JP2024035323A - Metal surface treatment agent, and coated metal material and method for producing the same - Google Patents
Metal surface treatment agent, and coated metal material and method for producing the same Download PDFInfo
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- JP2024035323A JP2024035323A JP2022139714A JP2022139714A JP2024035323A JP 2024035323 A JP2024035323 A JP 2024035323A JP 2022139714 A JP2022139714 A JP 2022139714A JP 2022139714 A JP2022139714 A JP 2022139714A JP 2024035323 A JP2024035323 A JP 2024035323A
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- Prior art keywords
- acid
- metal
- surface treatment
- treatment agent
- compound
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 70
- 239000002184 metal Substances 0.000 title claims abstract description 70
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 60
- 239000007769 metal material Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000002253 acid Substances 0.000 claims abstract description 45
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 22
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 8
- 239000010955 niobium Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 239000011135 tin Substances 0.000 claims abstract description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 13
- 235000011007 phosphoric acid Nutrition 0.000 claims description 13
- 150000003009 phosphonic acids Chemical class 0.000 claims description 12
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 9
- 150000003016 phosphoric acids Chemical class 0.000 claims description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 50
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 21
- 229910052721 tungsten Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000010937 tungsten Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- -1 alkali metal salts Chemical class 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000007747 plating Methods 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000012736 aqueous medium Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- NFVUDQKTAWONMJ-UHFFFAOYSA-I pentafluorovanadium Chemical compound [F-].[F-].[F-].[F-].[F-].[V+5] NFVUDQKTAWONMJ-UHFFFAOYSA-I 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000009582 asparagine Nutrition 0.000 description 2
- 229960001230 asparagine Drugs 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 2
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- 229940048102 triphosphoric acid Drugs 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
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- 150000003755 zirconium compounds Chemical class 0.000 description 2
- ZFYIQPIHXRFFCZ-QMMMGPOBSA-N (2s)-2-(cyclohexylamino)butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NC1CCCCC1 ZFYIQPIHXRFFCZ-QMMMGPOBSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- ISQSUCKLLKRTBZ-UHFFFAOYSA-N (phosphonomethylamino)methylphosphonic acid Chemical compound OP(O)(=O)CNCP(O)(O)=O ISQSUCKLLKRTBZ-UHFFFAOYSA-N 0.000 description 1
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- BOZRBIJGLJJPRF-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanenitrile Chemical compound FC(F)(F)C(F)(F)C(F)(F)C#N BOZRBIJGLJJPRF-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical group OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- SRSQDGQUERPXQS-UHFFFAOYSA-N 2-[bis(2-phosphonoethyl)amino]ethylphosphonic acid Chemical compound OP(O)(=O)CCN(CCP(O)(O)=O)CCP(O)(O)=O SRSQDGQUERPXQS-UHFFFAOYSA-N 0.000 description 1
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- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- IEQICHVXWFGDAN-UHFFFAOYSA-N 4-phosphonobenzoic acid Chemical compound OC(=O)C1=CC=C(P(O)(O)=O)C=C1 IEQICHVXWFGDAN-UHFFFAOYSA-N 0.000 description 1
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 1
- QLJOSEUOQHDGTQ-UHFFFAOYSA-N 8-hydroxyquinoline-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)N=C2C(O)=CC=CC2=C1 QLJOSEUOQHDGTQ-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical group OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical group OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- OBBXFSIWZVFYJR-UHFFFAOYSA-L tin(2+);sulfate Chemical compound [Sn+2].[O-]S([O-])(=O)=O OBBXFSIWZVFYJR-UHFFFAOYSA-L 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、金属材料の表面または表面上に皮膜を形成する金属表面処理剤、該金属表面処理剤を用いた皮膜を有する金属材料の製造方法、および該皮膜を有する金属材料に関する。 The present invention relates to a metal surface treatment agent that forms a film on or on the surface of a metal material, a method for manufacturing a metal material having a film using the metal surface treatment agent, and a metal material having the film.
亜鉛めっき鋼板、鋼板等の金属材料には、耐食性を付与するために、その表面に表面処理皮膜を形成させる。近年、環境面や安全面への配慮から、クロム含有の表面処理剤から他の金属含有表面処理剤へとシフトしている。例えば特許文献１には、ジルコニウム化合物を含む金属表面処理剤が開示されており、ジルコニウム化合物に加えて、更にＬｉ、Ｍｇ、Ａｌ、Ｃａ、Ｍｎ、Ｃｏ、Ｎｉ、Ｚｎ、Ｓｒ、Ｗ、Ｃｅ及びＭｏから選ばれる少なくとも１種の金属を含有する化合物を配合することが開示されている。 A surface treatment film is formed on the surface of metal materials such as galvanized steel sheets and steel sheets in order to impart corrosion resistance. In recent years, due to environmental and safety considerations, there has been a shift from chromium-containing surface treatment agents to other metal-containing surface treatment agents. For example, Patent Document 1 discloses a metal surface treatment agent containing a zirconium compound, and in addition to the zirconium compound, Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and It is disclosed that a compound containing at least one metal selected from Mo is blended.
また、特許文献２には、クロム含有の表面処理剤の代替として、エポキシ基またはアミノ基を有する少なくとも１種のシランカップリング剤と二つの加水分解基を有する少なくとも１種のチタンカップリング剤とを縮合してなる縮合体化合物と、Ｍｇ、Ａｌ、Ｔｉ、Ｖ、Ｍｎ、Ｚｎ、Ｚｒ、Ｍｏ、Ｗ、Ｌａ、Ｃｅ、ＮｂおよびＮｄからなる群より選ばれる少なくとも１種の金属化合物を含有する金属表面処理剤が開示されている。 Furthermore, Patent Document 2 discloses that as an alternative to the chromium-containing surface treatment agent, at least one silane coupling agent having an epoxy group or an amino group and at least one titanium coupling agent having two hydrolyzable groups are used. and at least one metal compound selected from the group consisting of Mg, Al, Ti, V, Mn, Zn, Zr, Mo, W, La, Ce, Nb and Nd. A metal surface treatment agent is disclosed.
特許文献１及び２などのように、表面処理皮膜に更なる性能を付与するために、金属化合物を含有させることが行われている。本発明者は、これらの金属化合物のうちタングステンに着目して研究を進めたところ、タングステンを一定量以上含有する金属表面処理剤から形成される表面処理皮膜は、良好な耐食性に加えて、親水性と耐アルカリ性とを両立できる皮膜となり得ることを見出した。一方で、タングステンを一定量以上含有する金属表面処理剤により形成された表面処理皮膜は、皮膜の焼付け工程や、皮膜を有する金属を加工する工程で、皮膜にひび割れが生じやすく、耐食性が悪化する場合があるという新たな課題に想到した。 As in Patent Documents 1 and 2, metal compounds have been incorporated in order to impart further performance to the surface treatment film. The present inventor conducted research focusing on tungsten among these metal compounds, and found that a surface treatment film formed from a metal surface treatment agent containing a certain amount or more of tungsten has good corrosion resistance as well as hydrophilic properties. We have discovered that it is possible to create a film that is both durable and alkali resistant. On the other hand, surface treatment films formed with metal surface treatment agents containing more than a certain amount of tungsten tend to crack during the baking process of the film or the process of processing metals with the film, resulting in poor corrosion resistance. I came up with a new problem:
本発明は、ひび割れを抑制し、良好な耐食性を有する皮膜を形成し得る、タングステンを一定量以上含有する金属表面処理剤を提供することを課題とする。 An object of the present invention is to provide a metal surface treatment agent containing a certain amount or more of tungsten, which can suppress cracking and form a film having good corrosion resistance.
本発明者は、上記課題を解決するために鋭意検討した結果、リン酸類、ホスホン酸類、有機スルホン酸、ポリカルボン酸、ヒドロキシ基を有するモノカルボン酸およびアミノ基を有するモノカルボン酸からなる群より選ばれる少なくとも１種の酸成分（Ａ）と、所定量のタングステン化合物（Ｂ）と、バナジウム、セリウム、モリブデン、マグネシウム、ニオブ、イットリウム、クロム、スズ、マンガン、銅およびランタンからなる群より選ばれる金属を含有する少なくとも１種の金属化合物（Ｃ）と、を配合した金属表面処理剤を用いることにより、金属材料の表面または表面上に、ひび割れを抑制し、良好な耐食性を有する皮膜を形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have determined that a group consisting of phosphoric acids, phosphonic acids, organic sulfonic acids, polycarboxylic acids, monocarboxylic acids having a hydroxy group, and monocarboxylic acids having an amino group. at least one selected acid component (A), a predetermined amount of a tungsten compound (B), selected from the group consisting of vanadium, cerium, molybdenum, magnesium, niobium, yttrium, chromium, tin, manganese, copper, and lanthanum. By using a metal surface treatment agent blended with at least one metal compound (C) containing a metal, it is possible to form a film that suppresses cracking and has good corrosion resistance on or on the surface of a metal material. They discovered this and completed the present invention.
すなわち、本発明は、
（１）リン酸類、ホスホン酸類、有機スルホン酸、ポリカルボン酸、ヒドロキシ基を有するモノカルボン酸およびアミノ基を有するモノカルボン酸からなる群より選ばれる少なくとも１種の酸成分（Ａ）と、タングステン化合物（Ｂ）と、バナジウム、セリウム、モリブデン、マグネシウム、ニオブ、イットリウム、クロム、スズ、マンガン、銅およびランタンからなる群より選ばれる金属を含有する少なくとも１種の金属化合物（Ｃ）と、を配合した金属表面処理剤であって、前記タングステン化合物（Ｂ）のＷ換算固形分質量が前記金属表面処理剤の全固形分質量に対して１８．０％以上である金属表面処理剤；
（２）上記（１）に記載の金属表面処理剤を金属材料の表面または表面上に接触させる工程と、前記金属材料の表面または表面上に接触させた前記金属表面処理剤を乾燥させる工程と、を含む皮膜を有する金属材料の製造方法；
（３）上記（２）に記載の製造方法により得られる、皮膜を有する金属材料；
等である。
That is, the present invention
(1) At least one acid component (A) selected from the group consisting of phosphoric acids, phosphonic acids, organic sulfonic acids, polycarboxylic acids, monocarboxylic acids having a hydroxy group, and monocarboxylic acids having an amino group, and tungsten. Compound (B) and at least one metal compound (C) containing a metal selected from the group consisting of vanadium, cerium, molybdenum, magnesium, niobium, yttrium, chromium, tin, manganese, copper and lanthanum. a metal surface treatment agent, wherein the solid mass of the tungsten compound (B) in terms of W is 18.0% or more with respect to the total solid mass of the metal surface treatment agent;
(2) A step of bringing the metal surface treatment agent described in (1) above into contact with or on the surface of a metal material, and a step of drying the metal surface treatment agent brought into contact with or on the surface of the metal material. A method for producing a metal material having a film comprising;
(3) A metal material having a film obtained by the manufacturing method described in (2) above;
etc.
本発明によれば、金属材料の表面または表面上に、ひび割れを抑制し、良好な耐食性を有する皮膜を形成可能な金属表面処理剤を提供することができる。 According to the present invention, it is possible to provide a metal surface treatment agent that can suppress cracking and form a film having good corrosion resistance on the surface of a metal material.
本実施形態に係る金属表面処理剤は、リン酸類、ホスホン酸類、有機スルホン酸、ポリカルボン酸、ヒドロキシ基を有するモノカルボン酸およびアミノ基を有するモノカルボン酸からなる群より選ばれる少なくとも１種の酸成分（Ａ）と、タングステン化合物（Ｂ）と、バナジウム、セリウム、モリブデン、マグネシウム、ニオブ、イットリウム、クロム、スズ、マンガン、銅およびランタンからなる群より選ばれる金属を含有する少なくとも１種の金属化合物（Ｃ）と、を所定量配合した、金属表面処理剤である。このような金属表面処理剤を用いることにより、金属材料の表面または表面上に、ひび割れを抑制し、良好な耐食性を有する皮膜を形成することができる。なお、本実施形態に係る金属表面処理剤は、水性媒体に、酸成分（Ａ）、タングステン化合物（Ｂ）、金属化合物（Ｃ）のみが配合されたものであってもよいし、その他の成分がさらに配合されたものであってもよいが、耐食性の観点からアルカリ金属は含まないほうが好ましい。また、酸成分（Ａ）、タングステン化合物（Ｂ）および金属化合物（Ｃ）は同一の化合物であってもよく、異なる化合物であってもよい。 The metal surface treatment agent according to the present embodiment is at least one type selected from the group consisting of phosphoric acids, phosphonic acids, organic sulfonic acids, polycarboxylic acids, monocarboxylic acids having a hydroxy group, and monocarboxylic acids having an amino group. At least one metal containing an acid component (A), a tungsten compound (B), and a metal selected from the group consisting of vanadium, cerium, molybdenum, magnesium, niobium, yttrium, chromium, tin, manganese, copper, and lanthanum. This is a metal surface treatment agent containing a predetermined amount of compound (C). By using such a metal surface treatment agent, a film that suppresses cracking and has good corrosion resistance can be formed on the surface of the metal material. Note that the metal surface treatment agent according to the present embodiment may be one in which only the acid component (A), the tungsten compound (B), and the metal compound (C) are blended in the aqueous medium, or may be one in which only the acid component (A), the tungsten compound (B), and the metal compound (C) are blended in the aqueous medium, or other components may be added. may be further blended, but from the viewpoint of corrosion resistance it is preferable that no alkali metal is included. Moreover, the acid component (A), the tungsten compound (B), and the metal compound (C) may be the same compound or may be different compounds.
＜酸成分（Ａ）＞
金属表面処理剤は、酸成分（Ａ）を配合する。酸成分（Ａ）としては、リン酸類、ホスホン酸類、有機スルホン酸、ポリカルボン酸、ヒドロキシ基を有するモノカルボン酸およびアミノ基を有するモノカルボン酸からなる群より選ばれる少なくとも１種の化合物であれば特に制限されるものではなく、これらのアルカリ金属塩、アルカリ土類金属塩、遷移金属塩、アンモニウム塩等を用いてもよい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。１種のみを用いる場合はリン酸類又はホスホン酸類を用いることが好ましい。２種以上を併用する場合は、リン酸類及びホスホン酸類、リン酸類及びポリカルボン酸、又はホスホン酸類及びポリカルボン酸の組み合わせが好ましい。
<Acid component (A)>
The metal surface treatment agent contains an acid component (A). The acid component (A) may be at least one compound selected from the group consisting of phosphoric acids, phosphonic acids, organic sulfonic acids, polycarboxylic acids, monocarboxylic acids having a hydroxy group, and monocarboxylic acids having an amino group. There are no particular limitations, and alkali metal salts, alkaline earth metal salts, transition metal salts, ammonium salts, and the like may be used. In addition, these may use only 1 type, and may use 2 or more types together. When using only one type, it is preferable to use phosphoric acids or phosphonic acids. When two or more types are used in combination, a combination of phosphoric acids and phosphonic acids, phosphoric acids and polycarboxylic acids, or phosphonic acids and polycarboxylic acids is preferred.
酸成分（Ａ）の分子量は特に制限されるものではないが、１，０００以下が好ましく、７００以下がより好ましく、４００以下が特に好ましい。 The molecular weight of the acid component (A) is not particularly limited, but is preferably 1,000 or less, more preferably 700 or less, and particularly preferably 400 or less.
リン酸類としては、リン酸、亜リン酸、次亜リン酸等のモノリン酸；二リン酸、三リン酸等のポリリン酸；フィチン酸等のリン酸エステル等が挙げられる。これらのうち、リン酸、二リン酸または三リン酸を用いることが好ましく、リン酸を用いることがより好まし
い。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。
Examples of the phosphoric acids include monophosphoric acids such as phosphoric acid, phosphorous acid, and hypophosphorous acid; polyphosphoric acids such as diphosphoric acid and triphosphoric acid; and phosphoric acid esters such as phytic acid. Among these, it is preferable to use phosphoric acid, diphosphoric acid or triphosphoric acid, and it is more preferable to use phosphoric acid. In addition, these may use only 1 type, and may use 2 or more types together.
ホスホン酸類とは、ホスホン酸または少なくとも１つのホスホン酸基｛－Ｐ（＝Ｏ）（ＯＨ）２｝を有する有機ホスホン酸を意味する。有機ホスホン酸は、カルボキシ基、ヒドロキシ基またはアミノ基を有していてもよい。有機ホスホン酸としては、例えば、メチルホスホン酸、プロピルホスホン酸、ヘキシルホスホン酸、ドデシルホスホン酸、ヘキサデシルホスホン酸、フェニルホスホン酸、４－ヒドロキシフェニルホスホン酸、４－カルボキシフェニルホスホン酸、（アミノメチル）ホスホン酸、３－ホスホノプロピオン酸、２－ホスホノブタン－１，２，４－トリカルボン酸等の１つのホスホン酸基を有する化合物；１，２－エチレンジホスホン酸、１，６－ヘキサンジホスホン酸、１－ヒドロキシエチリデン－１，１－ジホスホン酸、ｐ－キシリレンジホスホン酸、イミノジ（メチルホスホン酸）等の２つのホスホン酸基を有する化合物；ニトリロトリス（メチレンホスホン酸）、ニトリロトリス（エチレンホスホン酸）等の３つのホスホン酸基を有する化合物；Ｎ，Ｎ，Ｎ’，Ｎ’－エチレンジアミンテトラキス（メチレンホスホン酸）、ジエチレントリアミンペンタキス（メチレンホスホン酸）等の４つ以上のホスホン酸基を有する化合物等が挙げられる。これらのうち、１つのホスホン酸基と１つ以上のカルボキシ基とを有する化合物または２つ以上のホスホン酸基を有する化合物を用いることが好ましく、１つのホスホン酸基と３つ以上のカルボキシ基とを有する化合物または２つ以上のホスホン酸基を有する化合物を用いることがより好ましい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。 Phosphonic acids mean phosphonic acids or organic phosphonic acids having at least one phosphonic acid group {-P(=O)(OH) 2 }. The organic phosphonic acid may have a carboxy group, a hydroxy group or an amino group. Examples of organic phosphonic acids include methylphosphonic acid, propylphosphonic acid, hexylphosphonic acid, dodecylphosphonic acid, hexadecylphosphonic acid, phenylphosphonic acid, 4-hydroxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, (aminomethyl) Compounds with one phosphonic acid group such as phosphonic acid, 3-phosphonopropionic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid; 1,2-ethylenediphosphonic acid, 1,6-hexanediphosphonic acid , 1-hydroxyethylidene-1,1-diphosphonic acid, p-xylylene diphosphonic acid, iminodi(methylphosphonic acid), etc. Compounds with two phosphonic acid groups; nitrilotris (methylenephosphonic acid), nitrilotris (ethylenephosphonic acid) ) Compounds with three phosphonic acid groups such as N,N,N',N'-ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriaminepentakis (methylenephosphonic acid), etc. Compounds with four or more phosphonic acid groups etc. Among these, it is preferable to use a compound having one phosphonic acid group and one or more carboxy groups or a compound having two or more phosphonic acid groups, and a compound having one phosphonic acid group and three or more carboxy groups is preferably used. It is more preferable to use a compound having a phosphonic acid group or a compound having two or more phosphonic acid groups. In addition, these may use only 1 type, and may use 2 or more types together.
有機スルホン酸とは、少なくとも１つのスルホン酸基｛－Ｓ（＝Ｏ）２（ＯＨ）｝を有する化合物を意味する。有機スルホン酸は、カルボキシ基、ヒドロキシ基またはアミノ基を有していてもよい。ただし、ホスホン酸基を有する化合物は除く。例えば、メタンスルホン酸、エタンスルホン酸、２－ヒドロキシエタンスルホン酸等の１つのスルホン酸基を有する化合物；４，５－ジヒドロキシ－１，３－ベンゼンジスルホン酸等の２つのスルホン酸基を有する化合物等が挙げられる。これらのうち、メタンスルホン酸またはエタンスルホン酸を用いることが好ましい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。 Organic sulfonic acid means a compound having at least one sulfonic acid group {-S(=O) 2 (OH)}. The organic sulfonic acid may have a carboxy group, hydroxy group or amino group. However, compounds with phosphonic acid groups are excluded. For example, compounds with one sulfonic acid group such as methanesulfonic acid, ethanesulfonic acid, and 2-hydroxyethanesulfonic acid; compounds with two sulfonic acid groups such as 4,5-dihydroxy-1,3-benzenedisulfonic acid. etc. Among these, it is preferable to use methanesulfonic acid or ethanesulfonic acid. In addition, these may use only 1 type, and may use 2 or more types together.
ポリカルボン酸とは、２つ以上のカルボキシ基を有する化合物を意味する。ポリカルボン酸は、ヒドロキシ基またはアミノ基を有していてもよい。ただし、ホスホン酸基を有する化合物およびスルホン酸基を有する化合物は除く。例えば、シュウ酸、マロン酸、コハク酸、フマル酸、マレイン酸、アゼライン酸、ベンゼン－１，２－ジカルボン酸等の２つのカルボキシ基を有する化合物；酒石酸、リンゴ酸等のヒドロキシ基と２つのカルボキシ基とを有する化合物；アスパラギン酸、グルタミン酸等のアミノ基と２つのカルボキシ基とを有する化合物；アコニット酸等の３つのカルボキシ基を有する化合物；クエン酸等のヒドロキシ基と３つのカルボキシ基とを有する化合物；エチレンジアミン四酢酸、ニトリロ三酢酸、Ｎ－（２－ヒドロキシエチル）エチレンジアミン－Ｎ，Ｎ’，Ｎ’－三酢酸等の２つ以上のカルボキシ基を有するアミン化合物等が挙げられる。これらのうち、２つのカルボキシ基を有する化合物、ヒドロキシ基と２つのカルボキシ基とを有する化合物、ヒドロキシ基と３つのカルボキシ基とを有する化合物または２つ以上のカルボキシ基を有するアミン化合物を用いることが好ましく、ヒドロキシ基と２つのカルボキシ基とを有する化合物またはヒドロキシ基と３つのカルボキシ基とを有する化合物を用いることがより好ましく、ヒドロキシ基と３つのカルボキシ基とを有する化合物を用いることが特に好ましい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。 Polycarboxylic acid means a compound having two or more carboxy groups. The polycarboxylic acid may have a hydroxy group or an amino group. However, compounds with phosphonic acid groups and compounds with sulfonic acid groups are excluded. For example, compounds with two carboxyl groups such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, azelaic acid, and benzene-1,2-dicarboxylic acid; compounds with a hydroxy group and two carboxyl groups such as tartaric acid and malic acid. Compounds having an amino group and two carboxy groups such as aspartic acid and glutamic acid; Compounds having three carboxy groups such as aconitic acid; Compounds having a hydroxy group and three carboxy groups such as citric acid Compounds include amine compounds having two or more carboxy groups such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid, and the like. Among these, it is possible to use a compound having two carboxyl groups, a compound having a hydroxy group and two carboxyl groups, a compound having a hydroxy group and three carboxyl groups, or an amine compound having two or more carboxyl groups. Preferably, a compound having a hydroxy group and two carboxy groups or a compound having a hydroxy group and three carboxy groups is more preferably used, and a compound having a hydroxy group and three carboxy groups is particularly preferably used. In addition, these may use only 1 type, and may use 2 or more types together.
ヒドロキシ基を有するモノカルボン酸とは、１つ以上のヒドロキシ基と１つのカルボキシ基とを有する化合物を意味する。ヒドロキシ基を有するモノカルボン酸は、アミノ基を有していてもよい。ただし、ホスホン酸基を有する化合物およびスルホン酸基を有する化
合物は除く。例えば、グリコール酸、乳酸等の１つのヒドロキシ基と１つのカルボキシ基とを有する化合物；グルコン酸等の２つ以上のヒドロキシ基と１つのカルボキシ基とを有する化合物等が挙げられる。これらのうち、２つ以上のヒドロキシ基と１つのカルボキシ基とを有する化合物を用いることが好ましい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。
A monocarboxylic acid having a hydroxy group means a compound having one or more hydroxy groups and one carboxy group. The monocarboxylic acid having a hydroxy group may also have an amino group. However, compounds with phosphonic acid groups and compounds with sulfonic acid groups are excluded. Examples include compounds having one hydroxy group and one carboxy group such as glycolic acid and lactic acid; compounds having two or more hydroxy groups and one carboxy group such as gluconic acid. Among these, it is preferable to use a compound having two or more hydroxy groups and one carboxy group. In addition, these may use only 1 type, and may use 2 or more types together.
アミノ基を有するモノカルボン酸とは、１つ以上のアミノ基と１つのカルボキシ基とを有する化合物を意味する。ただし、ホスホン酸基を有する化合物、スルホン酸基を有する化合物およびヒドロキシ基を有する化合物は除く。例えば、アラニン、アスパラギン、グルタミン、システイン、グリシン、リシン等が挙げられる。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。 A monocarboxylic acid having an amino group means a compound having one or more amino groups and one carboxy group. However, compounds with phosphonic acid groups, compounds with sulfonic acid groups, and compounds with hydroxyl groups are excluded. Examples include alanine, asparagine, glutamine, cysteine, glycine, lysine, and the like. In addition, these may use only 1 type, and may use 2 or more types together.
金属表面処理剤中の酸成分（Ａ）の濃度は特に制限されるものではないが、酸成分（Ａ）の固形分質量が表面処理剤の全固形分質量に対して通常１．０％以上であり、２０．０％～７６．０％の範囲内であることが好ましく、５０．０％～６０．０％の範囲内であることがより好ましい。なお、金属表面処理剤中において酸成分（Ａ）は、それぞれの酸の形態で存在する場合、イオン化していない形態で存在する場合、一部又は全部の官能基がイオン化した形態で存在する場合、アルカリ金属塩やアンモニウム塩などの塩の形態で存在する場合、金属錯体の形態で存在する場合、これらの形態が交じり合った状態で存在する場合、などがある。酸成分（Ａ）が存在することで、皮膜に生じるひび割れを抑制することができ、タングステンを皮膜中に留めて良好な耐食性を有する皮膜を形成することができる。 The concentration of the acid component (A) in the metal surface treatment agent is not particularly limited, but the solid mass of the acid component (A) is usually 1.0% or more based on the total solid mass of the surface treatment agent. It is preferably within the range of 20.0% to 76.0%, and more preferably within the range of 50.0% to 60.0%. In addition, when the acid component (A) in the metal surface treatment agent exists in the form of each acid, when it exists in a non-ionized form, when it exists in a form where some or all of the functional groups are ionized. , in the form of a salt such as an alkali metal salt or ammonium salt, in the form of a metal complex, or in a mixture of these forms. The presence of the acid component (A) can suppress cracks that occur in the film, retain tungsten in the film, and form a film with good corrosion resistance.
＜タングステン化合物（Ｂ）＞
金属表面処理剤は、タングステン化合物（Ｂ）を配合する。タングステン化合物（Ｂ）としては、１分子中に１つ以上のタングステン元素を含む化合物であれば特に制限されるものではなく、またタングステン元素を含む化合物は、無水物であってもよく、水和物であってもよい。例えば、タングステン酸、タングステン酸ナトリウム等のタングステンを含有するオキソ酸の無水物及び水和物；メタタングステン酸ナトリウム、メタタングステン酸アンモニウム、タングステン酸アンモニウム等のタングステンを含有するイソポリ酸の無水物及び水和物；ケイタングステン酸、リンタングステン酸、リンタングストモリブデン酸等のタングステンを含有するヘテロポリ酸等の無水物及び水和物が挙げられる。これらのうち、タングステンを含有するオキソ酸またはタングステンを含有するイソポリ酸を用いることが好ましく、タングステン酸、メタタングステン酸アンモニウム、タングステン酸アンモニウムまたはこれらの水和物を用いることがより好ましく、メタタングステン酸アンモニウム、タングステン酸アンモニウムまたはこれらの水和物を用いることが特に好ましい。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。
<Tungsten compound (B)>
The metal surface treatment agent contains a tungsten compound (B). The tungsten compound (B) is not particularly limited as long as it is a compound containing one or more tungsten elements in one molecule, and compounds containing tungsten elements may be anhydrous or hydrated. It may be a thing. For example, anhydrides and hydrates of tungsten-containing oxoacids such as tungstic acid and sodium tungstate; anhydrides and hydrates of tungsten-containing isopoly acids such as sodium metatungstate, ammonium metatungstate, and ammonium tungstate. Examples include anhydrides and hydrates of tungsten-containing heteropolyacids such as silicotungstic acid, phosphotungstic acid, and phosphotungstomolybdic acid. Among these, it is preferable to use tungsten-containing oxoacid or tungsten-containing isopoly acid, and it is more preferable to use tungstic acid, ammonium metatungstate, ammonium tungstate, or hydrates thereof, and metatungstic acid Particular preference is given to using ammonium, ammonium tungstate or hydrates thereof. In addition, these may use only 1 type, and may use 2 or more types together.
金属表面処理剤中のタングステン化合物（Ｂ）の濃度は、Ｗ（タングステン）換算固形分質量が表面処理剤の全固形分質量に対して１８．０％以上であればよい。２０．０％～５５．０％の範囲内であることが好ましく、２２．０％～４５．０％の範囲内であることがより好ましく、２４．０％～４０．０％の範囲内であることが特に好ましい。なお、金属表面処理剤中においてタングステン化合物（Ｂ）は、タングステンを含有する酸の形態で存在する場合、イオン化していない形態で存在する場合、一部又は全部の官能基がイオン化した形態で存在する場合、アルカリ金属塩やアンモニウム塩などの塩の形態で存在する場合、金属錯体の形態で存在する場合、これらの形態が交じり合った状態で存在する場合、などがある。タングステンが存在することで、良好な耐食性を有する皮膜を形成することができる。また、皮膜中にタングステンが多く存在することで、抗菌性能が向上するとともに、耐酸性及び耐アルカリ性が向上する。 The concentration of the tungsten compound (B) in the metal surface treatment agent may be such that the solid mass in terms of W (tungsten) is 18.0% or more with respect to the total solid mass of the surface treatment agent. It is preferably within the range of 20.0% to 55.0%, more preferably within the range of 22.0% to 45.0%, and within the range of 24.0% to 40.0%. It is particularly preferable that there be. In addition, in the metal surface treatment agent, when the tungsten compound (B) exists in the form of an acid containing tungsten, when it exists in a non-ionized form, it exists in a form in which some or all of the functional groups are ionized. It exists in the form of a salt such as an alkali metal salt or an ammonium salt, it exists in the form of a metal complex, and it exists in a mixture of these forms. The presence of tungsten makes it possible to form a film with good corrosion resistance. Furthermore, the presence of a large amount of tungsten in the film improves antibacterial performance, as well as acid resistance and alkali resistance.
金属表面処理剤中に配合する、タングステン化合物（Ｂ）のＷ換算固形分質量（ＢＭ）に対する酸成分（Ａ）の固形分質量（ＡＭ）の割合［ＡＭ／ＢＭ］は、皮膜のひび割れを抑制する観点から、１．２～４．４の範囲内であることが好ましく、２．５～３．８の範囲内であることがより好ましい。 The ratio [A M /B M ] of the solid content mass (A M ) of the acid component (A) to the W-equivalent solid content mass (B M ) of the tungsten compound (B), which is blended into the metal surface treatment agent, is From the viewpoint of suppressing cracking, it is preferably within the range of 1.2 to 4.4, and more preferably within the range of 2.5 to 3.8.
＜金属化合物（Ｃ）＞
金属表面処理剤は、金属化合物（Ｃ）を配合する。金属化合物（Ｃ）としては、バナジウム、セリウム、モリブデン、マグネシウム、ニオブ、イットリウム、クロム、スズ、マンガン、銅およびランタンからなる群より選ばれる金属を含有する少なくとも１種の化合物であれば特に制限されるものではなく、前記金属の酸化物、水酸化物、炭酸塩、硝酸塩、硫酸塩、塩化物、フッ化物、有機酸塩、錯化合物等が挙げられる。ただし、セリウム、ニオブ、イットリウム、スズおよびランタンの酸化物は除く。なお、これらは１種のみを用いてもよいし、２種以上を併用してもよい。これらのうち、バナジウム化合物、モリブデン化合物、マグネシウム化合物またはクロム化合物を用いることが好ましく、バナジウム化合物を用いることがより好ましい。
<Metal compound (C)>
The metal surface treatment agent contains a metal compound (C). The metal compound (C) is not particularly limited as long as it is a compound containing at least one metal selected from the group consisting of vanadium, cerium, molybdenum, magnesium, niobium, yttrium, chromium, tin, manganese, copper and lanthanum. Examples include oxides, hydroxides, carbonates, nitrates, sulfates, chlorides, fluorides, organic acid salts, and complex compounds of the metals. However, oxides of cerium, niobium, yttrium, tin and lanthanum are excluded. In addition, these may use only 1 type, and may use 2 or more types together. Among these, it is preferable to use a vanadium compound, a molybdenum compound, a magnesium compound, or a chromium compound, and it is more preferable to use a vanadium compound.
バナジウム化合物としては、例えば、水酸化バナジウム、硫酸バナジウム等のバナジウムの酸化数が２価の化合物；三酸化バナジウム、硫酸バナジウム、フッ化バナジウム、ヘキサフルオロバナジウム酸、ヘキサフルオロバナジウム酸アンモニウム、バナジウムアセチルアセトネート等のバナジウムの酸化数が３価の化合物；二酸化バナジウム、オキシ硫酸バナジウム、フッ化バナジウム、バナジルアセチルアセトネート等のバナジウムの酸化数が４価の化合物；五酸化バナジウム、フッ化バナジウム、メタバナジン酸、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、オキシ三塩化バナジウム等のバナジウムの酸化数が５価の化合物等が挙げられる。 Examples of vanadium compounds include compounds in which the oxidation number of vanadium is divalent, such as vanadium hydroxide and vanadium sulfate; vanadium trioxide, vanadium sulfate, vanadium fluoride, hexafluorovanadate, ammonium hexafluorovanadate, and vanadium acetylaceto. Compounds with a trivalent vanadium oxidation number such as ester; compounds with a tetravalent vanadium oxidation number such as vanadium dioxide, vanadium oxysulfate, vanadium fluoride, vanadyl acetylacetonate; vanadium pentoxide, vanadium fluoride, metavanadic acid , ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride, and other compounds in which the oxidation number of vanadium is pentavalent.
セリウム化合物としては、例えば、酢酸セリウム、硝酸セリウム、硝酸セリウムアンモニウム、硫酸セリウム、塩化セリウム等が挙げられる。 Examples of the cerium compound include cerium acetate, cerium nitrate, cerium ammonium nitrate, cerium sulfate, and cerium chloride.
モリブデン化合物としては、例えば、酸化モリブデン、モリブデン酸、モリブデン酸アンモニウム、パラモリブデン酸アンモニウム、モリブデン酸ナトリウム等が挙げられる。 Examples of molybdenum compounds include molybdenum oxide, molybdic acid, ammonium molybdate, ammonium paramolybdate, and sodium molybdate.
マグネシウム化合物としては、例えば、硝酸マグネシウム、硫酸マグネシウム、酢酸マグネシウム、フッ化マグネシウム、水酸化マグネシウム、シュウ酸マグネシウム、酸化マグネシウム、塩基性炭酸マグネシウム等が挙げられる。 Examples of the magnesium compound include magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium fluoride, magnesium hydroxide, magnesium oxalate, magnesium oxide, and basic magnesium carbonate.
ニオブ化合物としては、例えば、ニオブ酸ナトリウム、フッ化ニオブ、塩化ニオブ、ヘキサフルオロニオブ酸アンモニウム等が挙げられる。 Examples of the niobium compound include sodium niobate, niobium fluoride, niobium chloride, ammonium hexafluoroniobate, and the like.
イットリウム化合物としては、例えば、硝酸イットリウム、イットリウムアセチルアセトネート等が挙げられる。 Examples of the yttrium compound include yttrium nitrate, yttrium acetylacetonate, and the like.
クロム化合物としては、例えば、硝酸クロム、硫酸クロム、フッ化クロム、塩化クロム、ギ酸クロム、酸化クロム等が挙げられる。 Examples of the chromium compound include chromium nitrate, chromium sulfate, chromium fluoride, chromium chloride, chromium formate, and chromium oxide.
スズ化合物としては、例えば、スズ酸ナトリウム、フッ化スズ、塩化スズ、硝酸スズ、硫酸スズ、ヘキサフルオロスズ酸アンモニウム等が挙げられる。 Examples of the tin compound include sodium stannate, tin fluoride, tin chloride, tin nitrate, tin sulfate, and ammonium hexafluorostannate.
マンガン化合物としては、例えば、炭酸マンガン、硝酸マンガン、硫酸マンガン、酢酸マンガン、フッ化マンガン、酸化マンガン、三酸化マンガン等が挙げられる。 Examples of the manganese compound include manganese carbonate, manganese nitrate, manganese sulfate, manganese acetate, manganese fluoride, manganese oxide, and manganese trioxide.
銅化合物としては、例えば、炭酸銅、硝酸銅、硫酸銅、塩化銅、酸化銅、フッ化銅等が挙げられる。 Examples of the copper compound include copper carbonate, copper nitrate, copper sulfate, copper chloride, copper oxide, and copper fluoride.
ランタン化合物としては、例えば、水酸化ランタン、硝酸ランタン、フッ化ランタン、塩化ランタン、炭酸ランタン、硫酸ランタン、リン酸ランタン、リン酸水素ランタン、シュウ酸ランタン、酢酸ランタン、トリフルオロメタンスルホン酸ランタン等が挙げられる。 Examples of lanthanum compounds include lanthanum hydroxide, lanthanum nitrate, lanthanum fluoride, lanthanum chloride, lanthanum carbonate, lanthanum sulfate, lanthanum phosphate, lanthanum hydrogen phosphate, lanthanum oxalate, lanthanum acetate, and lanthanum trifluoromethanesulfonate. Can be mentioned.
金属表面処理剤中の金属化合物（Ｃ）の濃度は特に制限されるものではないが、金属換算固形分質量が表面処理剤の全固形分質量に対して通常０．１％以上であり、０．５％～２０．０％の範囲内であることが好ましく、１．０％～１５．０％の範囲内であることがより好ましく、２．０％～６．０％の範囲内であることが特に好ましい。なお、金属表面処理剤中において金属化合物（Ｃ）は、金属を含有する酸の形態で存在する場合、イオン化していない形態で存在する場合、一部又は全部の官能基がイオン化した形態で存在する場合、アルカリ金属塩やアンモニウム塩などの塩の形態で存在する場合、金属錯体の形態で存在する場合、これらの形態が交じり合った状態で存在する場合、などがある。 The concentration of the metal compound (C) in the metal surface treatment agent is not particularly limited, but the solid mass in terms of metal is usually 0.1% or more with respect to the total solid mass of the surface treatment agent, and 0. It is preferably within the range of .5% to 20.0%, more preferably within the range of 1.0% to 15.0%, and within the range of 2.0% to 6.0%. It is particularly preferable. In addition, in the metal surface treatment agent, the metal compound (C) is present in the form of an acid containing metal, in a non-ionized form, or in a form in which some or all of the functional groups are ionized. It exists in the form of a salt such as an alkali metal salt or an ammonium salt, it exists in the form of a metal complex, and it exists in a mixture of these forms.
＜水性媒体＞
金属表面処理剤は、水性媒体に上記酸成分（Ａ）、タングステン化合物（Ｂ）及び金属化合物（Ｃ）を配合してなる。水性媒体としては、水または水と水混和性有機溶媒との混合物（水性媒体の体積を基準として５０体積％以上の水を含有するもの）であれば特に制限されるものではない。水混和性有機溶媒としては、水と混和するものであれば特に制限されるものではなく、例えば、アセトン、メチルエチルケトン等のケトン系溶媒；Ｎ，Ｎ’－ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒；メタノール、エタノール、イソプロパノール等のアルコール系溶媒；エチレングリコールモノブチルエーテル、エチレングリコールモノへキシルエーテル等のエーテル系溶媒；１－メチル－２－ピロリドン、１－エチル－２－ピロリドン等のピロリドン系溶媒等が挙げられる。これらの水混和性有機溶媒は１種を水と混合させてもよいし、２種以上を水と混合させてもよい。
<Aqueous medium>
The metal surface treatment agent is made by blending the above acid component (A), tungsten compound (B), and metal compound (C) in an aqueous medium. The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). Water-miscible organic solvents are not particularly limited as long as they are miscible with water; examples include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide. ; Alcohol solvents such as methanol, ethanol, and isopropanol; Ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; Pyrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone, etc. can be mentioned. One kind of these water-miscible organic solvents may be mixed with water, or two or more kinds thereof may be mixed with water.
＜その他の成分＞
その他の成分としては特に制限されるものではないが、例えば、界面活性剤、消泡剤、レベリング剤、架橋剤、可塑剤、防菌防黴剤、着色剤等が挙げられる。
<Other ingredients>
Other components include, but are not particularly limited to, surfactants, antifoaming agents, leveling agents, crosslinking agents, plasticizers, antibacterial and fungicidal agents, colorants, and the like.
＜金属表面処理剤のｐＨ＞
金属表面処理剤のｐＨは特に制限されないが、１～１０の範囲内であることが好ましく、２～９の範囲内であることがより好ましく、３～８の範囲内であることが特に好ましい。ここで、本明細書における金属表面処理剤のｐＨ値は、ｐＨメーターを用いて２５℃で測定した値を意味する。
金属表面処理剤のｐＨは、例えば、塩酸、硫酸、硝酸、フッ化水素酸、ホウ酸、有機酸等の酸成分；水酸化リチウム、水酸化カリウム、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム、アルカリ金属塩、アンモニア水、アンモニウム塩、アミン類等のアルカリ成分；等のｐＨ調整剤を用いて調整することができるが、これらの成分に制限されるものではない。なお、ｐＨ調整剤は、１種のみを用いてもよいし、２種以上を用いてもよい。
<pH of metal surface treatment agent>
The pH of the metal surface treatment agent is not particularly limited, but is preferably within the range of 1 to 10, more preferably within the range of 2 to 9, and particularly preferably within the range of 3 to 8. Here, the pH value of the metal surface treatment agent in this specification means a value measured at 25° C. using a pH meter.
The pH of the metal surface treatment agent is determined by acid components such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, and organic acids; lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide. , barium hydroxide, alkali metal salts, aqueous ammonia, ammonium salts, alkaline components such as amines; etc., but are not limited to these components. In addition, only 1 type of pH adjuster may be used, and 2 or more types may be used.
＜金属表面処理剤の製造方法＞
本実施形態に係る金属表面処理剤の製造方法は特に制限されないが、例えば、酸成分（Ａ）、タングステン化合物（Ｂ）および金属化合物（Ｃ）をこの順序で水性媒体に所定量配合することにより製造可能である。ｐＨ調整剤を配合する場合は、酸成分（Ａ）、タングステン化合物（Ｂ）、ｐＨ調整剤および金属化合物（Ｃ）をこの順序で水性媒体に所定
量配合して製造することが好ましい。なお、その他の成分を配合する場合には、例えば、上記の各原料を水性媒体に配合した後、その他の成分を配合することにより製造できる。
<Method for producing metal surface treatment agent>
Although the method for producing the metal surface treatment agent according to the present embodiment is not particularly limited, for example, by blending a predetermined amount of an acid component (A), a tungsten compound (B), and a metal compound (C) in this order into an aqueous medium. Manufacturable. When blending a pH adjuster, it is preferable to mix predetermined amounts of the acid component (A), tungsten compound (B), pH adjuster, and metal compound (C) in this order into an aqueous medium. In addition, when blending other components, it can be manufactured by, for example, blending each of the above-mentioned raw materials in an aqueous medium and then blending the other components.
＜皮膜を有する金属材料の製造方法＞
本実施形態に係る皮膜を有する金属材料の製造方法は、金属材料の表面または表面上に本実施形態に係る金属表面処理剤を接触させる接触工程と、金属材料の表面または表面上に接触させた金属表面処理剤を乾燥させる乾燥工程と、を含む。これにより、金属材料の表面または表面上に皮膜が形成される。なお、接触工程の前に脱脂工程等を行ってもよい。
<Method for producing metal material with film>
The method for producing a metal material having a film according to the present embodiment includes a contact step of bringing the metal surface treatment agent according to the present embodiment into contact with the surface of the metal material or on the surface of the metal material; The method includes a drying step of drying the metal surface treatment agent. As a result, a film is formed on or on the surface of the metal material. Note that a degreasing step or the like may be performed before the contact step.
＜接触工程＞
接触方法としては、例えば、スプレー法、浸漬法、ロールコート法、バーコート法、カーテンコート法、スピンコート法、またはこれらの組み合わせ等の方法が挙げられるが、これらに制限されるものではない。接触温度や接触時間は、金属表面処理剤の組成や濃度によって適宜設定される。通常、接触温度は１０℃～９０℃以下の範囲内であり、接触時間は５秒～６００秒の範囲内であるが、これらに制限されるものではない。
<Contact process>
Examples of the contact method include, but are not limited to, a spray method, a dipping method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, or a combination thereof. The contact temperature and contact time are appropriately set depending on the composition and concentration of the metal surface treatment agent. Usually, the contact temperature is within the range of 10° C. to 90° C. or less, and the contact time is within the range of 5 seconds to 600 seconds, but is not limited thereto.
＜乾燥工程＞
乾燥方法は特に制限されず、公知の乾燥機器、例えば、バッチ式の乾燥炉、連続式の熱風循環式乾燥炉、コンベアー式の熱風乾燥炉、電磁誘導加熱炉等を用いた乾燥方法等を挙げることができる。乾燥温度や乾燥時間は、金属材料の種類や接触させた金属表面処理剤の組成または量によって適宜設定される。乾燥温度は、特に制限されるものではないが、金属材料の最高到達温度（ＰＭＴ）が５０℃～２００℃の範囲内であることが好ましく、８０℃～１７０℃の範囲内であることがより好ましく、１００℃～１３０℃の範囲内であることが特に好ましい。乾燥時間も特に制限されるものではないが、通常２秒～１８００秒の範囲内である。
<Drying process>
The drying method is not particularly limited, and examples include drying methods using known drying equipment, such as a batch type drying oven, a continuous hot air circulation drying oven, a conveyor type hot air drying oven, an electromagnetic induction heating oven, etc. be able to. The drying temperature and drying time are appropriately set depending on the type of metal material and the composition or amount of the metal surface treatment agent brought into contact. The drying temperature is not particularly limited, but the maximum temperature (PMT) of the metal material is preferably within the range of 50 ° C to 200 ° C, more preferably within the range of 80 ° C to 170 ° C. Preferably, the temperature is particularly preferably within the range of 100°C to 130°C. The drying time is also not particularly limited, but is usually within the range of 2 seconds to 1800 seconds.
＜脱脂工程＞
脱脂方法としては、金属材料の表面に付着している油脂類や汚れを除去することができればいかなる方法であってもよく、例えば、溶剤脱脂、アルカリ系または酸系の脱脂剤等を用いた公知の方法を挙げることができる。なお、脱脂工程を行った後に接触工程を行う場合には、脱脂工程後であって、接触工程の前に金属材料の表面または表面上を水洗する工程を行ってもよいし、行わなくてもよい。水洗を行った場合には、続いて金属材料の表面または表面上を乾燥してもよいし、乾燥しなくてもよい。
<Degreasing process>
The degreasing method may be any method as long as it can remove oils and dirt adhering to the surface of the metal material, such as solvent degreasing, known methods using alkaline or acid degreasing agents, etc. The following methods can be mentioned. In addition, when the contact step is performed after the degreasing step, a step of washing the surface of the metal material with water may or may not be performed after the degreasing step and before the contact step. good. When washing with water is performed, the surface of the metal material may or may not be subsequently dried.
＜金属材料＞
皮膜を形成させる金属材料の形状や構造等は特に限定されず、例えば、板状、箔状等を挙げることができる。金属材料の種類についても特に限定されず、例えば、鉄鋼材料（例えば、冷間圧延鋼板、熱間圧延鋼板、黒皮材、酸洗鋼板、高張力鋼板、工具鋼、合金工具鋼、球状化黒鉛鋳鉄、ねずみ鋳鉄等）；めっき材料、例えば、亜鉛めっき材（例えば、電気亜鉛めっき、溶融亜鉛めっき、アルミニウム含有亜鉛めっき、電気亜鉛めっき、亜鉛ニッケルめっき、亜鉛コバルトめっき、蒸着亜鉛めっき等）、亜鉛合金めっき材（例えば、合金化溶融亜鉛めっき、Ｚｎ－Ａｌ合金めっき、Ｚｎ－Ａｌ－Ｍｇ合金めっき、電気亜鉛合金めっき等）、アルミめっき材、ニッケルめっき材、スズめっき材、クロムめっき材、クロム合金めっき材（例えば、Ｃｒ－Ｎｉ合金めっき等）等；アルミニウム材またはアルミニウム合金材（例えば、１０００系、２０００系、３０００系、４０００系、５０００系、６０００系、アルミニウム鋳物、アルミニウム合金鋳物、ダイキャスト材等）；銅材または銅合金材；チタン材またはチタン合金材；マグネシウム材またはマグネシウム合金材等が挙げられる。
<Metal materials>
The shape and structure of the metal material on which the film is formed are not particularly limited, and examples thereof include a plate shape, a foil shape, and the like. The type of metal material is not particularly limited, and examples include steel materials (e.g., cold-rolled steel sheets, hot-rolled steel sheets, black-covered steel sheets, pickled steel sheets, high-strength steel sheets, tool steels, alloy tool steels, and spheroidized graphite). cast iron, gray cast iron, etc.); plating materials, such as galvanized materials (e.g., electrogalvanizing, hot-dip galvanizing, aluminum-containing galvanizing, electrogalvanizing, zinc-nickel plating, zinc-cobalt plating, vapor deposited galvanizing, etc.), zinc Alloy plating materials (e.g. alloyed hot dip galvanizing, Zn-Al alloy plating, Zn-Al-Mg alloy plating, electrolytic zinc alloy plating, etc.), aluminum plating materials, nickel plating materials, tin plating materials, chrome plating materials, chromium Alloy plated materials (for example, Cr-Ni alloy plating, etc.); Aluminum materials or aluminum alloy materials (for example, 1000 series, 2000 series, 3000 series, 4000 series, 5000 series, 6000 series, aluminum castings, aluminum alloy castings, die cast material, etc.); copper material or copper alloy material; titanium material or titanium alloy material; magnesium material or magnesium alloy material.
＜皮膜＞
金属表面処理剤によって金属材料の表面または表面上に形成される皮膜の付着量は、本発明の性能が発揮できれば特に制限されるものではないが、例えば、０．０５ｇ／ｍ２～３．０ｇ／ｍ２の範囲内であることが好ましく、０．１ｇ／ｍ２～１．０ｇ／ｍ２の範囲内であることがより好ましい。前記皮膜が形成された金属材料は、耐食性が向上することで長寿命化が可能となり、もって資源の有効活用を図ることができる。
<Film>
The amount of the film formed on the surface of the metal material by the metal surface treatment agent is not particularly limited as long as the performance of the present invention can be achieved, but for example, it is 0.05 g/m 2 to 3.0 g. /m 2 , and more preferably 0.1 g/m 2 to 1.0 g/m 2 . The metal material on which the film is formed can have a longer lifespan due to its improved corrosion resistance, thereby making it possible to effectively utilize resources.
＜塗装工程＞
皮膜を有する金属材料は、塗装工程により塗装されてもよい。塗装方法としては特に制限されないが、例えば、電着塗装（例えば、カチオン電着塗装）、バーコート塗装、スプレー塗装、粉体塗装、ラミネート圧着等の方法を挙げることができる。
<Painting process>
The metal material having the film may be painted by a painting process. The coating method is not particularly limited, but examples include electrodeposition coating (for example, cationic electrodeposition coating), bar coat coating, spray coating, powder coating, lamination pressure bonding, and the like.
以下、実施例により本発明の効果を詳細に説明するが、本発明は以下の実施例によって制限されるものではない。 EXAMPLES Hereinafter, the effects of the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples.
＜金属表面処理剤の製造＞
下記に示す酸成分（Ａ）、タングステン化合物（Ｂ）、ｐＨ調整剤（アンモニア水）および金属化合物（Ｃ）をこの順序で脱イオン水に配合し、表１に示す金属表面処理剤を調製した。
<Manufacture of metal surface treatment agent>
The acid component (A), tungsten compound (B), pH adjuster (ammonia water), and metal compound (C) shown below were mixed in deionized water in this order to prepare the metal surface treatment agent shown in Table 1. .
＜酸成分（Ａ）＞
Ａ１：リン酸
Ａ２：２－ホスホノブタン－１，２，４－トリカルボン酸
Ａ３：メタンスルホン酸
Ａ４：クエン酸（無水物）
Ａ５：グリコール酸
Ａ６：アスパラギン
<Acid component (A)>
A1: Phosphoric acid A2: 2-phosphonobutane-1,2,4-tricarboxylic acid A3: Methanesulfonic acid A4: Citric acid (anhydride)
A5: Glycolic acid A6: Asparagine
＜タングステン化合物（Ｂ）＞
Ｂ１：タングステン酸アンモニウムパラ五水和物
Ｂ２：メタタングステン酸アンモニウム
<Tungsten compound (B)>
B1: Ammonium tungstate parapentahydrate B2: Ammonium metatungstate
＜金属化合物（Ｃ）＞
Ｃ１：バナジルアセチルアセトネート
Ｃ２：メタバナジン酸アンモニウム
Ｃ３：硫酸セリウム（ＩＶ）四水和物
Ｃ４：モリブデン酸（ＶＩ）アンモニウム四水和物
Ｃ５：硝酸マグネシウム六水和物
Ｃ６：塩化ニオブ（Ｖ）
Ｃ７：硝酸イットリウム（ＩＩＩ）六水和物
Ｃ８：硝酸クロム（ＩＩＩ）九水和物
Ｃ９：硫酸スズ（ＩＩ）
Ｃ１０：炭酸マンガン
Ｃ１１：硝酸銅（ＩＩ）三水和物
Ｃ１２：硝酸ランタン（ＩＩＩ）六水和物
<Metal compound (C)>
C1: Vanadyl acetylacetonate C2: Ammonium metavanadate C3: Cerium (IV) sulfate tetrahydrate C4: Ammonium molybdate (VI) tetrahydrate C5: Magnesium nitrate hexahydrate C6: Niobium (V) chloride
C7: Yttrium (III) nitrate hexahydrate C8: Chromium (III) nitrate nonahydrate C9: Tin (II) sulfate
C10: Manganese carbonate C11: Copper (II) nitrate trihydrate C12: Lanthanum (III) nitrate hexahydrate
＊１は、金属表面処理剤の全固形分質量に対する酸成分（Ａ）の固形分質量をパーセント表記した濃度である。
＊２は、金属表面処理剤の全固形分質量に対するタングステン化合物（Ｂ）のＷ換算固形分質量をパーセント表記した濃度である。
＊３は、金属表面処理剤の全固形分質量に対する金属化合物（Ｃ）の金属換算固形分質量をパーセント表記した濃度である。
*1 is the concentration expressed as a percentage of the solid mass of the acid component (A) with respect to the total solid mass of the metal surface treatment agent.
*2 is the concentration expressed as a percentage of the W-equivalent solid mass of the tungsten compound (B) relative to the total solid mass of the metal surface treatment agent.
*3 is the concentration expressed as a percentage of the metal equivalent solid mass of the metal compound (C) with respect to the total solid mass of the metal surface treatment agent.
＜金属材料＞
下記に示す金属材料を使用した。
ＧＩ：溶融亜鉛めっき鋼板
ＧＬ：溶融５５％アルミニウム－亜鉛合金めっき鋼板
ＳＵＳ：オーステナイト系ステンレス鋼板（ＳＵＳ３０４）
Ｃｕ：無酸素銅板（Ｃ１０２０Ｐ）
<Metal materials>
The metal materials shown below were used.
GI: Hot dip galvanized steel sheet GL: Hot dip 55% aluminum-zinc alloy coated steel sheet SUS: Austenitic stainless steel sheet (SUS304)
Cu: Oxygen-free copper plate (C1020P)
＜皮膜を有する金属材料の製造方法＞
前記金属材料を６０℃のアルカリ脱脂剤［ファインクリーナーＥ６４０６（日本パーカライジング株式会社製）を２０ｇ／Ｌとなるように水に混合した溶液］に１０秒間浸漬し、純水で水洗した後乾燥した。その後、表１に示した金属表面処理剤を乾燥後の皮膜質量が０．５ｇ／ｍ２となるように塗布し、１００℃（金属材料の最高到達板温度）で乾燥して皮膜を有する金属材料（試験板）を作製した。
<Method for producing metal material with film>
The metal material was immersed for 10 seconds in an alkaline degreaser [a solution of Fine Cleaner E6406 (manufactured by Nippon Parkerizing Co., Ltd.) mixed in water at a concentration of 20 g/L] at 60°C, washed with pure water, and then dried. Thereafter, the metal surface treatment agent shown in Table 1 was applied so that the coating mass after drying was 0.5 g/ m2 , and dried at 100°C (the highest plate temperature of the metal material). A material (test plate) was prepared.
＜評価＞
試験板を用いて、下記の評価を行った。表２に評価結果を示す。
<Evaluation>
The following evaluations were performed using the test plates. Table 2 shows the evaluation results.
＜平面部耐食性＞
ＪＩＳ Ｚ ２３７１：２０１５に基づき中性塩水噴霧試験を２４時間行った後、錆発生面積率を目視で確認し４段階で評価した。
４：５％未満
３：５％以上、１０％未満
２：１０％以上、２０％未満
１：２０％以上
<Corrosion resistance of flat part>
After conducting a neutral salt spray test for 24 hours based on JIS Z 2371:2015, the rust occurrence area ratio was visually confirmed and evaluated on a four-level scale.
4: Less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 20% 1: 20% or more
＜耐加工性＞
試験板をエリクセン試験機で５ｍｍ押し出し加工した。この試験板の加工部を走査電子顕微鏡［ＪＳＭ－ＩＴ１００（日本電子株式会社製）；倍率２００倍］で観察し、３段階で評価した。
３：クラックおよび金属素地の露出なし
２：クラックあり
１：金属素地の露出あり
<Working resistance>
The test plate was extruded to 5 mm using an Erichsen testing machine. The processed portion of this test plate was observed with a scanning electron microscope [JSM-IT100 (manufactured by JEOL Ltd.); magnification: 200 times] and evaluated on a three-level scale.
3: No cracks or exposed metal base 2: Cracks 1: Exposed metal base
＜加工部耐食性＞
前記押し出し加工した試験板に対して、ＪＩＳ Ｚ ２３７１：２０１５に基づき中性塩水噴霧試験を２４時間行った後、押し出し加工部の錆発生面積率を目視で確認し４段階で評価した。
４：１０％未満
３：１０％以上、２０％未満
２：２０％以上、３０％未満
１：３０％以上
<Corrosion resistance of processed parts>
The extruded test plate was subjected to a neutral salt spray test for 24 hours based on JIS Z 2371:2015, and then the rust occurrence area ratio of the extruded portion was visually confirmed and evaluated on a four-level scale.
4: Less than 10% 3: 10% or more, less than 20% 2: 20% or more, less than 30% 1: 30% or more
＜親水性＞
試験板の表面に１μＬの水滴を滴下し、滴下直後の水滴と試験板との接触角を接触角測定装置で測定した。その後、水滴を布で拭き取って水滴痕を目視で確認した。水滴痕が認められた場合は１点とし、水滴痕が認められなかった場合は接触角に基づき２段階で評価した。
３：５°未満
２：５°以上２０°未満
１：水滴拭き取り後、水滴痕が認められる
<Hydrophilicity>
A 1 μL water droplet was dropped on the surface of the test plate, and the contact angle between the water droplet and the test plate immediately after dropping was measured using a contact angle measuring device. Thereafter, the water droplets were wiped off with a cloth and the traces of water droplets were visually confirmed. If water drop marks were observed, it was given one point, and if no water drop marks were observed, it was evaluated in two stages based on the contact angle.
3: Less than 5° 2: 5° or more and less than 20° 1: Water drop marks are observed after wiping off water droplets
＜抗菌性＞
ＪＩＳ Ｚ ２８０１：２０１０に基づき抗菌性試験を行い、細菌の減少率を２段階で評価した。評価部に腐食または変色が認められた場合は１点とした。細菌には黄色ぶどう球菌と大腸菌を用いた。試験板の評価部以外はマスキングして抗菌性試験への影響がでないようにした。無加工試験片および比較用の試験片には清浄なガラス板を用いた。細菌の減少率は式［対象菌の減少率（％）＝１００－Ｙ／Ｚ×１００］で算出した。式中、Ｙは試験板を用いた際の生菌数を意味し、Ｚはガラス板を用いた際の生菌数を意味する。
３：９９．０％以上
２：９９．０％未満９５．０％以上
１：評価部に腐食または変色が認められる
<Antibacterial>
An antibacterial test was conducted based on JIS Z 2801:2010, and the bacterial reduction rate was evaluated in two stages. If corrosion or discoloration was observed in the evaluation area, it was given 1 point. Staphylococcus aureus and Escherichia coli were used as bacteria. All parts of the test plate other than the evaluation area were masked to prevent any influence on the antibacterial test. A clean glass plate was used for the unprocessed test piece and the comparative test piece. The reduction rate of bacteria was calculated using the formula [reduction rate (%) of target bacteria = 100-Y/Z×100]. In the formula, Y means the number of viable bacteria when using a test plate, and Z means the number of viable bacteria when using a glass plate.
3: 99.0% or more 2: Less than 99.0% 95.0% or more 1: Corrosion or discoloration is observed in the evaluation area
Claims (3)
タングステン化合物（Ｂ）と、
バナジウム、セリウム、モリブデン、マグネシウム、ニオブ、イットリウム、クロム、スズ、マンガン、銅およびランタンからなる群より選ばれる金属を含有する少なくとも１種の金属化合物（Ｃ）と、
を配合した金属表面処理剤であって、
前記タングステン化合物（Ｂ）のＷ換算固形分質量が前記金属表面処理剤の全固形分質量に対して１８．０％以上である金属表面処理剤。 At least one acid component (A) selected from the group consisting of phosphoric acids, phosphonic acids, organic sulfonic acids, polycarboxylic acids, monocarboxylic acids having a hydroxy group, and monocarboxylic acids having an amino group;
A tungsten compound (B),
at least one metal compound (C) containing a metal selected from the group consisting of vanadium, cerium, molybdenum, magnesium, niobium, yttrium, chromium, tin, manganese, copper and lanthanum;
A metal surface treatment agent containing
A metal surface treatment agent, wherein the solid mass of the tungsten compound (B) in terms of W is 18.0% or more based on the total solid mass of the metal surface treatment agent.
A metal material having a film obtained by the manufacturing method according to claim 2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022139714A JP2024035323A (en) | 2022-09-02 | 2022-09-02 | Metal surface treatment agent, and coated metal material and method for producing the same |
| PCT/JP2023/031267 WO2024048597A1 (en) | 2022-09-02 | 2023-08-29 | Metal-surface treatment agent, and metallic material having coating film and production method therefor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022139714A JP2024035323A (en) | 2022-09-02 | 2022-09-02 | Metal surface treatment agent, and coated metal material and method for producing the same |
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| JP2024035323A true JP2024035323A (en) | 2024-03-14 |
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| JP3851106B2 (en) * | 2000-05-11 | 2006-11-29 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| JP2004143549A (en) * | 2002-10-25 | 2004-05-20 | Nisshin Steel Co Ltd | Chemical treatment liquid for zinc plated steel plate |
| JP4167046B2 (en) * | 2002-11-29 | 2008-10-15 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
| CN106544663B (en) * | 2016-10-26 | 2019-04-19 | 博罗县东明化工有限公司 | Magnesium alloy Ca-W-Mn conversion film treating agent and magnesium alloy Ca-W-Mn processing method |
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