal-Containing Substance The zinc alloy plating bath according to one embodiment of the present invention contains a bath-soluble metal-containing substance. In the present specification, the bath-soluble metal-containing substance is a source of metal other than zinc contained in the zinc alloy plating film, and is selected from the group consisting of cations of metal elements and bath-soluble substances containing the same. Refers to one or more components. Examples of metal elements contained in the bath-soluble metal-containing substance include iron, nickel, and tin. In one preferred example, the metal element contained in the metal-containing substance is selected from the group consisting of iron, nickel, and tin.
浴可溶性金属含有物質をめっき浴に供給する原料物質（本発明において、「金属源」ともいう。）はその浴可溶性金属含有物質に含有される金属元素の種類に応じて適宜選択すればよい。例えば、浴可溶性金属含有物質に含有される金属元素が鉄である場合、すなわち、亜鉛合金めっき浴が浴可溶性鉄含有物質を含有する場合には、Ｆｅ2（ＳＯ4）3・７Ｈ2Ｏ、ＦｅＳＯ4・７Ｈ2Ｏ、Ｆｅ（ＯＨ）3、ＦｅＣｌ3・６Ｈ2Ｏ、ＦｅＣｌ2・４Ｈ2Ｏなどが鉄源として例示される。浴可溶性金属含有物質に含有される金属元素がニッケルである場合、すなわち、亜鉛合金めっき浴が浴可溶性ニッケル含有物質を含有する場合には、ＮｉＳＯ4・６Ｈ2Ｏ、ＮｉＣｌ2・６Ｈ2Ｏ，Ｎｉ（ＯＨ）2などがニッケル源として例示される。浴可溶性金属含有物質に含有される金属元素がスズである場合、すなわち、亜鉛合金めっき浴が浴可溶性スズ含有物質を含有する場合には、ＳｎＳＯ4、ＳｎＣｌ2、ＳｎＣｌ2・２Ｈ2Ｏなどがスズ源として例示される。
The raw material for supplying the bath-soluble metal-containing substance to the plating bath (also referred to as "metal source" in the present invention) may be appropriately selected according to the type of metal element contained in the bath-soluble metal-containing substance. For example, when the metal element contained in the bath-soluble metal-containing substance is iron, that is, when the zinc alloy plating bath contains the bath-soluble iron-containing substance, Fe 2 (SO 4 ) 3.7H 2 O, FeSO 4 .7H 2 O, Fe(OH) 3 , FeCl 3 .6H 2 O, FeCl 2 .4H 2 O and the like are exemplified as iron sources. When the metal element contained in the bath-soluble metal-containing substance is nickel, that is, when the zinc alloy plating bath contains the bath-soluble nickel-containing substance, NiSO 4 .6H 2 O, NiCl 2 .6H 2 O, Ni(OH) 2 and the like are exemplified as nickel sources. When the metal element contained in the bath-soluble metal-containing substance is tin, that is, when the zinc alloy plating bath contains the bath-soluble tin-containing substance, SnSO 4 , SnCl 2 , SnCl 2 .2H 2 O, etc. Exemplified as a tin source.
本発明の一実施形態に係る亜鉛合金めっき浴における浴可溶性金属含有物質の金属換算含有量は、目的とする亜鉛合金めっきの組成に応じて適宜設定される。亜鉛合金めっき浴が浴可溶性鉄含有物質を含有する場合には、浴可溶性鉄含有物質の鉄換算含有量を１ｇ／Ｌ以上１００ｇ／Ｌ以下程度とすることが例示される。亜鉛合金めっき浴が浴可溶性ニッケル含有物質を含有する場合には、浴可溶性ニッケル含有物質のニッケル換算含有量を０．１ｇ／Ｌ以上６０ｇ／Ｌ以下程度とすることが例示される。亜鉛合金めっき浴が浴可溶性スズ含有物質を含有する場合には、浴可溶性スズ含有物質のスズ換算含有量を１ｇ／Ｌ以上１００ｇ／Ｌ以下程度とすることが例示される。亜鉛合金めっき皮膜における合金元素の含有率（共析率）は、めっき浴の特性、合金元素の種類、用途などにより設定される。
The metal equivalent content of the bath-soluble metal-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is appropriately set according to the composition of the target zinc alloy plating. When the zinc alloy plating bath contains a bath-soluble iron-containing substance, the content of the bath-soluble iron-containing substance in terms of iron is exemplified to be about 1 g/L or more and 100 g/L or less. When the zinc alloy plating bath contains a bath-soluble nickel-containing substance, the content of the bath-soluble nickel-containing substance in terms of nickel is exemplified to be about 0.1 g/L or more and 60 g/L or less. When the zinc alloy plating bath contains a bath-soluble tin-containing substance, the tin-equivalent content of the bath-soluble tin-containing substance is exemplified to be about 1 g/L or more and 100 g/L or less. The alloying element content (eutectoid ratio) in the zinc alloy plating film is set according to the properties of the plating bath, the type of alloying elements, the application, and the like.
本発明の一実施形態に係る亜鉛合金めっき浴に含有される合金元素がニッケルである場合には、亜鉛合金めっき浴により得られる亜鉛ニッケル合金めっき皮膜のニッケルの共析率は、耐食性を高める観点から、５質量％以上２０質量％以下であることが好ましい。ニッケルの含有率が１０質量％以上である亜鉛ニッケル合金は耐食性に特に優れることから、耐食性に特に優れることが求められる場合には、亜鉛ニッケル合金めっき皮膜におけるニッケルの共析率は１０質量％以上２０質量％以下であることが好ましく、耐食性の高さと皮膜の組成の均一性を高める観点から、ニッケルの共析率は１２質量％以上１８質量％以下であることがより好ましい。特に高い耐食性は要求されない用途である場合には、耐食性と生産性（生産コスト）とのバランスを考慮して、亜鉛ニッケル合金めっき皮膜におけるニッケルの共析率を５質量％以上１０質量％未満とすることが好ましい場合がある。なお、ニッケルの共析率は、浴組成や電流密度を変更することにより調整することが可能である。
When the alloying element contained in the zinc alloy plating bath according to one embodiment of the present invention is nickel, the eutectoid ratio of nickel in the zinc-nickel alloy plating film obtained from the zinc alloy plating bath is from the viewpoint of enhancing corrosion resistance. Therefore, it is preferably 5% by mass or more and 20% by mass or less. A zinc-nickel alloy with a nickel content of 10% by mass or more is particularly excellent in corrosion resistance. Therefore, when particularly excellent corrosion resistance is required, the nickel eutectoid ratio in the zinc-nickel alloy plating film should be 10% by mass or more. The eutectoid ratio of nickel is preferably 20% by mass or less, and more preferably 12% by mass or more and 18% by mass or less from the viewpoint of enhancing corrosion resistance and uniformity of the composition of the coating. If the application does not require particularly high corrosion resistance, the eutectoid ratio of nickel in the zinc-nickel alloy plating film should be 5% by mass or more and less than 10% by mass in consideration of the balance between corrosion resistance and productivity (production cost). It may be preferable to The eutectoid rate of nickel can be adjusted by changing the bath composition and current density.
（２）添加剤成分
本発明の一実施形態に係る亜鉛合金めっき浴は前述のグリシン含有水溶性物質およびポリアミン（Ａ）を有効成分として含有する。他の添加剤成分を含有してもよい。 (2) Additive component A zinc alloy plating bath according to one embodiment of the present invention contains the aforementioned glycine-containing water-soluble substance and polyamine (A) as active components. It may contain other additive components.
本発明の一実施形態に係る亜鉛合金めっき浴は前述のグリシン含有水溶性物質およびポリアミン（Ａ）を有効成分として含有する。他の添加剤成分を含有してもよい。 (2) Additive component A zinc alloy plating bath according to one embodiment of the present invention contains the aforementioned glycine-containing water-soluble substance and polyamine (A) as active components. It may contain other additive components.
（２－１）グリシン含有水溶性物質
本発明の一実施形態に係る亜鉛合金めっき浴は、前述のグリシン含有水溶性物質を含有する。グリシン含有水溶性物質の含有量は、亜鉛合金めっき浴に含有されるグリシン含有水溶性物質以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。本発明の一実施形態に係る亜鉛合金めっき浴におけるグリシン含有水溶性物質のグリシン換算含有量は、限定されない一例として、０．１ｇ／Ｌ以上１００ｇ／Ｌ以下が挙げられる。グリシン含有水溶性物質が０．１ｇ／Ｌ以上であることにより、グリシン含有水溶性物質を含有させた効果が得られやすくなる。また、グリシン含有水溶性物質が１００ｇ／Ｌ以下であればめっき浴への当該物質の溶解は十分に可能である。めっき浴の組成を設定するにあたり、他の成分の含有量の調整範囲に与える影響を少なくする観点から、グリシン含有水溶性物質は、７０ｇ／Ｌ以下であることが好ましい場合がある。 (2-1) Glycine-Containing Water-Soluble Substance A zinc alloy plating bath according to an embodiment of the present invention contains the above-described glycine-containing water-soluble substance. The content of the glycine-containing water-soluble substance depends on the type and content of components other than the glycine-containing water-soluble substance contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, etc. Appropriately set. A non-limiting example of the glycine-equivalent content of the glycine-containing water-soluble substance in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less. When the glycine-containing water-soluble substance is 0.1 g/L or more, the effect of containing the glycine-containing water-soluble substance can be easily obtained. Also, if the glycine-containing water-soluble substance is 100 g/L or less, the substance can be sufficiently dissolved in the plating bath. In setting the composition of the plating bath, it is sometimes preferable that the content of the glycine-containing water-soluble substance is 70 g/L or less from the viewpoint of reducing the influence on the adjustment range of the contents of other components.
本発明の一実施形態に係る亜鉛合金めっき浴は、前述のグリシン含有水溶性物質を含有する。グリシン含有水溶性物質の含有量は、亜鉛合金めっき浴に含有されるグリシン含有水溶性物質以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。本発明の一実施形態に係る亜鉛合金めっき浴におけるグリシン含有水溶性物質のグリシン換算含有量は、限定されない一例として、０．１ｇ／Ｌ以上１００ｇ／Ｌ以下が挙げられる。グリシン含有水溶性物質が０．１ｇ／Ｌ以上であることにより、グリシン含有水溶性物質を含有させた効果が得られやすくなる。また、グリシン含有水溶性物質が１００ｇ／Ｌ以下であればめっき浴への当該物質の溶解は十分に可能である。めっき浴の組成を設定するにあたり、他の成分の含有量の調整範囲に与える影響を少なくする観点から、グリシン含有水溶性物質は、７０ｇ／Ｌ以下であることが好ましい場合がある。 (2-1) Glycine-Containing Water-Soluble Substance A zinc alloy plating bath according to an embodiment of the present invention contains the above-described glycine-containing water-soluble substance. The content of the glycine-containing water-soluble substance depends on the type and content of components other than the glycine-containing water-soluble substance contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, etc. Appropriately set. A non-limiting example of the glycine-equivalent content of the glycine-containing water-soluble substance in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less. When the glycine-containing water-soluble substance is 0.1 g/L or more, the effect of containing the glycine-containing water-soluble substance can be easily obtained. Also, if the glycine-containing water-soluble substance is 100 g/L or less, the substance can be sufficiently dissolved in the plating bath. In setting the composition of the plating bath, it is sometimes preferable that the content of the glycine-containing water-soluble substance is 70 g/L or less from the viewpoint of reducing the influence on the adjustment range of the contents of other components.
亜鉛合金めっきの合金元素がニッケルである場合には、上記のように、グリシン含有水溶性物質およびポリアミン（Ａ）は、めっき初期（通電開始直後）にニッケルの優先析出が生じることを抑制することができる。この機能を安定的に果たす観点から、亜鉛合金めっき浴におけるグリシン含有水溶性物質は、１ｇ／Ｌ以上とすることが好ましい場合があり、１０ｇ／Ｌ以上とすることがより好ましい場合がある。
When the alloying element of the zinc alloy plating is nickel, as described above, the glycine-containing water-soluble substance and the polyamine (A) suppress the preferential deposition of nickel at the initial stage of plating (immediately after the start of energization). can be done. From the viewpoint of stably performing this function, the glycine-containing water-soluble substance in the zinc alloy plating bath may be preferably 1 g/L or more, and more preferably 10 g/L or more.
また、グリシン含有水溶性物質はニッケル析出との関連性が深いことから、グリシン含有水溶性物質のグリシン換算モル濃度の浴可溶性ニッケル含有物質のニッケル換算モル濃度に対する比であるグリシン／ニッケル比が０．１以上であることが好ましい場合があり、０．５以上であることがより好ましい場合があり、１．２以上であることが特に好ましい場合があり、１．４以上であることが極めて好ましい場合がある。グリシン／ニッケル比の上限はめっき皮膜の外観を向上させる観点からは設定されない。グリシン含有水溶性物質の含有量が大過剰であると、他の成分（例えばカリウム含有成分）の含有量を調整することが必要になる場合があるため、グリシン／ニッケル比は、３以下とすることが好ましいこともあり、２以下とすることがより好ましいことがある。なお、グリシン／ニッケル比が亜鉛合金めっき皮膜におけるニッケルの共析率に与える影響は少ない。
In addition, since the glycine-containing water-soluble substance is closely related to nickel deposition, the glycine/nickel ratio, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance, is 0. .1 or greater may be preferred, 0.5 or greater may be more preferred, 1.2 or greater may be particularly preferred, and 1.4 or greater is highly preferred. Sometimes. The upper limit of the glycine/nickel ratio is not set from the viewpoint of improving the appearance of the plating film. If the content of the glycine-containing water-soluble substance is excessively large, it may be necessary to adjust the content of other components (for example, potassium-containing components), so the glycine/nickel ratio is 3 or less. is sometimes preferable, and sometimes it is more preferable to be 2 or less. The glycine/nickel ratio has little effect on the eutectoid ratio of nickel in the zinc alloy plating film.
（２－２）ポリアミン（Ａ）
本発明の一実施形態に係る亜鉛合金めっき浴は、前述のポリアミン（Ａ）を含有する。ポリアミン（Ａ）の含有量は、ポリアミン（Ａ）の種類、亜鉛合金めっき浴に含有されるポリアミン（Ａ）以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。本発明の一実施形態に係る亜鉛合金めっき浴におけるポリアミン（Ａ）の含有量は、限定されない一例として、０．１ｇ／Ｌ以上１００ｇ／Ｌ以下が挙げられる。ポリアミン（Ａ）が０．１ｇ／Ｌ以上であることにより、ポリアミン（Ａ）を含有させた効果が得られやすくなる。また、ポリアミン（Ａ）が１００ｇ／Ｌ以下であることにより、浴中に不溶性物質が生じる可能性が低減される。 (2-2) Polyamine (A)
A zinc alloy plating bath according to one embodiment of the present invention contains the polyamine (A) described above. The content of polyamine (A) depends on the type of polyamine (A), the type and content of components other than polyamine (A) contained in the zinc alloy plating bath, and the zinc alloy plating film formed from the zinc alloy plating bath. It is appropriately set according to the composition and the like. A non-limiting example of the content of the polyamine (A) in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less. When the polyamine (A) is 0.1 g/L or more, the effect of containing the polyamine (A) can be easily obtained. In addition, when the polyamine (A) is 100 g/L or less, the possibility of generating insoluble substances in the bath is reduced.
本発明の一実施形態に係る亜鉛合金めっき浴は、前述のポリアミン（Ａ）を含有する。ポリアミン（Ａ）の含有量は、ポリアミン（Ａ）の種類、亜鉛合金めっき浴に含有されるポリアミン（Ａ）以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。本発明の一実施形態に係る亜鉛合金めっき浴におけるポリアミン（Ａ）の含有量は、限定されない一例として、０．１ｇ／Ｌ以上１００ｇ／Ｌ以下が挙げられる。ポリアミン（Ａ）が０．１ｇ／Ｌ以上であることにより、ポリアミン（Ａ）を含有させた効果が得られやすくなる。また、ポリアミン（Ａ）が１００ｇ／Ｌ以下であることにより、浴中に不溶性物質が生じる可能性が低減される。 (2-2) Polyamine (A)
A zinc alloy plating bath according to one embodiment of the present invention contains the polyamine (A) described above. The content of polyamine (A) depends on the type of polyamine (A), the type and content of components other than polyamine (A) contained in the zinc alloy plating bath, and the zinc alloy plating film formed from the zinc alloy plating bath. It is appropriately set according to the composition and the like. A non-limiting example of the content of the polyamine (A) in the zinc alloy plating bath according to one embodiment of the present invention is 0.1 g/L or more and 100 g/L or less. When the polyamine (A) is 0.1 g/L or more, the effect of containing the polyamine (A) can be easily obtained. In addition, when the polyamine (A) is 100 g/L or less, the possibility of generating insoluble substances in the bath is reduced.
亜鉛合金めっき浴の種類によっては、亜鉛合金めっき浴におけるポリアミン（Ａ）が所定の含有量以下であることにより、亜鉛合金めっき浴から形成された亜鉛合金めっき皮膜の外観をより安定的に良好にすることが可能となる場合もある。例えば、亜鉛合金めっきが亜鉛ニッケル合金めっきである場合には、ポリアミン（Ａ）の含有量が３０ｇ／Ｌ以下であることにより、当該亜鉛ニッケル合金めっき浴から形成された亜鉛ニッケル合金めっき皮膜の外観が良好となることが安定的に生じやすくなることがある。亜鉛ニッケル合金めっき皮膜の外観が良好となることをより安定的に生じさせる観点から、ポリアミン（Ａ）の含有量は、２０ｇ／Ｌ以下であることが好ましいこともある。
Depending on the type of zinc alloy plating bath, the appearance of the zinc alloy plating film formed from the zinc alloy plating bath can be more stably improved by setting the polyamine (A) in the zinc alloy plating bath to a predetermined content or less. It may be possible to do so. For example, when the zinc alloy plating is zinc-nickel alloy plating, the content of the polyamine (A) is 30 g/L or less, so that the appearance of the zinc-nickel alloy plating film formed from the zinc-nickel alloy plating bath is It may become easier to stably produce good results. In some cases, the content of the polyamine (A) is preferably 20 g/L or less from the viewpoint of more stably improving the appearance of the zinc-nickel alloy plating film.
（２－３）その他の添加剤成分
本発明の一実施形態に係る亜鉛合金めっき浴は、上記のポリアミン（Ａ）以外の添加剤成分を含有してもよい。そのような添加剤成分または亜鉛合金めっき浴中で添加剤成分を与える材料として、次のようなものが例示される。 (2-3) Other Additive Components The zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the polyamine (A) described above. Examples of such additive components or materials that provide additive components in zinc alloy plating baths include the following.
本発明の一実施形態に係る亜鉛合金めっき浴は、上記のポリアミン（Ａ）以外の添加剤成分を含有してもよい。そのような添加剤成分または亜鉛合金めっき浴中で添加剤成分を与える材料として、次のようなものが例示される。 (2-3) Other Additive Components The zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the polyamine (A) described above. Examples of such additive components or materials that provide additive components in zinc alloy plating baths include the following.
（２－３－１）一次光沢剤
本発明の一実施形態に係る亜鉛合金めっき浴は、添加剤成分の一種として一次光沢剤を含有してもよい。かかる一次光沢剤の例として、各種亜鉛めっき浴に使用されるアニオン系界面活性剤、ノニオン系界面活性剤および水溶性カチオン高分子化合物などの水溶性の有機化合物などを挙げることができる。 (2-3-1) Primary Brightener The zinc alloy plating bath according to one embodiment of the present invention may contain a primary brightener as one of additive components. Examples of such primary brighteners include anionic surfactants, nonionic surfactants and water-soluble organic compounds such as water-soluble cationic polymer compounds used in various zinc plating baths.
本発明の一実施形態に係る亜鉛合金めっき浴は、添加剤成分の一種として一次光沢剤を含有してもよい。かかる一次光沢剤の例として、各種亜鉛めっき浴に使用されるアニオン系界面活性剤、ノニオン系界面活性剤および水溶性カチオン高分子化合物などの水溶性の有機化合物などを挙げることができる。 (2-3-1) Primary Brightener The zinc alloy plating bath according to one embodiment of the present invention may contain a primary brightener as one of additive components. Examples of such primary brighteners include anionic surfactants, nonionic surfactants and water-soluble organic compounds such as water-soluble cationic polymer compounds used in various zinc plating baths.
一次光沢剤は、スルホン酸基のようなアニオン系界面活性剤に含有される構造およびポリエーテルのようなノニオン系界面活性剤に含有される構造の双方を有していてもよい。そのような化合物として、芳香族または脂肪族のポリエーテル硫酸エステルのアルカリ金属塩が挙げられる。
The primary brightener may have both a structure contained in anionic surfactants such as sulfonic acid groups and a structure contained in nonionic surfactants such as polyethers. Such compounds include alkali metal salts of aromatic or aliphatic polyether sulfates.
本発明の一実施形態に係る亜鉛合金めっき浴が一次光沢剤を含有する場合において、一次光沢剤は窒素を含有しない界面活性剤であることが好ましい場合もある。そのような界面活性剤の具体例として、上記の芳香族または脂肪族のポリエーテル硫酸エステルアルカリ金属塩、アセチレン系ジアルコールのポリエーテル化合物が挙げられる。
When the zinc alloy plating bath according to one embodiment of the present invention contains a primary brightener, the primary brightener may preferably be a nitrogen-free surfactant. Specific examples of such surfactants include the above aromatic or aliphatic polyether sulfate ester alkali metal salts and polyether compounds of acetylenic dialcohols.
本発明の一実施形態に係る亜鉛合金めっき浴が一次光沢剤を含有する場合において、一次光沢剤の亜鉛合金めっき浴中含有量は限定されない。一次光沢剤の種類、亜鉛合金めっき浴に含有される一次光沢剤以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。一例を挙げれば、一次光沢剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。
When the zinc alloy plating bath according to one embodiment of the present invention contains a primary brightener, the content of the primary brightener in the zinc alloy plating bath is not limited. It is appropriately set according to the type of primary brightener, the type and content of components other than the primary brightener contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, and the like. For example, the content of the primary brightener is preferably 0.1 g/L or more and 100 g/L or less, more preferably 0.5 g/L or more and 20 g/L or less.
なお、前述のように、ポリアミン（Ａ）は一次光沢剤としての機能を有することから、界面活性剤からなる一次光沢剤の含有量を低減させることができる。めっき浴中の界面活性剤の含有量が低減されることにより、亜鉛合金めっきの作業性を低下させる発泡の問題を緩和することができる。
As described above, since the polyamine (A) functions as a primary brightener, it is possible to reduce the content of the primary brightener composed of a surfactant. By reducing the content of the surfactant in the plating bath, the problem of foaming that reduces the workability of zinc alloy plating can be alleviated.
（２－３－２）二次光沢剤
本発明の一実施形態に係る亜鉛合金めっき浴は、添加剤成分の一種として二次光沢剤を含有してもよい。特に、光沢性の向上などの観点からは、二次光沢剤として、カルボニル基を有する芳香族化合物を含有してもよい。そのような化合物として、アニスアルデヒド、ベラトルアルデヒド、ｏ－クロロベンズアルデヒド（ＯＣＡＤ）、サリチルアルデヒド、バニリン、ピペロナールおよびｐ－ヒドロキシベンズアルデヒド等の芳香族アルデヒド；ベンジリデンアセトン等の芳香環を有するアセトンなどが例示される。 (2-3-2) Secondary Brightener The zinc alloy plating bath according to one embodiment of the present invention may contain a secondary brightener as one of additive components. In particular, from the viewpoint of improving glossiness, etc., an aromatic compound having a carbonyl group may be contained as a secondary brightener. Examples of such compounds include aromatic aldehydes such as anisaldehyde, veratraldehyde, o-chlorobenzaldehyde (OCAD), salicylaldehyde, vanillin, piperonal and p-hydroxybenzaldehyde; acetone having an aromatic ring such as benzylideneacetone; be done.
本発明の一実施形態に係る亜鉛合金めっき浴は、添加剤成分の一種として二次光沢剤を含有してもよい。特に、光沢性の向上などの観点からは、二次光沢剤として、カルボニル基を有する芳香族化合物を含有してもよい。そのような化合物として、アニスアルデヒド、ベラトルアルデヒド、ｏ－クロロベンズアルデヒド（ＯＣＡＤ）、サリチルアルデヒド、バニリン、ピペロナールおよびｐ－ヒドロキシベンズアルデヒド等の芳香族アルデヒド；ベンジリデンアセトン等の芳香環を有するアセトンなどが例示される。 (2-3-2) Secondary Brightener The zinc alloy plating bath according to one embodiment of the present invention may contain a secondary brightener as one of additive components. In particular, from the viewpoint of improving glossiness, etc., an aromatic compound having a carbonyl group may be contained as a secondary brightener. Examples of such compounds include aromatic aldehydes such as anisaldehyde, veratraldehyde, o-chlorobenzaldehyde (OCAD), salicylaldehyde, vanillin, piperonal and p-hydroxybenzaldehyde; acetone having an aromatic ring such as benzylideneacetone; be done.
本発明の一実施形態に係る亜鉛合金めっき浴が二次光沢剤を含有する場合において、二次光沢剤の亜鉛合金めっき浴中含有量は限定されない。二次光沢剤の種類、亜鉛合金めっき浴に含有される二次光沢剤以外の成分の種類や含有量、亜鉛系めっき浴から形成される亜鉛合金めっき皮膜の組成などに応じて適宜設定される。一例を挙げれば、二次光沢剤の含有量は０．００１ｇ／Ｌ以上１０ｇ／Ｌ以下とすることが好ましく、０．００５ｇ／Ｌ以上１ｇ／Ｌ以下とすることがより好ましい。
When the zinc alloy plating bath according to one embodiment of the present invention contains a secondary brightener, the content of the secondary brightener in the zinc alloy plating bath is not limited. It is appropriately set according to the type of secondary brightener, the type and content of components other than the secondary brightener contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc-based plating bath, etc. . For example, the content of the secondary brightener is preferably 0.001 g/L or more and 10 g/L or less, more preferably 0.005 g/L or more and 1 g/L or less.
（２－３－３）その他
本発明の一実施形態に係る亜鉛合金めっき浴は、上記の成分以外の添加剤成分を含有してもよい。そのような添加剤成分として、酸化防止剤、消泡剤、金属封鎖剤などが例示される。 (2-3-3) Others The zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the above components. Examples of such additive components include antioxidants, antifoaming agents, sequestering agents, and the like.
本発明の一実施形態に係る亜鉛合金めっき浴は、上記の成分以外の添加剤成分を含有してもよい。そのような添加剤成分として、酸化防止剤、消泡剤、金属封鎖剤などが例示される。 (2-3-3) Others The zinc alloy plating bath according to one embodiment of the present invention may contain additive components other than the above components. Examples of such additive components include antioxidants, antifoaming agents, sequestering agents, and the like.
酸化防止剤として、フェノール、カテコール、レゾルシン、ヒドロキノン、ピロガロール等のヒドロキシフェニル化合物や、Ｌ－アスコルビン酸、ソルビトール等が例示される。
Examples of antioxidants include phenol, catechol, resorcinol, hydroquinone, hydroxyphenyl compounds such as pyrogallol, L-ascorbic acid, sorbitol, and the like.
消泡剤として、シリコーン系消泡剤や、界面活性剤、ポリエーテル、高級アルコール等の有機系消泡剤が例示される。
Examples of antifoaming agents include silicone antifoaming agents and organic antifoaming agents such as surfactants, polyethers, and higher alcohols.
金属封鎖剤として、珪酸塩（具体例としてケイ酸ナトリウムが挙げられる。）、シリカ（具体例としてコロイダルシリカが挙げられる。）などが例示される。金属封鎖剤の亜鉛合金めっき浴中含有量は限定されない。金属封鎖剤の種類や、溶媒の組成などを勘案して適宜設定すればよい。一例を挙げれば、金属封鎖剤の含有量は０．１ｇ／Ｌ以上１００ｇ／Ｌ以下とすることが好ましく、０．５ｇ／Ｌ以上２０ｇ／Ｌ以下とすることがより好ましい。
Examples of sequestering agents include silicates (specific examples include sodium silicate), silica (specific examples include colloidal silica), and the like. The content of the sequestering agent in the zinc alloy plating bath is not limited. It may be appropriately set in consideration of the type of sequestering agent, the composition of the solvent, and the like. For example, the content of the sequestering agent is preferably 0.1 g/L or more and 100 g/L or less, more preferably 0.5 g/L or more and 20 g/L or less.
（３）緩衝剤、無機電解質
本発明の一実施形態に係る亜鉛合金めっき浴は緩衝作用を有する物質を緩衝剤として含有してもよい。緩衝剤を含有することにより、被めっき部材の表面近傍のｐＨが過度に高くなることが抑制される。その結果、被めっき部材への亜鉛などの金属の析出形態が安定化して、異常析出が生じにくくなる。 (3) Buffering Agent, Inorganic Electrolyte The zinc alloy plating bath according to one embodiment of the present invention may contain a substance having a buffering action as a buffering agent. By containing the buffering agent, excessive increase in the pH in the vicinity of the surface of the member to be plated is suppressed. As a result, the deposition form of metal such as zinc on the member to be plated is stabilized, and abnormal deposition is less likely to occur.
本発明の一実施形態に係る亜鉛合金めっき浴は緩衝作用を有する物質を緩衝剤として含有してもよい。緩衝剤を含有することにより、被めっき部材の表面近傍のｐＨが過度に高くなることが抑制される。その結果、被めっき部材への亜鉛などの金属の析出形態が安定化して、異常析出が生じにくくなる。 (3) Buffering Agent, Inorganic Electrolyte The zinc alloy plating bath according to one embodiment of the present invention may contain a substance having a buffering action as a buffering agent. By containing the buffering agent, excessive increase in the pH in the vicinity of the surface of the member to be plated is suppressed. As a result, the deposition form of metal such as zinc on the member to be plated is stabilized, and abnormal deposition is less likely to occur.
本発明の一実施形態に係る亜鉛合金めっき浴が緩衝剤を含有する場合において、緩衝剤の種類は限定されない。緩衝剤の具体例として、酢酸および酢酸イオンの少なくとも一方を含有する物質である酢酸含有物質、アンモニアおよびアンモニウムイオンの少なくとも一方を含有する物質であるアンモニア含有物質、ホウ酸およびホウ酸イオンの少なくとも一方を含有する物質であるホウ酸含有物質などが挙げられる。亜鉛合金めっき浴にかかる亜鉛合金めっきが亜鉛合金めっきである場合には、酢酸含有物質を緩衝剤として含有することにより、亜鉛合金めっきの析出が安定化することもある。このめっき析出の安定化の観点から、亜鉛合金めっきにおける合金元素はニッケルであることが好ましい。また、酢酸含有物質をめっき浴に供給するための酢酸源として、酢酸カリウムが好ましい。
When the zinc alloy plating bath according to one embodiment of the present invention contains a buffering agent, the type of buffering agent is not limited. Specific examples of buffering agents include acetate-containing substances that contain at least one of acetate and acetate ions, ammonia-containing substances that contain at least one of ammonia and ammonium ions, and at least one of boric acid and borate ions. boric acid-containing substances, which are substances containing When the zinc alloy plating applied to the zinc alloy plating bath is a zinc alloy plating, the inclusion of an acetic acid-containing substance as a buffer may stabilize the deposition of the zinc alloy plating. From the viewpoint of stabilizing the plating deposition, the alloying element in the zinc alloy plating is preferably nickel. Potassium acetate is preferred as an acetic acid source for supplying the acetic acid-containing substance to the plating bath.
環境負荷を低減させる観点から、本発明の一実施形態に係る亜鉛合金めっき浴における酢酸含有物質の含有量は、酢酸換算で、２００ｇ／Ｌ以下であることが好ましく、１００ｇ／Ｌ以下であることがより好ましく、５０ｇ／Ｌ以下であることがさらに好ましい。緩衝剤としての機能を安定的に発現させる観点から、本発明の一実施形態に係る亜鉛合金めっき浴における酢酸含有物質の含有量は、酢酸換算で、１ｇ／Ｌ以上であることが好ましく、５ｇ／Ｌ以上であることがより好ましく、１０ｇ／Ｌ以上であることが特に好ましい。
From the viewpoint of reducing the environmental load, the content of the acetic acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 200 g/L or less, and 100 g/L or less in terms of acetic acid. is more preferable, and 50 g/L or less is even more preferable. From the viewpoint of stably exerting the function as a buffering agent, the content of the acetic acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 1 g/L or more in terms of acetic acid. /L or more, and particularly preferably 10 g/L or more.
環境負荷を低減させる観点から、本発明の一実施形態に係る亜鉛合金めっき浴におけるアンモニア含有物質の含有量は、アンモニア換算で、１００ｇ／Ｌ以下であることが好ましく、５０ｇ／Ｌ以下であることがより好ましく、１０ｇ／Ｌ以下であることがさらに好ましく、本発明の一実施形態に係る亜鉛合金めっき浴はアンモニア含有物質を実質的に含有しないこと（アンモニアフリー）が特に好ましい。本明細書において、アンモニアフリーとは、めっき浴中で緩衝剤として機能する程度にはアンモニアおよびアンモニウムイオンを含有していないことを意味する。
From the viewpoint of reducing the environmental load, the content of the ammonia-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 100 g/L or less, and 50 g/L or less in terms of ammonia. is more preferably 10 g/L or less, and it is particularly preferable that the zinc alloy plating bath according to one embodiment of the present invention does not substantially contain an ammonia-containing substance (ammonia-free). As used herein, "ammonia-free" means not containing ammonia and ammonium ions to the extent that they function as a buffer in the plating bath.
環境負荷を低減させる観点から、本発明の一実施形態に係る亜鉛合金めっき浴におけるホウ酸含有物質の含有量は、ホウ酸換算で、５ｇ／Ｌ以下であることが好ましく、１ｇ／Ｌ以下であることがより好ましく、０．１ｇ／Ｌ以下であることがさらに好ましく、本発明の一実施形態に係る亜鉛合金めっき浴は、ホウ酸含有物質を実質的に含有しないこと（ホウ酸フリー）が特に好ましい。本明細書において、ホウ酸フリーとは、めっき浴中で緩衝剤として機能する程度にはホウ酸およびホウ酸イオンを含有していないことを意味する。
From the viewpoint of reducing the environmental load, the content of the boric acid-containing substance in the zinc alloy plating bath according to one embodiment of the present invention is preferably 5 g / L or less, and 1 g / L or less in terms of boric acid. more preferably 0.1 g/L or less, and the zinc alloy plating bath according to one embodiment of the present invention contains substantially no boric acid-containing substance (boric acid free). Especially preferred. As used herein, boric acid-free means not containing boric acid and borate ions to the extent that it functions as a buffer in the plating bath.
このように、本実施形態に係る亜鉛合金めっき浴がホウ酸フリー、アンモニアフリーの少なくとも一方、好ましくは両方を満たす場合であっても、亜鉛合金めっき浴が酢酸含有物質を含有していれば、酢酸含有物質がめっき浴の緩衝剤となりうる。酢酸含有物質の具体例として、酢酸カリウム、酢酸ナトリウムなどの酢酸源に基づく物質（酢酸、酢酸イオン）が挙げられる。亜鉛合金めっき浴がホウ酸フリー、アンモニアフリーの少なくとも一方、好ましくは両方を満たす場合であって、酢酸カリウムを酢酸源とするときには、酢酸カリウムの配合量を、１００ｇ／Ｌ以下とすることが好ましいことがあり、７０／Ｌ以下とすることがより好ましいことがある。
Thus, even if the zinc alloy plating bath according to the present embodiment satisfies at least one of boric acid-free and ammonia-free, preferably both, if the zinc alloy plating bath contains an acetic acid-containing substance, An acetic acid-containing substance can serve as a buffer for the plating bath. Specific examples of acetic acid-containing substances include substances (acetic acid, acetate ion) based on acetic acid sources such as potassium acetate and sodium acetate. When the zinc alloy plating bath satisfies at least one of boric acid-free and ammonia-free, preferably both, and potassium acetate is used as the acetic acid source, the compounding amount of potassium acetate is preferably 100 g/L or less. There are cases where it is more preferable to make it 70/L or less.
本発明の一実施形態に係る亜鉛合金めっき浴においてアンモニア含有物質やホウ酸含有物質の含有量が低く、亜鉛合金めっき浴が環境に与える負荷が低い場合には、本発明の一実施形態に係る亜鉛合金めっき浴が排水処理性に優れることを意味している。
When the zinc alloy plating bath according to an embodiment of the present invention has a low content of ammonia-containing substances and boric acid-containing substances, and the zinc alloy plating bath has a low environmental load, This means that the zinc alloy plating bath has excellent wastewater treatment properties.
本発明の一実施形態に係る亜鉛合金めっき浴は、無機電解質を含有してもよい。無機電解質として、塩化物イオン、硫酸イオン、硝酸イオン、リン酸イオン、ナトリウムイオン、カリウムイオン、マグネシウムイオン、アルミニウムイオンなどが例示され、これらは陽イオンと陰イオンとからなる塩として亜鉛合金めっき浴に配合されていてもよい。そのような塩として、塩化カリウムなどのカリウム塩が、溶解のしやすさの観点から好ましい場合がある。本発明の一実施形態に係る亜鉛合金めっき浴に含有される無機電解質の含有量の総和は限定されない。無機電解質の種類、亜鉛合金めっき浴に含有される無機電解質以外の成分の種類や含有量、亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜の組成、めっき条件などに応じて適宜設定される。一例を挙げれば、亜鉛合金めっき浴に含有される無機電解質の含有量の総和は、１０ｇ／Ｌ以上１０００ｇ／Ｌ以下とすることが好ましく、５０ｇ／Ｌ以上５００ｇ／Ｌ以下とすることがより好ましい。亜鉛合金めっきの合金元素がニッケルであって、酸性亜鉛合金めっき浴塩化物イオンを含む場合には、浴の安定性を確保する観点から、塩化物イオンの浴中濃度が、１００ｇ／Ｌ以上４００ｇ／Ｌ以下であることが好ましい場合があり、１２０ｇ／Ｌ以上２８０ｇ／Ｌ以下であることがより好ましい場合がある。
A zinc alloy plating bath according to one embodiment of the present invention may contain an inorganic electrolyte. Examples of inorganic electrolytes include chloride ions, sulfate ions, nitrate ions, phosphate ions, sodium ions, potassium ions, magnesium ions, and aluminum ions. may be blended in. As such a salt, a potassium salt such as potassium chloride may be preferred from the viewpoint of ease of dissolution. The total content of the inorganic electrolyte contained in the zinc alloy plating bath according to one embodiment of the present invention is not limited. It is appropriately set according to the type of inorganic electrolyte, the type and content of components other than the inorganic electrolyte contained in the zinc alloy plating bath, the composition of the zinc alloy plating film formed from the zinc alloy plating bath, the plating conditions, and the like. For example, the total content of the inorganic electrolyte contained in the zinc alloy plating bath is preferably 10 g/L or more and 1000 g/L or less, more preferably 50 g/L or more and 500 g/L or less. . When the alloy element of zinc alloy plating is nickel and the acidic zinc alloy plating bath contains chloride ions, the concentration of chloride ions in the bath is 100 g/L or more and 400 g from the viewpoint of ensuring the stability of the bath. /L or less may be preferable, and 120 g/L or more and 280 g/L or less may be more preferable.
（４）溶媒、液性
本発明の一実施形態に係る亜鉛合金めっき浴の溶媒は水を主成分とする。水以外の溶媒としてアルコール、エーテル、ケトンなど水への溶解度が高い有機溶媒を混在させてもよい。この場合には、めっき浴全体の安定性および廃液処理への負荷の緩和の観点から、その比率は全溶媒に対して１０体積％以下とすることが好ましい。 (4) Solvent and Liquidity The solvent of the zinc alloy plating bath according to one embodiment of the present invention has water as its main component. As a solvent other than water, an organic solvent having high solubility in water such as alcohol, ether, ketone, etc. may be mixed. In this case, from the viewpoint of the stability of the plating bath as a whole and the reduction of the load on waste liquid treatment, the ratio is preferably 10% by volume or less with respect to the total solvent.
本発明の一実施形態に係る亜鉛合金めっき浴の溶媒は水を主成分とする。水以外の溶媒としてアルコール、エーテル、ケトンなど水への溶解度が高い有機溶媒を混在させてもよい。この場合には、めっき浴全体の安定性および廃液処理への負荷の緩和の観点から、その比率は全溶媒に対して１０体積％以下とすることが好ましい。 (4) Solvent and Liquidity The solvent of the zinc alloy plating bath according to one embodiment of the present invention has water as its main component. As a solvent other than water, an organic solvent having high solubility in water such as alcohol, ether, ketone, etc. may be mixed. In this case, from the viewpoint of the stability of the plating bath as a whole and the reduction of the load on waste liquid treatment, the ratio is preferably 10% by volume or less with respect to the total solvent.
本発明の一実施形態に係る亜鉛合金めっき浴は酸性であり、そのｐＨは、４以上６以下であることが好ましく、５．０以上５．８以下であることがより好ましい。めっき浴のｐＨを調整するために用いられる材料の種類は特に限定されない。塩酸、硫酸、硝酸、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物など公知の材料を用いればよい。
The zinc alloy plating bath according to one embodiment of the present invention is acidic, and its pH is preferably 4 or more and 6 or less, more preferably 5.0 or more and 5.8 or less. The type of material used for adjusting the pH of the plating bath is not particularly limited. Known materials such as hydrochloric acid, sulfuric acid, nitric acid, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide may be used.
（５）調製方法
本実施形態に係る亜鉛合金めっき浴の調製方法は特に限定されない。亜鉛合金めっき浴は、亜鉛源、金属源、グリシン源、およびめっき浴においてポリアミン（Ａ）を生成できる物質であるポリアミン（Ａ）源、ならびに必要に応じ任意添加成分として前述のその他の添加剤成分、緩衝剤、無機電解質などを溶媒に溶解させることによって調製することができる。なお、グリシン源はグリシンを含み、ポリアミン（Ａ）源はポリアミン（Ａ）を含む。 (5) Preparation method The preparation method of the zinc alloy plating bath according to the present embodiment is not particularly limited. The zinc alloy plating bath contains a zinc source, a metal source, a glycine source, a polyamine (A) source which is a substance capable of producing polyamine (A) in the plating bath, and optionally the other additive components described above as optional additive components. , a buffering agent, an inorganic electrolyte, etc., in a solvent. The glycine source contains glycine, and the polyamine (A) source contains polyamine (A).
本実施形態に係る亜鉛合金めっき浴の調製方法は特に限定されない。亜鉛合金めっき浴は、亜鉛源、金属源、グリシン源、およびめっき浴においてポリアミン（Ａ）を生成できる物質であるポリアミン（Ａ）源、ならびに必要に応じ任意添加成分として前述のその他の添加剤成分、緩衝剤、無機電解質などを溶媒に溶解させることによって調製することができる。なお、グリシン源はグリシンを含み、ポリアミン（Ａ）源はポリアミン（Ａ）を含む。 (5) Preparation method The preparation method of the zinc alloy plating bath according to the present embodiment is not particularly limited. The zinc alloy plating bath contains a zinc source, a metal source, a glycine source, a polyamine (A) source which is a substance capable of producing polyamine (A) in the plating bath, and optionally the other additive components described above as optional additive components. , a buffering agent, an inorganic electrolyte, etc., in a solvent. The glycine source contains glycine, and the polyamine (A) source contains polyamine (A).
３．亜鉛合金めっき部材の製造方法
亜鉛合金めっき部材は、本実施形態に係る亜鉛合金めっき浴を被めっき部材に接触させ、被めっき部材をカソード（陰極）として電解を行うことによって得ることができる。亜鉛合金めっき浴と被めっき部材との接触方法は限定されない。典型的には亜鉛合金めっき浴内に被めっき部材を接触させることが挙げられ、亜鉛合金めっき浴を構成するめっき液を被めっき部材に噴射することによって上記の接触を行ってもよい。 3. Method for Producing Zinc Alloy Plated Member A zinc alloy plated member can be obtained by bringing the zinc alloy plating bath according to the present embodiment into contact with a member to be plated, and performing electrolysis using the member to be plated as a cathode. The contact method between the zinc alloy plating bath and the member to be plated is not limited. Typically, the member to be plated is brought into contact with the zinc alloy plating bath, and the contact may be performed by spraying the plating solution that constitutes the zinc alloy plating bath onto the member to be plated.
亜鉛合金めっき部材は、本実施形態に係る亜鉛合金めっき浴を被めっき部材に接触させ、被めっき部材をカソード（陰極）として電解を行うことによって得ることができる。亜鉛合金めっき浴と被めっき部材との接触方法は限定されない。典型的には亜鉛合金めっき浴内に被めっき部材を接触させることが挙げられ、亜鉛合金めっき浴を構成するめっき液を被めっき部材に噴射することによって上記の接触を行ってもよい。 3. Method for Producing Zinc Alloy Plated Member A zinc alloy plated member can be obtained by bringing the zinc alloy plating bath according to the present embodiment into contact with a member to be plated, and performing electrolysis using the member to be plated as a cathode. The contact method between the zinc alloy plating bath and the member to be plated is not limited. Typically, the member to be plated is brought into contact with the zinc alloy plating bath, and the contact may be performed by spraying the plating solution that constitutes the zinc alloy plating bath onto the member to be plated.
被めっき部材の材質は導電性を有する限り特に限定されない。鉄系材料などの金属系材料、および樹脂系材料やセラミックス系材料などからなる導電性を有さない材料の表面に無電解めっきなどにより導電性材料からなる層が形成されたものが例示される。被めっき部材の形状も特に限定されない。板材や棒材、線材などの一次加工品；ねじ、ボルト、金型等の切削・研削加工品（さらに研磨加工が施されていてもよい。）、車体フレーム、機器の筐体等のプレス加工品、ブレーキキャリパー、エンジンブロック等の鋳物などの二次加工品が挙げられる。なお、被めっき部材が鉄系材料からなる鋳物である場合には、鋳造性を高めるために含有させた成分などの影響により、アルカリ性亜鉛合金めっき浴からは亜鉛合金めっき皮膜を形成することができないこともある。
The material of the member to be plated is not particularly limited as long as it has conductivity. Metal materials such as iron materials, and non-conductive materials such as resin materials and ceramic materials having a layer made of a conductive material formed by electroless plating on the surface are exemplified. . The shape of the member to be plated is also not particularly limited. Primary processed products such as plates, rods, and wires; cut and ground products such as screws, bolts, and molds (which may be further polished); press processing such as vehicle body frames and equipment housings products, and secondary products such as castings such as brake calipers and engine blocks. If the member to be plated is a casting made of an iron-based material, a zinc alloy plating film cannot be formed from an alkaline zinc alloy plating bath due to the influence of the components contained to improve castability. Sometimes.
アノード（陽極）を構成する材料は特に限定されない。亜鉛や合金元素を含有する金属系材料を可溶性陽極として用いてもよい。可溶性陽極として、亜鉛系の材料からなる陽極と、合金元素を含有する材料からなる陽極とを個別に用意してもよい。そして、これらの陽極を異なる電源に接続し、各々の陽極への電圧印加を独立に制御してもよい。
The material that constitutes the anode (anode) is not particularly limited. A metallic material containing zinc or an alloying element may be used as the soluble anode. As soluble anodes, an anode made of a zinc-based material and an anode made of a material containing an alloy element may be separately prepared. Then, these anodes may be connected to different power sources and voltage application to each anode may be independently controlled.
電解における電流密度は特に限定されない。電流密度が過度に低い場合には得られる亜鉛合金めっき皮膜の析出速度が低く生産性に劣る場合があり、電流密度が過度に高い場合には得られる亜鉛めっき皮膜の外観が劣化したり、均一電着性、付き廻り性などが低下したりすることが懸念される場合があることを考慮して、適宜設定すればよい。生産性を高めることとめっき皮膜の品質を高めることとを両立する観点から、０．１Ａ／ｄｍ2以上１５Ａ／ｄｍ2以下とすることが好ましく、０．５Ａ／ｄｍ2以上１３Ａ／ｄｍ2以下とすることがより好ましい。上記のとおり、酸性亜鉛合金めっき浴がグリシン含有水溶性物質およびポリアミン（Ａ）を含有することにより、高電流密度、具体的には１０Ａ／ｄｍ2を超える電流密度であっても、亜鉛ニッケル合金めっき皮膜にニッケル濃縮領域が形成されにくくなるため、得られためっき皮膜に外観不良が生じにくい。
The current density in electrolysis is not particularly limited. If the current density is too low, the deposition rate of the resulting zinc alloy plating film may be low and productivity may be poor. Considering that there is a possibility that the electrodepositability, throwing power, etc. may be deteriorated, it may be appropriately set. From the viewpoint of improving productivity and improving the quality of the plating film, it is preferably 0.1 A/dm 2 or more and 15 A/dm 2 or less, and 0.5 A/dm 2 or more and 13 A/dm 2 or less. is more preferable. As described above, even at high current densities, specifically current densities exceeding 10 A/dm 2 , the acidic zinc alloy plating bath containing the glycine-containing water-soluble substance and polyamine (A) can Since nickel-enriched regions are less likely to be formed in the plated film, the obtained plated film is less likely to have poor appearance.
電解におけるめっき浴の温度（めっき浴温度）は１５℃程度から５０℃程度の範囲で行えばよく、室温程度（２５℃程度）で行ってもよい。
The temperature of the plating bath (plating bath temperature) in electrolysis may be in the range of about 15°C to about 50°C, and may be performed at about room temperature (about 25°C).
電解時間（めっき時間）は、亜鉛合金めっき浴の組成、上記の電流密度、めっき浴温度などによって決定されるめっき皮膜の析出速度と求めるめっき皮膜の厚さとから適宜設定される。
The electrolysis time (plating time) is appropriately set from the deposition rate of the plating film determined by the composition of the zinc alloy plating bath, the above-mentioned current density, plating bath temperature, etc., and the desired thickness of the plating film.
めっき設備の構成は特に限定されない。板状または棒状のアノードに対向するようにカソードとしての被めっき部材を亜鉛合金めっき浴中に配置し、亜鉛合金めっき浴内で液攪拌を適宜行いながら電解して被めっき部材に亜鉛合金めっき皮膜を形成してもよい。この場合には、液撹拌は液循環ポンプを用いてもよいし、エアレーションを用いてもよいし、被めっき部材などをめっき浴中で移動させることによって撹拌してもよい。
The configuration of the plating equipment is not particularly limited. A member to be plated as a cathode is placed in a zinc alloy plating bath so as to face a plate-shaped or rod-shaped anode, and electrolysis is performed while appropriately stirring the liquid in the zinc alloy plating bath to form a zinc alloy plating film on the member to be plated. may be formed. In this case, the liquid may be stirred by using a liquid circulation pump, by aeration, or by moving the member to be plated or the like in the plating bath.
他のめっき設備の例として、ボルトなどの被めっき部材がその内部に入っているバレルを亜鉛合金めっき浴中に浸漬させ、バレルを回転させながら電解を行うことで被めっき部材に亜鉛合金めっき皮膜を形成するバレルめっき設備が挙げられる。バレルめっき設備を用いる被めっき部材の具体例として、ボルト、ナット、ねじなどが挙げられる。本発明の一実施形態に係る亜鉛合金めっき浴を用いると、被めっき部材がボルトのような形状異方性が高い（長細い）場合であっても、得られた亜鉛合金めっき皮膜について、端部とそれ以外の部分とで、外観、膜厚および共析率の変動を生じにくくすることが可能である。電流効率の低いアルカリ性亜鉛合金めっき浴を用いず、電流効率の高い酸性亜鉛合金めっき浴を用いた場合には、従来、端部とそれ以外の部分とで、外観、膜厚および共析率の変動を生じにくくすることは困難であった。
As an example of other plating equipment, a barrel containing a member to be plated such as a bolt is immersed in a zinc alloy plating bath, and electrolysis is performed while rotating the barrel to form a zinc alloy plating film on the member to be plated. A barrel plating facility that forms a Specific examples of members to be plated using barrel plating equipment include bolts, nuts, and screws. When the zinc alloy plating bath according to one embodiment of the present invention is used, even if the member to be plated has high shape anisotropy (elongated) such as a bolt, the obtained zinc alloy plating film can be It is possible to make it difficult for variations in appearance, film thickness and eutectoid ratio to occur between the part and the other parts. When an acidic zinc alloy plating bath with a high current efficiency is used instead of an alkaline zinc alloy plating bath with a low current efficiency, conventionally, the appearance, film thickness and eutectoid rate of the edge and other parts are different. It has been difficult to make fluctuations less likely to occur.
４．亜鉛合金めっき皮膜
本添加剤を用いて形成された亜鉛ニッケル合金めっき皮膜では、鉄系材料からなる被めっき部材に形成された亜鉛合金めっき部材の深さプロファイルを測定したときに、被めっき部材に近位な側にニッケル濃度が相対的に高いニッケル濃縮領域が形成されにくい。 4. Zinc alloy plated film In the zinc-nickel alloy plated film formed using this additive, when the depth profile of the zinc alloy plated member formed on the member to be plated made of iron-based material is measured, A nickel-enriched region having a relatively high nickel concentration is less likely to be formed on the proximal side.
本添加剤を用いて形成された亜鉛ニッケル合金めっき皮膜では、鉄系材料からなる被めっき部材に形成された亜鉛合金めっき部材の深さプロファイルを測定したときに、被めっき部材に近位な側にニッケル濃度が相対的に高いニッケル濃縮領域が形成されにくい。 4. Zinc alloy plated film In the zinc-nickel alloy plated film formed using this additive, when the depth profile of the zinc alloy plated member formed on the member to be plated made of iron-based material is measured, A nickel-enriched region having a relatively high nickel concentration is less likely to be formed on the proximal side.
ニッケル濃縮領域は、めっき部材の成分濃度のめっき皮膜の厚さ方向の変化を示すグラフ（深さプロファイル）により確認することができる。具体的には、鉄系材料からなる被めっき部材に形成された亜鉛合金めっき部材の深さプロファイルを測定したときに、亜鉛濃度が６０質量％以上であって最表面に最も近い位置を亜鉛合金めっき皮膜の表面側端部と定義する。また、亜鉛濃度が被めっき部材に由来する鉄濃度に等しくなる位置を亜鉛合金めっきの被めっき部材側端部と定義する。そして、表面側端部から被めっき側端部までの領域の長さを亜鉛合金めっき皮膜の厚さと定義する。
The nickel-enriched region can be confirmed by a graph (depth profile) showing changes in the thickness direction of the plating film in the component concentration of the plating member. Specifically, when the depth profile of a zinc alloy plated member formed on a member to be plated made of an iron-based material is measured, the zinc concentration is 60% by mass or more and the position closest to the outermost surface is the zinc alloy It is defined as the surface side edge of the plating film. Further, the position where the concentration of zinc is equal to the concentration of iron derived from the member to be plated is defined as the side end portion of the member to be plated for zinc alloy plating. The length of the region from the surface-side end to the plated-side end is defined as the thickness of the zinc alloy plating film.
このように定義したときに、亜鉛合金めっき皮膜の被めっき部材側端部から亜鉛合金めっきの厚さの３０％だけ表面側に移動した位置と被めっき部材側端部との範囲からなる初期領域に、その初期領域よりも表面側の領域よりもニッケル濃度（合金元素濃度の合金元素がニッケルの場合である。）が特異的に高い部分領域が認められた場合には、その部分領域をニッケル濃縮領域（合金元素濃縮領域の合金元素がニッケルの場合である。）と呼ぶ。
When defined in this way, the initial region consisting of the position shifted from the end of the zinc alloy plating film on the side of the member to be plated to the surface side by 30% of the thickness of the zinc alloy plating and the end on the side of the member to be plated. , if a partial region with a nickel concentration (in the case where the alloying element in the alloying element concentration is nickel) is found to be specifically higher than that of the region on the surface side of the initial region, that partial region is treated with nickel It is called an enriched region (when the alloying element in the alloying element enriched region is nickel).
ニッケル濃縮領域の存在は、深さプロファイルの全体形状から判断すべきものであるが、次のような評価方法もニッケル濃縮領域の存在を確認するための一助となる。すなわち、表面側端部から亜鉛合金めっきの厚さの４０％から６０％の範囲を中間領域と定義したときに、ニッケル濃縮領域を有する亜鉛ニッケル合金めっき皮膜では、この中間領域におけるニッケル濃度の平均値（この平均値を「中間領域平均値」ともいう。）［Ｎｉ１］と、上記の初期領域におけるニッケル濃度の最大値（この最大値を「初期領域最大値」ともいう。）［Ｎｉ２］と、が、下記式（２）を満たす時には、初期領域にニッケル濃縮領域が生じている可能性が高い。
［Ｎｉ１］＜［Ｎｉ２］ （２） The presence of nickel-enriched regions should be judged from the overall shape of the depth profile, but the following evaluation method also helps to confirm the presence of nickel-enriched regions. That is, when the range of 40% to 60% of the thickness of the zinc alloy plating from the surface side edge is defined as the intermediate region, the zinc nickel alloy plating film having the nickel enriched region has an average nickel concentration in this intermediate region value (this average value is also referred to as “intermediate region average value”) [Ni1], and the maximum value of nickel concentration in the initial region (this maximum value is also referred to as “initial region maximum value”) [Ni2]. , satisfies the following formula (2), there is a high possibility that a nickel-enriched region occurs in the initial region.
[Ni1]<[Ni2] (2)
［Ｎｉ１］＜［Ｎｉ２］ （２） The presence of nickel-enriched regions should be judged from the overall shape of the depth profile, but the following evaluation method also helps to confirm the presence of nickel-enriched regions. That is, when the range of 40% to 60% of the thickness of the zinc alloy plating from the surface side edge is defined as the intermediate region, the zinc nickel alloy plating film having the nickel enriched region has an average nickel concentration in this intermediate region value (this average value is also referred to as “intermediate region average value”) [Ni1], and the maximum value of nickel concentration in the initial region (this maximum value is also referred to as “initial region maximum value”) [Ni2]. , satisfies the following formula (2), there is a high possibility that a nickel-enriched region occurs in the initial region.
[Ni1]<[Ni2] (2)
亜鉛ニッケル合金めっき皮膜の被めっき部材に近位な側にこのようなニッケル濃縮領域が存在する場合には、外観不良が生じやすく、電流密度が高い場合にこの傾向は顕著となる。
When such a nickel-enriched region exists on the side of the zinc-nickel alloy plating film proximal to the member to be plated, poor appearance is likely to occur, and this tendency becomes noticeable when the current density is high.
これに対し、本実施形態に係る亜鉛合金めっき皮膜（亜鉛ニッケル合金めっき皮膜）は、グリシン含有水溶性物質およびポリアミン（Ａ）を含有するめっき浴から形成されたものであることから、ニッケル濃縮領域が生じにくく、下記式（１）を満たしやすい。
［Ｎｉ１］≧［Ｎｉ２］ （１） On the other hand, the zinc alloy plating film (zinc-nickel alloy plating film) according to the present embodiment is formed from a plating bath containing a glycine-containing water-soluble substance and polyamine (A). is less likely to occur, and the following formula (1) is likely to be satisfied.
[Ni1]≧[Ni2] (1)
［Ｎｉ１］≧［Ｎｉ２］ （１） On the other hand, the zinc alloy plating film (zinc-nickel alloy plating film) according to the present embodiment is formed from a plating bath containing a glycine-containing water-soluble substance and polyamine (A). is less likely to occur, and the following formula (1) is likely to be satisfied.
[Ni1]≧[Ni2] (1)
それゆえ、本実施形態に係る亜鉛合金めっき皮膜（亜鉛ニッケル合金めっき皮膜）は、電流密度が高い、具体的には、１０Ａ／ｄｍ2を超える条件で形成された部分であっても、外観不良が生じにくい。
Therefore, the zinc alloy plating film (zinc-nickel alloy plating film) according to the present embodiment has a high current density, specifically, even at a portion formed under conditions exceeding 10 A / dm is less likely to occur.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更や均等物をも含む趣旨である。
The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiments is meant to include all design changes and equivalents that fall within the technical scope of the present invention.
例えば、亜鉛合金めっき部材が備える亜鉛合金めっき皮膜上に化成処理などが施されていてもよい。
For example, a chemical conversion treatment may be applied to the zinc alloy plating film of the zinc alloy plated member.
以下、本発明の効果を実施例に基づいて説明するが、本発明はこれに限定されるものではない。
The effects of the present invention will be described below based on examples, but the present invention is not limited to these.
（実施例１から実施例３および比較例１から比較例３）
次の組成を有し、ｐＨが５．３の亜鉛合金めっき浴を調製した。
塩化亜鉛：６２．５ｇ／Ｌ（亜鉛濃度：３０ｇ／Ｌ）
塩化ニッケル６水和物：８１ｇ／Ｌ（ニッケル濃度：２０ｇ／Ｌ）
塩化カリウム：１９６ｇ／Ｌ（塩化亜鉛、塩化ニッケル６水和物由来も含めた塩素濃度：１５０ｇ／Ｌ）
酢酸カリウム：６５ｇ／Ｌ
グリシン源：グリシン（Ｇｌｙ）を表１に示される量（表中の単位はｇ／Ｌ）で配合
ポリアミン（Ａ）源：ポリアミン（Ａ）の一種であるジエチレントリアミン（ＤＥＴＡ）を表１に示される量（表中の単位はｇ／Ｌ）で配合
安息香酸ナトリウム：１ｇ／Ｌ
界面活性剤：１．６ｇ／Ｌ
ブライトナー：０．０１ｇ／Ｌ
ホウ酸：非含有
アンモニアまたはアンモニウム塩：非含有 (Examples 1 to 3 and Comparative Examples 1 to 3)
A zinc alloy plating bath having the following composition and a pH of 5.3 was prepared.
Zinc chloride: 62.5 g / L (zinc concentration: 30 g / L)
Nickel chloride hexahydrate: 81 g / L (nickel concentration: 20 g / L)
Potassium chloride: 196 g / L (chlorine concentration including zinc chloride and nickel chloride hexahydrate: 150 g / L)
Potassium acetate: 65g/L
Glycine source: Blend glycine (Gly) in the amount shown in Table 1 (the unit in the table is g/L) Polyamine (A) source: Diethylenetriamine (DETA), a type of polyamine (A), shown in Table 1 Formulated by amount (unit in the table is g/L) Sodium benzoate: 1 g/L
Surfactant: 1.6g/L
Brightener: 0.01g/L
Boric acid: not included Ammonia or ammonium salt: not included
次の組成を有し、ｐＨが５．３の亜鉛合金めっき浴を調製した。
塩化亜鉛：６２．５ｇ／Ｌ（亜鉛濃度：３０ｇ／Ｌ）
塩化ニッケル６水和物：８１ｇ／Ｌ（ニッケル濃度：２０ｇ／Ｌ）
塩化カリウム：１９６ｇ／Ｌ（塩化亜鉛、塩化ニッケル６水和物由来も含めた塩素濃度：１５０ｇ／Ｌ）
酢酸カリウム：６５ｇ／Ｌ
グリシン源：グリシン（Ｇｌｙ）を表１に示される量（表中の単位はｇ／Ｌ）で配合
ポリアミン（Ａ）源：ポリアミン（Ａ）の一種であるジエチレントリアミン（ＤＥＴＡ）を表１に示される量（表中の単位はｇ／Ｌ）で配合
安息香酸ナトリウム：１ｇ／Ｌ
界面活性剤：１．６ｇ／Ｌ
ブライトナー：０．０１ｇ／Ｌ
ホウ酸：非含有
アンモニアまたはアンモニウム塩：非含有 (Examples 1 to 3 and Comparative Examples 1 to 3)
A zinc alloy plating bath having the following composition and a pH of 5.3 was prepared.
Zinc chloride: 62.5 g / L (zinc concentration: 30 g / L)
Nickel chloride hexahydrate: 81 g / L (nickel concentration: 20 g / L)
Potassium chloride: 196 g / L (chlorine concentration including zinc chloride and nickel chloride hexahydrate: 150 g / L)
Potassium acetate: 65g/L
Glycine source: Blend glycine (Gly) in the amount shown in Table 1 (the unit in the table is g/L) Polyamine (A) source: Diethylenetriamine (DETA), a type of polyamine (A), shown in Table 1 Formulated by amount (unit in the table is g/L) Sodium benzoate: 1 g/L
Surfactant: 1.6g/L
Brightener: 0.01g/L
Boric acid: not included Ammonia or ammonium salt: not included
調製しためっき浴のそれぞれについて、ハルセル試験器（山本鍍金試験器社製「Ｂ－５５」）を用いて、次の条件で電解を行った。
電流：８Ａ
時間：１５秒間
液温：３５℃
液撹拌：なし
アノード板：ニッケル板（山本鍍金試験器社製「Ｂ－５９－Ｐ０２」）
カソード板：鉄板（山本鍍金試験器社製「Ｂ－６０－Ｐ０１Ａ」） For each of the prepared plating baths, electrolysis was performed under the following conditions using a Hull cell tester (“B-55” manufactured by Yamamoto Plating Tester Co., Ltd.).
Current: 8A
Time: 15 seconds Liquid temperature: 35°C
Liquid stirring: None Anode plate: Nickel plate (manufactured by Yamamoto Plating Tester "B-59-P02")
Cathode plate: Iron plate ("B-60-P01A" manufactured by Yamamoto Plating Tester Co., Ltd.)
電流：８Ａ
時間：１５秒間
液温：３５℃
液撹拌：なし
アノード板：ニッケル板（山本鍍金試験器社製「Ｂ－５９－Ｐ０２」）
カソード板：鉄板（山本鍍金試験器社製「Ｂ－６０－Ｐ０１Ａ」） For each of the prepared plating baths, electrolysis was performed under the following conditions using a Hull cell tester (“B-55” manufactured by Yamamoto Plating Tester Co., Ltd.).
Current: 8A
Time: 15 seconds Liquid temperature: 35°C
Liquid stirring: None Anode plate: Nickel plate (manufactured by Yamamoto Plating Tester "B-59-P02")
Cathode plate: Iron plate ("B-60-P01A" manufactured by Yamamoto Plating Tester Co., Ltd.)
カソード板上に形成された白銀色の亜鉛ニッケル合金めっき皮膜における電流密度１１Ａ／ｄｍ2の部分について外観観察を行った。結果を表１に示す。表１における「Ｇｌｙ／ＰＡ」はグリシン／ポリアミン比を意味する（以下同じ。）。
Appearance observation was carried out for a portion of the silver-white zinc-nickel alloy plating film formed on the cathode plate at a current density of 11 A/dm 2 . Table 1 shows the results. "Gly/PA" in Table 1 means the glycine/polyamine ratio (same below).
表１に示されるように、グリシン含有水溶性物質であるグリシンおよびポリアミン（Ａ）であるジエチレントリアミンを含有する本実施例に係る亜鉛ニッケルめっき浴から形成された亜鉛ニッケル合金めっき皮膜は、電流密度１１Ａ／ｄｍ2の部分において特段の外観不良は認められなかった。
As shown in Table 1, the zinc-nickel alloy plating film formed from the zinc-nickel plating bath according to this example containing glycine, which is a glycine-containing water-soluble substance, and diethylenetriamine, which is a polyamine (A), has a current density of 11A. No particular poor appearance was observed in the /dm 2 portion.
得られた亜鉛ニッケル合金めっき皮膜における電流密度１１Ａ／ｄｍ2の部分について、グロー放電発光分析（ＧＤ－ＯＥＳ）により深さプロファイルを測定した。実施例２の亜鉛ニッケル合金めっき皮膜の深さプロファイルを、具体例として図１に示した。なお、図１では、亜鉛ニッケル合金めっき皮膜に含まれる亜鉛およびニッケルならびにカソード板に含まれる鉄の濃度について深さプロファイルを示した。
The depth profile was measured by glow discharge optical emission spectroscopy (GD-OES) for the portion of the obtained zinc-nickel alloy plating film with a current density of 11 A/dm 2 . A specific example of the depth profile of the zinc-nickel alloy plating film of Example 2 is shown in FIG. In addition, FIG. 1 shows a depth profile of concentrations of zinc and nickel contained in the zinc-nickel alloy plating film and iron contained in the cathode plate.
図１において矢印に示される、亜鉛ニッケル合金めっき皮膜に由来する亜鉛の濃度と、被めっき部材であるカソード板に由来する鉄の濃度とが等しい深さを、亜鉛ニッケル合金めっき皮膜における被めっき部材側の端部とした。また、亜鉛の濃度が６０質量％以上であって最表面に最も近い位置を亜鉛合金めっき皮膜の表面側の端部とした。そして、表面側の端部から被めっき部材側の端部までの範囲（図１では白抜き矢印で示した。）の長さを亜鉛合金めっき皮膜の厚さとした。図１に示される深さプロファイルに基づくと、亜鉛合金めっき皮膜の厚さは、２７５ｎｍであった。なお、表面側の端部と最表面との間の長さは１ｎｍ程度であり、ＧＤ－ＯＥＳの深さプロファイルの測定精度を考慮すると、ほぼ無視できる長さであった。
In FIG. 1, the depth where the concentration of zinc derived from the zinc-nickel alloy plating film and the concentration of iron derived from the cathode plate, which is the member to be plated, is equal to the depth indicated by the arrow in the zinc-nickel alloy plating film is the member to be plated. side edge. In addition, the position closest to the outermost surface where the concentration of zinc was 60% by mass or more was defined as the edge on the surface side of the zinc alloy plating film. The length of the range from the end on the surface side to the end on the side of the member to be plated (indicated by the white arrow in FIG. 1) was defined as the thickness of the zinc alloy plating film. Based on the depth profile shown in FIG. 1, the thickness of the zinc alloy plating film was 275 nm. The length between the edge on the surface side and the outermost surface was about 1 nm, which was almost negligible considering the measurement accuracy of the depth profile of GD-OES.
実施例および比較例により作製された亜鉛ニッケル合金めっき皮膜のそれぞれにおける電流密度１１Ａ／ｄｍ2の部分のニッケル濃度について深さプロファイルを求めた。その結果を図２から図４に示す。なお、これらの図では、横軸をそれぞれのめっき皮膜の厚さで規格化し、電流密度の単位をＡＳＤとして示した。
Depth profiles were obtained for the nickel concentration at the current density of 11 A/dm 2 in each of the zinc-nickel alloy plating films produced by the examples and the comparative examples. The results are shown in FIGS. 2 to 4. FIG. In these figures, the horizontal axis is normalized by the thickness of each plating film, and the unit of current density is indicated as ASD.
図２から図４に示されるように、比較例に係る亜鉛ニッケル合金めっき皮膜では、被めっき部材側端部から亜鉛ニッケル合金めっきの厚さの３０％だけ表面側に移動した位置と被めっき部材側端部との範囲からなる初期領域に、ニッケル濃度が特異的に高い部分（ニッケル濃縮領域）が認められた。この傾向が顕著な比較例２の深さプロファイルを示す図３を用いて説明すると、図３の白抜き矢印で示される範囲が初期領域である。初期領域には、初期領域以外の領域、例えば、表面側端部から前記亜鉛合金めっきの厚さの４０％から６０％の範囲からなる中間領域（図３において黒矢印で示した。）よりもニッケル濃度が高い領域が存在する。このようなニッケル濃縮領域におけるめっき皮膜は白銀色ではなく黒色化するため、ニッケル濃縮領域を形成するめっき浴では、得られためっき皮膜はニッケル濃縮領域に由来して黒色外観となってしまう。
As shown in FIGS. 2 to 4, in the zinc-nickel alloy plating film according to the comparative example, the position moved from the side end of the member to be plated to the surface side by 30% of the thickness of the zinc-nickel alloy plating and the member to be plated A portion (nickel-enriched region) with a specific high nickel concentration was observed in the initial region consisting of the side end portion. Using FIG. 3 showing the depth profile of Comparative Example 2 in which this tendency is remarkable, the range indicated by the white arrow in FIG. 3 is the initial region. In the initial region, a region other than the initial region, for example, an intermediate region (indicated by a black arrow in FIG. 3) consisting of a range of 40% to 60% of the thickness of the zinc alloy plating from the surface side end There are areas of high nickel concentration. Since the plating film in such a nickel-enriched region turns black instead of white silver, in a plating bath that forms the nickel-enriched region, the obtained plating film has a black appearance due to the nickel-enriched region.
確認のため、図２から図４に示される深さプロファイルから、中間領域におけるニッケル濃度の平均値［Ｎｉ１］と、初期領域におけるニッケル濃度の最大値［Ｎｉ２］とを求めた。その結果を表２に示す。
For confirmation, from the depth profiles shown in FIGS. 2 to 4, the average nickel concentration [Ni1] in the intermediate region and the maximum nickel concentration [Ni2] in the initial region were obtained. Table 2 shows the results.
表２に示されるように、比較例の亜鉛ニッケル合金めっき皮膜は、初期領域の最大値［Ｎｉ２］が中間領域の平均値［Ｎｉ１］よりも大きくなる（［Ｎｉ１］＜［Ｎｉ２］）傾向が認められ、ニッケル濃縮領域の存在が確認された。これに対し、実施例の亜鉛合金ニッケルめっきは、中間領域の平均値［Ｎｉ１］が初期領域の最大値［Ｎｉ２］以上となる（［Ｎｉ１］≧［Ｎｉ２］）傾向が認められ、ニッケル濃縮領域は確認されなかった。
As shown in Table 2, in the zinc-nickel alloy plating film of the comparative example, the maximum value [Ni2] in the initial region tends to be larger than the average value [Ni1] in the intermediate region ([Ni1] < [Ni2]). observed, confirming the presence of a nickel-enriched region. On the other hand, in the zinc alloy nickel plating of the example, the average value [Ni1] in the intermediate region tends to be greater than or equal to the maximum value [Ni2] in the initial region ([Ni1] ≥ [Ni2]), and the nickel enriched region was not confirmed.
（実施例４から実施例１３および実施例２０）
実施例１のめっき液の組成をベースとして、表３に示されるように、浴可溶性ニッケル含有物質のニッケル換算モル濃度およびグリシンのモル濃度が異なる複数種類のめっき液を用意した。表４において、「Ｎｉ」、「Ｇｌｙ」および「ＤＥＴＡ」の列の数字はそれぞれ、ニッケルのモル濃度（単位：ｍｏｌ／Ｌ）、グリシンのモル濃度（単位：ｍｏｌ／Ｌ）およびジエチレントリアミンのモル濃度（単位：ｍｍｏｌ／Ｌ）である。また、「Ｇｌｙ／Ｎｉ」の列の数字は（グリシンのモル濃度）／（ニッケルのモル濃度）の計算結果（グリシン／ニッケル比）であり、「Ｇｌｙ／ＰＡ」の列の数字は（グリシンのモル濃度）／（ジエチレントリアミンのモル濃度）の計算結果（グリシン／ポリアミン比）である。 (Examples 4 to 13 and 20)
Using the composition of the plating solution of Example 1 as a base, as shown in Table 3, a plurality of types of plating solutions having different nickel equivalent molar concentrations of the bath-soluble nickel-containing substances and different glycine molar concentrations were prepared. In Table 4, the numbers in the columns "Ni", "Gly" and "DETA" are the molar concentrations of nickel (unit: mol/L), the molar concentrations of glycine (unit: mol/L) and the molar concentrations of diethylenetriamine, respectively. (Unit: mmol/L). The numbers in the "Gly/Ni" column are the calculation results (glycine/nickel ratio) of (molar concentration of glycine)/(molar concentration of nickel), and the numbers in the "Gly/PA" column are (molar concentration of glycine). It is a calculation result (glycine/polyamine ratio) of (molar concentration)/(molar concentration of diethylenetriamine).
実施例１のめっき液の組成をベースとして、表３に示されるように、浴可溶性ニッケル含有物質のニッケル換算モル濃度およびグリシンのモル濃度が異なる複数種類のめっき液を用意した。表４において、「Ｎｉ」、「Ｇｌｙ」および「ＤＥＴＡ」の列の数字はそれぞれ、ニッケルのモル濃度（単位：ｍｏｌ／Ｌ）、グリシンのモル濃度（単位：ｍｏｌ／Ｌ）およびジエチレントリアミンのモル濃度（単位：ｍｍｏｌ／Ｌ）である。また、「Ｇｌｙ／Ｎｉ」の列の数字は（グリシンのモル濃度）／（ニッケルのモル濃度）の計算結果（グリシン／ニッケル比）であり、「Ｇｌｙ／ＰＡ」の列の数字は（グリシンのモル濃度）／（ジエチレントリアミンのモル濃度）の計算結果（グリシン／ポリアミン比）である。 (Examples 4 to 13 and 20)
Using the composition of the plating solution of Example 1 as a base, as shown in Table 3, a plurality of types of plating solutions having different nickel equivalent molar concentrations of the bath-soluble nickel-containing substances and different glycine molar concentrations were prepared. In Table 4, the numbers in the columns "Ni", "Gly" and "DETA" are the molar concentrations of nickel (unit: mol/L), the molar concentrations of glycine (unit: mol/L) and the molar concentrations of diethylenetriamine, respectively. (Unit: mmol/L). The numbers in the "Gly/Ni" column are the calculation results (glycine/nickel ratio) of (molar concentration of glycine)/(molar concentration of nickel), and the numbers in the "Gly/PA" column are (molar concentration of glycine). It is a calculation result (glycine/polyamine ratio) of (molar concentration)/(molar concentration of diethylenetriamine).
調製しためっき液のそれぞれについて、実施例１と同じ条件で電解を行い、カソード板上に形成された亜鉛ニッケル合金めっき皮膜における電流密度１１Ａ／ｄｍ2の部分について外観観察を行った。結果は、表３に示したように、いずれの実施例に係る皮膜も光沢（白銀色の外観であり、カソード板に対面して覗いたときに観察者の目がはっきり確認できる）であった。
Electrolysis was performed for each of the prepared plating solutions under the same conditions as in Example 1, and the appearance of the zinc-nickel alloy plating film formed on the cathode plate at a current density of 11 A/dm 2 was observed. As a result, as shown in Table 3, the films according to any of the examples were glossy (appearance of silvery white color, and the observer's eyes could clearly see them when facing the cathode plate). .
得られた亜鉛ニッケル合金めっき皮膜における電流密度１１Ａ／ｄｍ2の部分について、グロー放電発光分析（ＧＤ－ＯＥＳ）により深さプロファイルを測定した。その結果を図５から図１４に示す。これらの図に示されるように、いずれのめっき皮膜の深さプロファイルにおいても、初期領域にニッケル濃縮領域は認められなかった。中間領域の平均値［Ｎｉ１］と初期領域の最大値［Ｎｉ２］とを対比すると、表３に示されるように、基本的には、中間領域の平均値［Ｎｉ１］が初期領域の最大値［Ｎｉ２］以上となる（［Ｎｉ１］≧［Ｎｉ２］）傾向が見られ、［Ｎｉ２］が［Ｎｉ１］を明確に上回る結果は得られなかった。すなわち、電流密度が１０Ａ／ｄｍ2を超える部分であっても、グリシン／ニッケル比が０．１以上２．０以下かつグリシン／ポリアミン比が０．３以上３４．４以下の範囲で、適切な外観を有する亜鉛ニッケル合金めっき皮膜が得られた。
The depth profile was measured by glow discharge optical emission spectroscopy (GD-OES) for the portion of the obtained zinc-nickel alloy plating film with a current density of 11 A/dm 2 . The results are shown in FIGS. 5 to 14. FIG. As shown in these figures, no nickel-enriched region was observed in the initial region in the depth profiles of any of the plating films. Comparing the average value [Ni1] in the intermediate region and the maximum value [Ni2] in the initial region, as shown in Table 3, basically the average value [Ni1] in the intermediate region is the maximum value [Ni2] in the initial region. Ni2] or more ([Ni1]≧[Ni2]), and no result was obtained in which [Ni2] clearly exceeded [Ni1]. That is, even in the portion where the current density exceeds 10 A/dm 2 , an appropriate A zinc-nickel alloy plating film having a good appearance was obtained.
（実施例１４から実施例１９および比較例４から比較例８）
表４に示されるめっき浴を調製した。比較例４のめっき浴は、特許文献３の実施例１として示される電解組成物の範囲に含まれる。
実施例１４のめっき浴は、比較例４のめっき浴に、本発明に係るポリアミンの一種であるジエチレントリアミンを、グリシン／ポリアミン比が実施例１の場合（６．０）と等しくなるように追加したものである。
実施例１５のめっき浴は実施例１のめっき浴とほぼ等しい組成である。比較例５のめっき浴は、実施例１５のめっき浴からジエチレントリアミンを非含有とするとともに、比較例４のめっき浴と同量のホウ酸を含有させたものである。換言すれば、比較例５のめっき浴は、比較例４のめっき浴について、ニッケル濃度および塩素濃度を実施例１５と同様にしたものである。
比較例６のめっき浴は、比較例４のめっき浴からホウ酸を非含有としたものである。この組成は、参考のため示した比較例１のめっき浴とニッケル濃度および塩素濃度が相違する。 (Examples 14 to 19 and Comparative Examples 4 to 8)
Plating baths shown in Table 4 were prepared. The plating bath of Comparative Example 4 is included in the scope of the electrolytic composition shown as Example 1 of Patent Document 3.
In the plating bath of Example 14, diethylenetriamine, which is a kind of polyamine according to the present invention, was added to the plating bath of Comparative Example 4 so that the glycine/polyamine ratio was the same as in Example 1 (6.0). It is a thing.
The plating bath of Example 15 has almost the same composition as the plating bath of Example 1. The plating bath of Comparative Example 5 was obtained by removing diethylenetriamine from the plating bath of Example 15 and containing the same amount of boric acid as in the plating bath of Comparative Example 4. In other words, the plating bath of Comparative Example 5 is the plating bath of Comparative Example 4 with the same nickel concentration and chlorine concentration as in Example 15.
The plating bath of Comparative Example 6 is the same as the plating bath of Comparative Example 4 except that it does not contain boric acid. This composition differs from the plating bath of Comparative Example 1 shown for reference in nickel concentration and chlorine concentration.
表４に示されるめっき浴を調製した。比較例４のめっき浴は、特許文献３の実施例１として示される電解組成物の範囲に含まれる。
実施例１４のめっき浴は、比較例４のめっき浴に、本発明に係るポリアミンの一種であるジエチレントリアミンを、グリシン／ポリアミン比が実施例１の場合（６．０）と等しくなるように追加したものである。
実施例１５のめっき浴は実施例１のめっき浴とほぼ等しい組成である。比較例５のめっき浴は、実施例１５のめっき浴からジエチレントリアミンを非含有とするとともに、比較例４のめっき浴と同量のホウ酸を含有させたものである。換言すれば、比較例５のめっき浴は、比較例４のめっき浴について、ニッケル濃度および塩素濃度を実施例１５と同様にしたものである。
比較例６のめっき浴は、比較例４のめっき浴からホウ酸を非含有としたものである。この組成は、参考のため示した比較例１のめっき浴とニッケル濃度および塩素濃度が相違する。 (Examples 14 to 19 and Comparative Examples 4 to 8)
Plating baths shown in Table 4 were prepared. The plating bath of Comparative Example 4 is included in the scope of the electrolytic composition shown as Example 1 of Patent Document 3.
In the plating bath of Example 14, diethylenetriamine, which is a kind of polyamine according to the present invention, was added to the plating bath of Comparative Example 4 so that the glycine/polyamine ratio was the same as in Example 1 (6.0). It is a thing.
The plating bath of Example 15 has almost the same composition as the plating bath of Example 1. The plating bath of Comparative Example 5 was obtained by removing diethylenetriamine from the plating bath of Example 15 and containing the same amount of boric acid as in the plating bath of Comparative Example 4. In other words, the plating bath of Comparative Example 5 is the plating bath of Comparative Example 4 with the same nickel concentration and chlorine concentration as in Example 15.
The plating bath of Comparative Example 6 is the same as the plating bath of Comparative Example 4 except that it does not contain boric acid. This composition differs from the plating bath of Comparative Example 1 shown for reference in nickel concentration and chlorine concentration.
表５に示されるめっき浴を調製した。比較例７のめっき浴は、特許文献３の実施例１として示される電解組成物の範囲に含まれる比較例４のめっき浴から、グリシンを非含有とするとともにジエチレントリアミンを実施例１４と同量含有させたものである。
比較例８のめっき浴は、比較例１のめっき浴にホウ酸を比較例４と同量含有させたものである。
実施例１６のめっき浴は、実施例１５のめっき浴と等しい組成である。
実施例１７のめっき浴は、実施例１６のめっき浴に、ホウ酸を比較例４と同量（１５ｇｌ／Ｌ＝０．２４ｍｏｌ／Ｌ）含有させたものである。
実施例１８のめっき浴は、実施例１６のめっき浴に、塩化アンモニウムを１００ｇ／Ｌ（１．９ｍｏｌ／Ｌ）含有させるとともに、塩化カリウムの濃度を１２０ｇ／Ｌ（１．６ｍｏｌ／Ｌ）に低下させ、塩素濃度を１８０ｇ／Ｌ（５．１ｍｏｌ／Ｌ）としたものである。なお、実施例１６の塩素濃度（１５２ｇ／Ｌ）は４．３ｍｏｌ／Ｌである。
実施例１９のめっき浴は、実施例１６のめっき浴に、塩化アンモニウムを２２０ｇ／Ｌ（４．１ｍｏｌ／Ｌ）含有させるとともに、ホウ酸を比較例４と同量（１５ｇｌ／Ｌ＝０．２４ｍｏｌ／Ｌ）含有させたものである。 Plating baths shown in Table 5 were prepared. The plating bath of Comparative Example 7 does not contain glycine from the plating bath of Comparative Example 4 included in the range of the electrolytic composition shown as Example 1 of Patent Document 3, and contains the same amount of diethylenetriamine as that of Example 14. It is what I let you do.
The plating bath of Comparative Example 8 was obtained by adding the same amount of boric acid as in Comparative Example 4 to the plating bath of Comparative Example 1.
The plating bath of Example 16 has the same composition as the plating bath of Example 15.
The plating bath of Example 17 was obtained by adding the same amount of boric acid as in Comparative Example 4 (15 gl/L=0.24 mol/L) to the plating bath of Example 16.
The plating bath of Example 18 was obtained by adding 100 g/L (1.9 mol/L) of ammonium chloride to the plating bath of Example 16 and lowering the concentration of potassium chloride to 120 g/L (1.6 mol/L). and a chlorine concentration of 180 g/L (5.1 mol/L). The chlorine concentration (152 g/L) of Example 16 is 4.3 mol/L.
The plating bath of Example 19 was obtained by adding 220 g/L (4.1 mol/L) of ammonium chloride to the plating bath of Example 16, and adding the same amount of boric acid as in Comparative Example 4 (15 g/L = 0.24 mol/L). /L).
比較例８のめっき浴は、比較例１のめっき浴にホウ酸を比較例４と同量含有させたものである。
実施例１６のめっき浴は、実施例１５のめっき浴と等しい組成である。
実施例１７のめっき浴は、実施例１６のめっき浴に、ホウ酸を比較例４と同量（１５ｇｌ／Ｌ＝０．２４ｍｏｌ／Ｌ）含有させたものである。
実施例１８のめっき浴は、実施例１６のめっき浴に、塩化アンモニウムを１００ｇ／Ｌ（１．９ｍｏｌ／Ｌ）含有させるとともに、塩化カリウムの濃度を１２０ｇ／Ｌ（１．６ｍｏｌ／Ｌ）に低下させ、塩素濃度を１８０ｇ／Ｌ（５．１ｍｏｌ／Ｌ）としたものである。なお、実施例１６の塩素濃度（１５２ｇ／Ｌ）は４．３ｍｏｌ／Ｌである。
実施例１９のめっき浴は、実施例１６のめっき浴に、塩化アンモニウムを２２０ｇ／Ｌ（４．１ｍｏｌ／Ｌ）含有させるとともに、ホウ酸を比較例４と同量（１５ｇｌ／Ｌ＝０．２４ｍｏｌ／Ｌ）含有させたものである。 Plating baths shown in Table 5 were prepared. The plating bath of Comparative Example 7 does not contain glycine from the plating bath of Comparative Example 4 included in the range of the electrolytic composition shown as Example 1 of Patent Document 3, and contains the same amount of diethylenetriamine as that of Example 14. It is what I let you do.
The plating bath of Comparative Example 8 was obtained by adding the same amount of boric acid as in Comparative Example 4 to the plating bath of Comparative Example 1.
The plating bath of Example 16 has the same composition as the plating bath of Example 15.
The plating bath of Example 17 was obtained by adding the same amount of boric acid as in Comparative Example 4 (15 gl/L=0.24 mol/L) to the plating bath of Example 16.
The plating bath of Example 18 was obtained by adding 100 g/L (1.9 mol/L) of ammonium chloride to the plating bath of Example 16 and lowering the concentration of potassium chloride to 120 g/L (1.6 mol/L). and a chlorine concentration of 180 g/L (5.1 mol/L). The chlorine concentration (152 g/L) of Example 16 is 4.3 mol/L.
The plating bath of Example 19 was obtained by adding 220 g/L (4.1 mol/L) of ammonium chloride to the plating bath of Example 16, and adding the same amount of boric acid as in Comparative Example 4 (15 g/L = 0.24 mol/L). /L).
実施例１４から実施例２０および比較例４から比較例８において調製しためっき浴のそれぞれについて、ハルセル試験器（山本鍍金試験器社製「Ｂ－５５Ｌ」）を用いて、次の条件で電解を行った。
電流：４Ａ
時間：５分間
液温：３５℃
液撹拌：スターラー撹拌（７００ｒｐｍ）
アノード板：ニッケル板（山本鍍金試験器社製「Ｂ－５９－Ｐ０２」）
カソード板：鉄板（山本鍍金試験器社製「Ｂ－６０－Ｐ０１ＬＡ」） For each of the plating baths prepared in Examples 14 to 20 and Comparative Examples 4 to 8, electrolysis was performed under the following conditions using a Hull cell tester ("B-55L" manufactured by Yamamoto Plating Tester Co., Ltd.). gone.
Current: 4A
Time: 5 minutes Liquid temperature: 35°C
Liquid stirring: stirrer stirring (700 rpm)
Anode plate: Nickel plate (“B-59-P02” manufactured by Yamamoto Plating Tester Co., Ltd.)
Cathode plate: Iron plate ("B-60-P01LA" manufactured by Yamamoto Plating Tester Co., Ltd.)
電流：４Ａ
時間：５分間
液温：３５℃
液撹拌：スターラー撹拌（７００ｒｐｍ）
アノード板：ニッケル板（山本鍍金試験器社製「Ｂ－５９－Ｐ０２」）
カソード板：鉄板（山本鍍金試験器社製「Ｂ－６０－Ｐ０１ＬＡ」） For each of the plating baths prepared in Examples 14 to 20 and Comparative Examples 4 to 8, electrolysis was performed under the following conditions using a Hull cell tester ("B-55L" manufactured by Yamamoto Plating Tester Co., Ltd.). gone.
Current: 4A
Time: 5 minutes Liquid temperature: 35°C
Liquid stirring: stirrer stirring (700 rpm)
Anode plate: Nickel plate (“B-59-P02” manufactured by Yamamoto Plating Tester Co., Ltd.)
Cathode plate: Iron plate ("B-60-P01LA" manufactured by Yamamoto Plating Tester Co., Ltd.)
得られた亜鉛ニッケル合金めっき皮膜のそれぞれについて、外観評価を行った。その結果を表６に示す。
Appearance evaluation was performed for each of the obtained zinc-nickel alloy plating films. Table 6 shows the results.
亜鉛ニッケル合金めっき被膜が形成されたカソード板を電流密度が異なる方向に等分して２０の領域を設定し、最も高電流密度の領域を除く１９領域のそれぞれについて、高電流密度側の端部の電流密度と低電流密度側の端部の電流密度との算術平均値を求めた。求めた算術平均値をその領域の平均的な電流密度とした。表６の二行目の数値（単位：Ａ／ｄｍ2）は、この平均的な電流密度を示している。
The cathode plate on which the zinc-nickel alloy plating film was formed was equally divided into 20 regions with different current densities. Arithmetic mean value of the current density of and the current density of the end on the low current density side was obtained. The calculated arithmetic average value was taken as the average current density in that region. The numerical value (unit: A/dm 2 ) in the second row of Table 6 indicates this average current density.
各実施例、比較例の行における太文字の数字は、各領域の外観評価の結果を次のように分類した結果である。
１：光沢（白銀色の外観であり、カソード板に対面して覗いたときに観察者の目がはっきり確認できる）
２：半光沢（白銀色の外観であるが観察者の目がぼやけて見える、または反射が確認できる程度である）
３：黒（外観が白銀色ではなく黒い）
４：焦げ（めっき面が粗い） The numbers in bold in the rows of each example and comparative example are the results of classifying the appearance evaluation results of each region as follows.
1: Glossy (It has a silvery white appearance, and the observer's eyes can be clearly seen when facing the cathode plate and looking into it.)
2: Semi-gloss (Appearance is silvery white, but the observer's eyes are blurred, or reflection can be confirmed)
3: Black (appearance is black instead of silvery white)
4: Burnt (plated surface is rough)
１：光沢（白銀色の外観であり、カソード板に対面して覗いたときに観察者の目がはっきり確認できる）
２：半光沢（白銀色の外観であるが観察者の目がぼやけて見える、または反射が確認できる程度である）
３：黒（外観が白銀色ではなく黒い）
４：焦げ（めっき面が粗い） The numbers in bold in the rows of each example and comparative example are the results of classifying the appearance evaluation results of each region as follows.
1: Glossy (It has a silvery white appearance, and the observer's eyes can be clearly seen when facing the cathode plate and looking into it.)
2: Semi-gloss (Appearance is silvery white, but the observer's eyes are blurred, or reflection can be confirmed)
3: Black (appearance is black instead of silvery white)
4: Burnt (plated surface is rough)
表６に示されるように、実施例１５から実施例２０に係る亜鉛ニッケル合金めっき皮膜はいずれも平均電流密度が０．０１Ａ／ｄｍ2の領域から１１Ａ／ｄｍ2の領域まで光沢外観となった。これに対し、比較例に係る亜鉛ニッケル合金めっき皮膜は、実施例ほど広い領域で光沢外観を得ることができなかった。特に、特許文献３の実施例１として示される電解組成物の範囲に含まれる比較例４に係る亜鉛ニッケル合金めっき皮膜は、低電流密度側の領域では、めっき皮膜中のニッケル濃度が過度に高いことに由来する黒色外観が確認され、平均電流密度が１１Ａ／ｄｍ2の領域では電流密度が過大であることに由来する焦げ外観となり、中程度の電流密度においても光沢外観を得ることができなかった。
As shown in Table 6, all of the zinc-nickel alloy plating films according to Examples 15 to 20 had a glossy appearance from an average current density of 0.01 A/dm 2 to 11 A/dm 2 . . On the other hand, the zinc-nickel alloy plating film according to the comparative example could not obtain a glossy appearance in a wider area than the example. In particular, the zinc-nickel alloy plating film according to Comparative Example 4, which is included in the range of the electrolytic composition shown as Example 1 of Patent Document 3, has an excessively high nickel concentration in the plating film in the region on the low current density side. A black appearance derived from this was confirmed, and in the region where the average current density was 11 A/dm 2 , the appearance was scorched due to excessive current density, and a glossy appearance could not be obtained even at a moderate current density. rice field.
比較例４、比較例６から比較例８および実施例１６から実施例２０に係る亜鉛ニッケル合金めっき皮膜における電流密度１１Ａ／ｄｍ2の部分について、グロー放電発光分析（ＧＤ－ＯＥＳ）により測定したニッケルの深さプロファイルを測定した（図１５から図２２）。いずれの図についても、図２などと同様に、深さを示す横軸を、それぞれのめっき皮膜の厚さ（亜鉛濃度と鉄濃度とが等しくなる深さ）で規格化した。図１５から図１８に示されるように、比較例４、比較例６から比較例８に係る亜鉛ニッケル合金めっき皮膜では、規格化された深さで０．８程度から０．８５程度に、ニッケルの濃度が特異的に高くなるニッケル濃縮領域の存在が確認された。これに対し、図１９から図２３に示されるように、実施例１６から実施例２０に係る亜鉛ニッケル合金めっき皮膜では、ニッケル濃縮領域は特に認められなかった。特に、グリシン／ポリアミン比が３０を超える実施例２０のめっき浴であっても、得られた亜鉛ニッケル合金めっき皮膜の深さプロファイルにはニッケル濃縮領域は認められなかった。
Nickel measured by glow discharge optical emission spectroscopy (GD-OES) for portions of the zinc-nickel alloy plating films according to Comparative Example 4, Comparative Examples 6 to 8, and Examples 16 to 20 at a current density of 11 A/dm 2 were measured (Figs. 15 to 22). As in FIG. 2 and the like, in each figure, the horizontal axis indicating the depth is standardized by the thickness of each plating film (the depth at which the zinc concentration and the iron concentration are equal). As shown in FIGS. 15 to 18 , in the zinc-nickel alloy plating films according to Comparative Examples 4 and 6 to 8, the standardized depth was about 0.8 to about 0.85. The existence of a nickel-enriched region where the concentration of is specifically increased was confirmed. In contrast, as shown in FIGS. 19 to 23, in the zinc-nickel alloy plating films according to Examples 16 to 20, no nickel-enriched regions were observed. In particular, even with the plating bath of Example 20 in which the glycine/polyamine ratio exceeds 30, no nickel-enriched region was observed in the depth profile of the obtained zinc-nickel alloy plating film.
Claims (14)
- グリシン含有水溶性物質および炭素数１２以下の脂肪族ポリアミンを有効成分として含有することを特徴とする酸性亜鉛合金めっき浴用添加剤。 An additive for an acidic zinc alloy plating bath characterized by containing a glycine-containing water-soluble substance and an aliphatic polyamine having 12 or less carbon atoms as active ingredients.
- 前記脂肪族ポリアミンは、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミンおよびテトラエチレンペンタミンからなる群から選ばれる１種または２種以上を含む、請求項１に記載の添加剤。 The additive according to claim 1, wherein the aliphatic polyamine contains one or more selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
- 前記グリシン含有水溶性物質のグリシン換算モル濃度の前記脂肪族ポリアミンのモル濃度に対する比であるグリシン／ポリアミン比が、０．１以上４０以下である、請求項１または請求項２に記載の添加剤。 The additive according to claim 1 or 2, wherein the glycine/polyamine ratio, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the molar concentration of the aliphatic polyamine, is 0.1 or more and 40 or less. .
- 浴可溶性亜鉛含有物質と、浴可溶性金属含有物質と、請求項１から請求項３のいずれかに記載される添加剤の前記有効成分と、を含有することを特徴とする酸性亜鉛合金めっき浴。 An acidic zinc alloy plating bath characterized by containing a bath-soluble zinc-containing substance, a bath-soluble metal-containing substance, and the active ingredient of the additive according to any one of claims 1 to 3.
- ｐＨが４以上６以下である、請求項４に記載の酸性亜鉛合金めっき浴。 The acidic zinc alloy plating bath according to claim 4, wherein the pH is 4 or more and 6 or less.
- ホウ酸フリーである、請求項４または請求項５に記載の酸性亜鉛合金めっき浴。 The acidic zinc alloy plating bath according to claim 4 or claim 5, which is free of boric acid.
- アンモニアフリーである、請求項４から請求項６のいずれか１項に記載の酸性亜鉛合金めっき浴。 The acidic zinc alloy plating bath according to any one of claims 4 to 6, which is ammonia-free.
- 酢酸含有物質を含有する、請求項４から請求項７のいずれか１項に記載の酸性亜鉛合金めっき浴。 The acidic zinc alloy plating bath according to any one of claims 4 to 7, which contains an acetic acid-containing substance.
- 前記浴可溶性金属含有物質として、浴可溶性ニッケル含有物質を含み、
前記酸性亜鉛合金めっき浴から形成される亜鉛合金めっき皮膜におけるニッケルの共析率は５質量％以上２０質量％以下である、請求項４から請求項８のいずれか１項に記載の酸性亜鉛合金めっき浴。 including a bath-soluble nickel-containing substance as the bath-soluble metal-containing substance,
The acidic zinc alloy according to any one of claims 4 to 8, wherein the zinc alloy plating film formed from the acidic zinc alloy plating bath has a nickel eutectoid rate of 5% by mass or more and 20% by mass or less. plating bath. - 前記浴可溶性ニッケル含有物質を含み、
前記グリシン含有水溶性物質のグリシン換算モル濃度の前記浴可溶性ニッケル含有物質のニッケル換算モル濃度に対する比であるグリシン／ニッケル比が０．１以上である、請求項９に記載の酸性亜鉛合金めっき浴。 comprising the bath-soluble nickel-containing material;
10. The acidic zinc alloy plating bath according to claim 9, wherein the glycine/nickel ratio, which is the ratio of the glycine-equivalent molar concentration of the glycine-containing water-soluble substance to the nickel-equivalent molar concentration of the bath-soluble nickel-containing substance, is 0.1 or more. . - 一次光沢剤および二次光沢剤の少なくとも一種を含有する、請求項４から請求項１０のいずれか１項に記載の酸性亜鉛合金めっき浴。 The acidic zinc alloy plating bath according to any one of claims 4 to 10, containing at least one of a primary brightener and a secondary brightener.
- 鉄系材料からなる被めっき部材に亜鉛合金めっき皮膜が形成された亜鉛合金めっき部材の深さプロファイルを測定したときに、前記亜鉛合金めっきにおける前記被めっき部材に近位な側に合金元素濃度が相対的に高い合金元素濃縮領域を有しないことを特徴とする亜鉛合金めっき皮膜。 When measuring the depth profile of a zinc alloy-plated member in which a zinc alloy plating film is formed on a member to be plated made of an iron-based material, the alloy element concentration is on the side proximal to the member to be plated in the zinc alloy plating. A zinc alloy plating film characterized by not having a relatively high alloying element concentration region.
- ニッケルを合金元素とする亜鉛合金めっき皮膜であって、グリシンおよび炭素数１２以下の脂肪族ポリアミンを含有するめっき浴から形成された、請求項１２に記載の亜鉛合金めっき皮膜。 The zinc alloy plating film according to claim 12, which is a zinc alloy plating film containing nickel as an alloying element and formed from a plating bath containing glycine and an aliphatic polyamine having 12 or less carbon atoms.
- 前記深さプロファイルにおいて、
亜鉛濃度が６０質量％以上であって最表面に最も近い位置を前記亜鉛合金めっき皮膜の表面側端部、亜鉛濃度が前記被めっき部材に由来する鉄濃度に等しくなる位置を前記亜鉛合金めっき皮膜の前記被めっき部材側端部と定義し、前記表面側端部から前記被めっき部材側端部までの領域の長さを前記亜鉛合金めっき皮膜の厚さと定義したときに、
前記表面側端部から前記亜鉛合金めっきの厚さの４０％から６０％の範囲からなる中間領域におけるニッケル濃度の平均値［Ｎｉ１］と、
前記被めっき部材側端部から前記亜鉛合金めっきの厚さの３０％だけ表面側に移動した位置と前記被めっき部材側端部との範囲からなる初期領域におけるニッケル濃度の最大値［Ｎｉ２］と、間における、ニッケル濃度の最大値［Ｎｉ２］と、
は、下記式（１）を満たす、請求項１２または請求項１３に記載の亜鉛合金めっき皮膜。
［Ｎｉ１］≧［Ｎｉ２］ （１） In the depth profile,
The zinc concentration is 60% by mass or more and the position closest to the outermost surface is the surface side edge of the zinc alloy plating film, and the position where the zinc concentration is equal to the iron concentration derived from the member to be plated is the zinc alloy plating film. defined as the end portion on the side of the member to be plated, and the length of the region from the end portion on the surface side to the end portion on the side of the member to be plated is defined as the thickness of the zinc alloy plating film,
an average value [Ni1] of the nickel concentration in an intermediate region ranging from 40% to 60% of the thickness of the zinc alloy plating from the surface side end,
The maximum value [Ni2] of the nickel concentration in an initial region consisting of a position moved from the side end of the member to be plated to the surface side by 30% of the thickness of the zinc alloy plating and the end portion of the member to be plated; , the maximum value of the nickel concentration [Ni2] between
The zinc alloy plating film according to claim 12 or 13, which satisfies the following formula (1).
[Ni1]≧[Ni2] (1)
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| JPH0874089A (en) * | 1994-09-09 | 1996-03-19 | Nkk Corp | Electrogalvanized steel sheet excellent in whiteness and production of the same |
| JP2016065295A (en) * | 2014-09-25 | 2016-04-28 | ユケン工業株式会社 | Additive for acidic zinc alloy plating bath, acidic zinc alloy plating bath and manufacturing method of zinc alloy plating member |
| JP2018523017A (en) * | 2015-08-11 | 2018-08-16 | ポスコＰｏｓｃｏ | Zinc flash plating solution for electrogalvanized steel sheet with excellent surface appearance, method for producing electrogalvanized steel sheet using the same, and electrogalvanized steel sheet |
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| JPWO2022186183A1 (en) | 2022-09-09 |
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