JP7385275B2 - Cobalt-free chemical conversion coating treatment solution and chemical conversion coating treatment method using the same - Google Patents
Cobalt-free chemical conversion coating treatment solution and chemical conversion coating treatment method using the same Download PDFInfo
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- JP7385275B2 JP7385275B2 JP2020167973A JP2020167973A JP7385275B2 JP 7385275 B2 JP7385275 B2 JP 7385275B2 JP 2020167973 A JP2020167973 A JP 2020167973A JP 2020167973 A JP2020167973 A JP 2020167973A JP 7385275 B2 JP7385275 B2 JP 7385275B2
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- Prior art keywords
- chemical conversion
- conversion coating
- titanium
- ion
- coating treatment
- Prior art date
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- 239000000126 substance Substances 0.000 title claims description 93
- 238000011282 treatment Methods 0.000 title claims description 78
- 238000007739 conversion coating Methods 0.000 title claims description 67
- 238000000034 method Methods 0.000 title claims description 14
- -1 carboxylic acid ions Chemical class 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 239000008119 colloidal silica Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- 229910001430 chromium ion Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 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 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 3
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 3
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 claims description 3
- 235000010215 titanium dioxide Nutrition 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- SOBXOQKKUVQETK-UHFFFAOYSA-H titanium(3+);trisulfate Chemical compound [Ti+3].[Ti+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SOBXOQKKUVQETK-UHFFFAOYSA-H 0.000 claims description 3
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- NLPMQGKZYAYAFE-UHFFFAOYSA-K titanium(iii) fluoride Chemical compound F[Ti](F)F NLPMQGKZYAYAFE-UHFFFAOYSA-K 0.000 claims description 3
- ZQVHTTABFLHMPA-UHFFFAOYSA-N 2-(4-chlorophenoxy)-5-nitropyridine Chemical compound N1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1 ZQVHTTABFLHMPA-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 2
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229960001759 cerium oxalate Drugs 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 claims description 2
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 claims description 2
- QBEGYEWDTSUVHH-UHFFFAOYSA-P diazanium;cerium(3+);pentanitrate Chemical compound [NH4+].[NH4+].[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBEGYEWDTSUVHH-UHFFFAOYSA-P 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 claims description 2
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 claims description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 2
- 125000005287 vanadyl group Chemical group 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-L Oxalate Chemical compound [O-]C(=O)C([O-])=O MUBZPKHOEPUJKR-UHFFFAOYSA-L 0.000 claims 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 claims 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- BJEPYKJPYRNKOW-UWTATZPHSA-M malate ion Chemical compound [O-]C(=O)[C@H](O)CC(O)=O BJEPYKJPYRNKOW-UWTATZPHSA-M 0.000 claims 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 30
- 238000005260 corrosion Methods 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 15
- 150000003609 titanium compounds Chemical class 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
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- 239000011347 resin Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 239000003788 bath preparation Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
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- 150000003892 tartrate salts Chemical class 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
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- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 231100000615 substance of very high concern Toxicity 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Description
本発明は、コバルトフリーの化成皮膜処理液、及び、それを用いた化成皮膜処理方法に関する。 The present invention relates to a cobalt-free chemical conversion coating treatment solution and a chemical conversion coating treatment method using the same.
鉄系材料や鉄系部品の防錆方法として亜鉛又は亜鉛合金めっきが広く用いられ、めっき上に保護皮膜を形成させることが一般的である。保護皮膜の一種である化成皮膜処理の分野においては、かつて六価クロメートが多用されていたが、環境問題等の理由により現在は三価クロム化成皮膜処理が主流となっている。この三価クロム化成皮膜処理液には耐食性や耐傷性の向上を目的として、コバルト化合物が含有されているものが一般的である。 Zinc or zinc alloy plating is widely used as a rust prevention method for iron-based materials and iron-based parts, and it is common to form a protective film on the plating. In the field of chemical conversion coating, which is a type of protective coating, hexavalent chromate was once widely used, but due to environmental issues and other reasons, trivalent chromium chemical conversion coating has now become mainstream. This trivalent chromium chemical conversion coating treatment solution generally contains a cobalt compound for the purpose of improving corrosion resistance and scratch resistance.
しかしながら、コバルト化合物は環境への影響が指摘されており、ＲＥＡＣＨ（Registration, Evaluation, Authorization and Restriction of Chemicals）規則の高懸念物質として登録されている。日本国内においても、安全衛生法施行令、特定化学物性障害予防規則によって、コバルトへの対策が強化されている。そのため、今後三価クロム化成皮膜処理液に含有されるコバルト化合物についても使用が制限されるという可能性がある。 However, cobalt compounds have been pointed out to have an impact on the environment, and are registered as substances of very high concern under the REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulations. In Japan, measures against cobalt are being strengthened under the Safety and Health Law Enforcement Order and the Specified Chemical Hazard Prevention Ordinance. Therefore, there is a possibility that the use of cobalt compounds contained in trivalent chromium chemical conversion coating treatment solutions will be restricted in the future.
このような問題に対し、種々のコバルトフリーの化成皮膜処理液が研究・開発されている（特許文献１～３）。 To address these problems, various cobalt-free chemical conversion coating treatment solutions have been researched and developed (Patent Documents 1 to 3).
めっきを保護するための化成皮膜には、良好な耐食性や耐傷性を有することが望まれ、また、当該化成皮膜を形成するための処理液は良好な安定性を有することも望まれている。このような観点から、従来の化成皮膜処理液には更なる開発の余地がある。 It is desired that the chemical conversion film for protecting the plating has good corrosion resistance and scratch resistance, and it is also desired that the treatment liquid for forming the chemical conversion film has good stability. From this point of view, there is room for further development of conventional chemical conversion coating treatment solutions.
本発明は、耐食性及び耐傷性に優れた化成皮膜を形成することができ、良好な液安定性を有するコバルトフリーの化成皮膜処理液、及び、それを用いた化成皮膜処理方法を提供するものである。 The present invention provides a cobalt-free chemical conversion coating treatment liquid that can form a chemical conversion coating with excellent corrosion resistance and scratch resistance and has good liquid stability, and a chemical conversion coating treatment method using the same. be.
本発明者らは上記課題を解決するために鋭意検討した結果、（Ａ）三価クロムイオン、（Ｂ）コロイダルシリカ、（Ｃ）所定の二種類のカルボン酸化合物、（Ｄ）チタン化合物、及び、（Ｅ）硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上を含有するコバルトフリーの化成皮膜処理液を用いることで、上記課題が解決されることを見出した。 As a result of intensive studies to solve the above problems, the present inventors found that (A) trivalent chromium ions, (B) colloidal silica, (C) two predetermined types of carboxylic acid compounds, (D) titanium compounds, and , (E) It has been found that the above problems can be solved by using a cobalt-free chemical conversion coating treatment solution containing one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions.
以上の知見を基礎として完成した本発明は一側面において、
（Ａ）三価クロムイオン、
（Ｂ）コロイダルシリカ、
（Ｃ）下記（１）～（６）のいずれか一つに記載の二種類のカルボン酸化合物、
（１）シュウ酸化合物とマロン酸化合物、
（２）シュウ酸化合物と酒石酸化合物、
（３）シュウ酸化合物とリンゴ酸化合物、
（４）シュウ酸化合物と酢酸化合物、
（５）酒石酸化合物とクエン酸化合物、
（６）酒石酸化合物とマロン酸化合物、
（Ｄ）チタン化合物、及び、
（Ｅ）硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上
を含有するコバルトフリーの化成皮膜処理液である。
In one aspect, the present invention, which was completed based on the above knowledge,
(A) trivalent chromium ion,
(B) colloidal silica,
(C) two types of carboxylic acid compounds described in any one of the following (1) to (6),
(1) Oxalic acid compound and malonic acid compound,
(2) oxalic acid compound and tartaric acid compound,
(3) oxalic acid compounds and malic acid compounds,
(4) oxalic acid compound and acetic acid compound,
(5) tartaric acid compound and citric acid compound,
(6) tartaric acid compound and malonic acid compound,
(D) a titanium compound, and
(E) A cobalt-free chemical conversion coating treatment solution containing one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions.
本発明のコバルトフリーの化成皮膜処理液は一実施形態において、前記三価クロムイオンが、硝酸クロム、硫酸クロム、塩化クロム及び酢酸クロムからなる群のうちの一種または二種以上である。 In one embodiment of the cobalt-free chemical conversion coating treatment solution of the present invention, the trivalent chromium ion is one or more of the group consisting of chromium nitrate, chromium sulfate, chromium chloride, and chromium acetate.
本発明のコバルトフリーの化成皮膜処理液は別の一実施形態において、前記チタン化合物が、酸化チタン(ＩＶ)、塩化チタン(ＩＩＩ)、塩化チタン（ＩＶ）、フッ化チタン（ＩＩＩ）、フッ化チタン（ＩＶ）、硫酸チタン（ＩＩＩ）、硫酸チタン（ＩＶ）、チタンフッ化アンモニウム、チタンフッ化カリウム、チタンラクテート、シュウ酸チタンカリウムからなる群のうちの一種または二種以上である。 In another embodiment of the cobalt-free chemical conversion coating treatment liquid of the present invention, the titanium compound is titanium (IV) oxide, titanium (III) chloride, titanium (IV) chloride, titanium (III) fluoride, fluoride, etc. One or more of the group consisting of titanium (IV), titanium (III) sulfate, titanium (IV) sulfate, ammonium titanium fluoride, potassium titanium fluoride, titanium lactate, and potassium titanium oxalate.
本発明のコバルトフリーの化成皮膜処理液は更に別の一実施形態において、（Ｆ）Ｖ、Ｃｅ、Ｍｏ及びＷからなる群のうちの一種または二種以上をさらに含有する。 In yet another embodiment, the cobalt-free chemical conversion coating treatment solution of the present invention further contains one or more of the group consisting of (F)V, Ce, Mo, and W.
本発明のコバルトフリーの化成皮膜処理液は更に別の一実施形態において、前記化成皮膜処理液の処理対象の金属が、亜鉛または亜鉛合金である。 In yet another embodiment of the cobalt-free chemical conversion coating treatment liquid of the present invention, the metal to be treated by the chemical conversion coating treatment liquid is zinc or a zinc alloy.
本発明は別の一側面において、本発明のコバルトフリーの化成皮膜処理液を、処理対象の金属の表面に接触させることを含む化成皮膜処理方法である。 In another aspect, the present invention is a chemical conversion coating treatment method that includes bringing the cobalt-free chemical conversion coating treatment solution of the present invention into contact with the surface of a metal to be treated.
本発明の化成皮膜処理方法は、前記処理対象の金属が、亜鉛または亜鉛合金である。 In the chemical conversion coating treatment method of the present invention, the metal to be treated is zinc or a zinc alloy.
本発明によれば、耐食性及び耐傷性に優れた化成皮膜を形成することができ、良好な液安定性を有するコバルトフリーの化成皮膜処理液、及び、それを用いた化成皮膜処理方法を提供することができる。 According to the present invention, there is provided a cobalt-free chemical conversion coating treatment liquid that can form a chemical conversion coating with excellent corrosion resistance and scratch resistance and has good liquid stability, and a chemical conversion coating treatment method using the same. be able to.
＜コバルトフリーの化成皮膜処理液＞
本発明の実施形態に係るコバルトフリーの化成皮膜処理液は、（Ａ）三価クロムイオン、（Ｂ）コロイダルシリカ、（Ｃ）所定の二種類のカルボン酸化合物、（Ｄ）チタン化合物、及び、（Ｅ）硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上を含有する。化成皮膜処理液が所定の二種類のカルボン酸、チタン化合物及びコロイダルシリカを含有することで良好な耐食性、耐傷性が得られる。また、化成皮膜処理液がチタン化合物を含有することでシリカ層の緻密化もしくは厚膜化が起こると考えられ、クロムを特定の組み合わせのカルボン酸でキレートさせることにより緻密なクロム皮膜が得られることによる耐食性、耐傷性の向上や液の安定性が向上する。
<Cobalt-free chemical conversion coating treatment liquid>
The cobalt-free chemical conversion coating treatment solution according to the embodiment of the present invention includes (A) trivalent chromium ions, (B) colloidal silica, (C) two predetermined carboxylic acid compounds, (D) a titanium compound, and (E) Contains one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions. Good corrosion resistance and scratch resistance can be obtained because the chemical conversion coating treatment solution contains two predetermined types of carboxylic acids, a titanium compound, and colloidal silica. It is also believed that the densification or thickening of the silica layer occurs when the chemical conversion coating treatment solution contains a titanium compound, and a dense chromium coating can be obtained by chelating chromium with a specific combination of carboxylic acids. This improves corrosion resistance, scratch resistance, and liquid stability.
＜被処理金属＞
本発明のコバルトフリーの化成皮膜処理液で化成皮膜を形成する被処理金属（処理対象の金属）としては、亜鉛、または、亜鉛ニッケル合金、亜鉛鉄合金、錫亜鉛合金、亜鉛ダイカスト等の亜鉛合金が挙げられる。処理対象の金属は、例えば、鉄系材料や鉄系部品などの金属基材の表面に形成された、これらのめっきであってもよい。
<Metal to be processed>
The metal to be treated (metal to be treated) on which a chemical conversion coating is formed with the cobalt-free chemical conversion coating treatment solution of the present invention is zinc, or a zinc alloy such as a zinc-nickel alloy, a zinc-iron alloy, a tin-zinc alloy, or a zinc die-casting. can be mentioned. The metal to be treated may be, for example, a plating formed on the surface of a metal base material such as an iron-based material or an iron-based component.
＜三価クロムイオン＞
本発明のコバルトフリーの化成皮膜処理液の構成成分である三価クロムイオンの供給源としては、硝酸クロム、硫酸クロム、塩化クロム、酢酸クロム等の三価クロム塩、及び、クロム酸や重クロム酸等の六価クロムを還元剤により三価に還元した三価クロム等の三価クロム化合物が利用できる。三価クロムの化合物であれば、上記以外の物質でも三価クロムの供給源として利用できる。これら三価クロム化合物は一種または二種以上を使用することができる。
<Trivalent chromium ion>
Sources of trivalent chromium ions, which are components of the cobalt-free chemical conversion coating treatment solution of the present invention, include trivalent chromium salts such as chromium nitrate, chromium sulfate, chromium chloride, and chromium acetate, as well as chromic acid and dichromium ions. Trivalent chromium compounds such as trivalent chromium, which is obtained by reducing hexavalent chromium such as acid to trivalent chromium using a reducing agent, can be used. Substances other than those mentioned above can also be used as sources of trivalent chromium as long as they are trivalent chromium compounds. One or more types of these trivalent chromium compounds can be used.
三価クロムイオンの濃度は、０．０１～１００ｇ／Ｌが好ましく、０．０１～２０ｇ／Ｌがより好ましく、０．０５～１０ｇ／Ｌであるのが更により好ましく、０．０５～５ｇ／Ｌであるのが更により好ましい。三価クロムイオンの濃度が上記範囲内で良好な化成皮膜が形成でき、良好な耐食性及び耐傷性が得られる。三価クロムイオンの濃度が０．０１ｇ／Ｌより低下すると耐食性及び耐傷性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの観点から好ましくない。 The concentration of trivalent chromium ions is preferably 0.01 to 100 g/L, more preferably 0.01 to 20 g/L, even more preferably 0.05 to 10 g/L, and even more preferably 0.05 to 5 g/L. Even more preferred is L. When the concentration of trivalent chromium ions is within the above range, a good chemical conversion film can be formed and good corrosion resistance and scratch resistance can be obtained. If the concentration of trivalent chromium ions is lower than 0.01 g/L, corrosion resistance and scratch resistance will be deteriorated, and if it exceeds 100 g/L, it is not preferable from the viewpoint of cost merit.
＜コロイダルシリカ＞
本発明のコバルトフリーの化成皮膜処理液の構成成分であるコロイダルシリカは、球状コロイダルシリカであってもよく、鎖状コロイダルシリカであってもよく、球状コロイダルシリカと鎖状コロイダルシリカとを両方用いてもよい。球状コロイダルシリカは通常のものを使用することができる。鎖状コロイダルシリカは、一次粒子が数個から数十個鎖状に結合したものである。鎖状コロイダルシリカは直鎖状であってもよく、分岐鎖状であってもよい。鎖状コロイダルシリカの粒子サイズについては、径３～３０ｎｍで、長さ３０～５００ｎｍの粒子であってもよい。球状コロイダルシリカ、鎖状コロイダルシリカは、公知のものを用いることができ、市販品のコロイダルシリカとして入手することができる。鎖状コロイダルシリカの具体例としては日産化学工業(株)のスノーテックスＵＰ(固形分２０質量％)、スノーテックスＯＵＰ(固形分１５質量％)が挙げられ、球状コロイダルシリカの具体例としては日産化学工業(株)スノーテックスＸＳ(固形分２０質量％)、スノーテックスＣＸＳ(固形分１４質量％)、スノーテックスＯＸＳ(固形分１０質量％)、スノーテックスＳ(固形分３０質量％)、スノーテックスＯＳ(固形分２０質量％)、スノーテックスＣ(固形分２０質量％)、スノーテックス３０(固形分３０質量％)、スノーテックスＯ(固形分２０質量％)、日揮触媒化成(株)のカタロイドＳＩ－３０(固形分３０質量％)、カタロイドＳＩ－５５０(固形分２０質量％)が挙げられる。コロイダルシリカとしては、特に、鎖状コロイダルシリカであるのが好ましい。鎖状コロイダルシリカを用いることで、効率的かつ緻密なシリカ層を形成することができ耐食性及び耐傷性が良好となる。
<Colloidal silica>
Colloidal silica, which is a component of the cobalt-free chemical conversion coating treatment solution of the present invention, may be spherical colloidal silica or chain colloidal silica, and both spherical colloidal silica and chain colloidal silica may be used. It's okay. Ordinary spherical colloidal silica can be used. Chain colloidal silica is composed of several to several dozen primary particles linked together in a chain. Chain colloidal silica may be linear or branched. The chain colloidal silica may have a particle size of 3 to 30 nm in diameter and 30 to 500 nm in length. Known spherical colloidal silica and chain colloidal silica can be used and can be obtained as commercially available colloidal silica. Specific examples of chain colloidal silica include Snowtex UP (solid content 20% by mass) and Snowtex OUP (solid content 15% by mass) manufactured by Nissan Chemical Industries, Ltd., and specific examples of spherical colloidal silica manufactured by Nissan Chemical Industries, Ltd. Chemical Industry Co., Ltd. Snowtex XS (solid content 20% by mass), Snowtex CXS (solid content 14% by mass), Snowtex OXS (solid content 10% by mass), Snowtex S (solid content 30% by mass), Snow Tex OS (solid content 20% by mass), Snowtex C (solid content 20% by mass), Snowtex 30 (solid content 30% by mass), Snowtex O (solid content 20% by mass), JGC Catalysts & Chemicals Co., Ltd. Examples include Cataloid SI-30 (solid content 30% by mass) and Cataloid SI-550 (solid content 20% by mass). As the colloidal silica, chain colloidal silica is particularly preferable. By using chain colloidal silica, an efficient and dense silica layer can be formed, resulting in good corrosion resistance and scratch resistance.
コロイダルシリカの濃度(ＳｉＯ2の濃度)は、０．１～６０ｇ／Ｌが好ましく、０．１～３０ｇ／Ｌがより好ましく、１～３０ｇ／Ｌであるのが更により好ましい。コロイダルシリカの濃度が上記範囲内で良好な化成皮膜が形成でき、良好な耐食性及び耐傷性が得られる。コロイダルシリカの濃度が０．１ｇ／Ｌより低下すると耐食性及び耐傷性の低下を招き、６０ｇ／Ｌを超えるとコストメリットの観点から好ましくない。 The concentration of colloidal silica (SiO 2 concentration) is preferably 0.1 to 60 g/L, more preferably 0.1 to 30 g/L, and even more preferably 1 to 30 g/L. When the concentration of colloidal silica is within the above range, a good chemical conversion film can be formed and good corrosion resistance and scratch resistance can be obtained. If the concentration of colloidal silica is lower than 0.1 g/L, corrosion resistance and scratch resistance will be lowered, and if it exceeds 60 g/L, it is not preferable from the viewpoint of cost merit.
＜二種類のカルボン酸化合物＞
本発明のコバルトフリーの化成皮膜処理液の構成成分である二種類のカルボン酸化合物の供給源は、下記（１）～（６）のいずれか一つである。
（１）シュウ酸化合物とマロン酸化合物、（２）シュウ酸化合物と酒石酸化合物、（３）シュウ酸化合物とリンゴ酸化合物、（４）シュウ酸化合物と酢酸化合物、（５）酒石酸化合物とクエン酸化合物、（６）酒石酸化合物とマロン酸化合物。
<Two types of carboxylic acid compounds>
The source of the two types of carboxylic acid compounds that are the constituent components of the cobalt-free chemical conversion coating treatment solution of the present invention is any one of the following (1) to (6).
(1) Oxalic acid compounds and malonic acid compounds, (2) Oxalic acid compounds and tartaric acid compounds, (3) Oxalic acid compounds and malic acid compounds, (4) Oxalic acid compounds and acetic acid compounds, (5) Tartaric acid compounds and citric acid. compounds, (6) tartaric acid compounds and malonic acid compounds.
上記（１）～（６）の二種類のカルボン酸化合物の組み合わせにより、良好な皮膜形成をしつつ、処理液の安定性向上が得られる。また、反応速度の異なるカルボン酸を組み合わせることで反応ムラの低減ができ、均一な外観が得られやすくなる。 By combining the above two types of carboxylic acid compounds (1) to (6), it is possible to form a good film and improve the stability of the treatment liquid. Furthermore, by combining carboxylic acids with different reaction rates, reaction unevenness can be reduced, making it easier to obtain a uniform appearance.
二種類のカルボン酸化合物の合計濃度は、０．０１～１００ｇ／Ｌが好ましく、０．１～５０ｇ／Ｌがより好ましく、１～３０ｇ／Ｌであるのが更により好ましい。二種類のカルボン酸化合物の合計濃度が上記範囲内で良好な化成皮膜が形成でき、良好な耐食性及び耐傷性が得られ、液安定性が良好となる。二種類のカルボン酸化合物の合計濃度が０．０１ｇ／Ｌより低下すると耐食性及び耐傷性、さらには液安定性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの観点から好ましくない。 The total concentration of the two types of carboxylic acid compounds is preferably 0.01 to 100 g/L, more preferably 0.1 to 50 g/L, and even more preferably 1 to 30 g/L. When the total concentration of the two types of carboxylic acid compounds is within the above range, a good chemical conversion film can be formed, good corrosion resistance and scratch resistance can be obtained, and liquid stability can be improved. If the total concentration of the two types of carboxylic acid compounds is lower than 0.01 g/L, corrosion resistance, scratch resistance, and even liquid stability will be deteriorated, and if it exceeds 100 g/L, it is not preferable from the viewpoint of cost merit.
＜チタン化合物＞
本発明のコバルトフリーの化成皮膜処理液の構成成分であるチタン化合物の供給源としては、酸化チタン(ＩＶ)、塩化チタン(ＩＩＩ)、塩化チタン（ＩＶ）、フッ化チタン（ＩＩＩ）、フッ化チタン（ＩＶ）、硫酸チタン（ＩＩＩ）、硫酸チタン（ＩＶ）、チタンフッ化アンモニウム、チタンフッ化カリウム、チタンラクテート、シュウ酸チタンカリウム等が利用できる。これらチタン化合物は一種または二種以上を使用することができる。チタン化合物の供給源としては、チタンフッ化アンモニウム、チタンラクテート、シュウ酸チタンカリウムがより好ましい。
<Titanium compound>
Sources of titanium compounds that are constituent components of the cobalt-free chemical conversion coating treatment solution of the present invention include titanium (IV) oxide, titanium (III) chloride, titanium (IV) chloride, titanium (III) fluoride, and fluoride. Titanium (IV), titanium (III) sulfate, titanium (IV) sulfate, ammonium titanium fluoride, potassium titanium fluoride, titanium lactate, potassium titanium oxalate, etc. can be used. These titanium compounds can be used alone or in combination of two or more. As the source of the titanium compound, titanium ammonium fluoride, titanium lactate, and titanium potassium oxalate are more preferable.
チタン化合物の濃度は、０．０１～１００ｇ／Ｌが好ましく、０．０１～２０ｇ／Ｌがより好ましく、０．０５～１０ｇ／Ｌであるのが更により好ましく、０．０５～５ｇ／Ｌであるのが更により好ましい。チタン化合物の濃度が上記範囲内で良好な化成皮膜が形成でき、良好な耐食性及び耐傷性が得られ、液安定性が良好となる。チタン化合物の濃度が０．０１ｇ／Ｌより低下すると耐食性及び耐傷性、さらには液安定性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの観点から好ましくない。 The concentration of the titanium compound is preferably 0.01 to 100 g/L, more preferably 0.01 to 20 g/L, even more preferably 0.05 to 10 g/L, and even more preferably 0.05 to 5 g/L. Even more preferably. When the concentration of the titanium compound is within the above range, a good chemical conversion film can be formed, good corrosion resistance and scratch resistance can be obtained, and liquid stability can be improved. If the concentration of the titanium compound is lower than 0.01 g/L, corrosion resistance, scratch resistance, and even liquid stability will be deteriorated, and if it exceeds 100 g/L, it is not preferable from the viewpoint of cost merit.
＜硫酸イオン、硝酸イオン及び塩化物イオン＞
本発明のコバルトフリーの化成皮膜処理液の構成成分である硫酸イオン、硝酸イオン及び、塩化物イオンの供給源としては、硫酸、硝酸、塩酸や、硫酸ナトリウム、硝酸ナトリウム、塩化ナトリウム、硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム等が利用できる。硫酸クロム、硝酸クロム等のクロム化合物に含有される各種アニオンも供給源として利用できる。硫酸イオン、硝酸イオン及び塩化物イオンの化合物であれば、上記以外の物質も硫酸イオン、硝酸イオン及び塩化物イオンの供給源として利用できる。硫酸イオン、硝酸イオン及び塩化物イオンは、一種または二種以上を使用することができる。硫酸イオン、硝酸イオン及び塩化物イオンの供給源としては、硝酸、硝酸ナトリウム、硫酸、硫酸ナトリウム、塩酸、塩化ナトリウムがより好ましい。
<Sulfate ion, nitrate ion, and chloride ion>
Sources of sulfate ions, nitrate ions, and chloride ions, which are the constituent components of the cobalt-free chemical conversion coating treatment solution of the present invention, include sulfuric acid, nitric acid, hydrochloric acid, sodium sulfate, sodium nitrate, sodium chloride, ammonium sulfate, and ammonium nitrate. , ammonium chloride, etc. can be used. Various anions contained in chromium compounds such as chromium sulfate and chromium nitrate can also be used as a supply source. Substances other than those mentioned above can also be used as sources of sulfate ions, nitrate ions, and chloride ions as long as they are compounds of sulfate ions, nitrate ions, and chloride ions. One kind or two or more kinds of sulfate ions, nitrate ions, and chloride ions can be used. As sources of sulfate ions, nitrate ions, and chloride ions, nitric acid, sodium nitrate, sulfuric acid, sodium sulfate, hydrochloric acid, and sodium chloride are more preferable.
硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上の濃度は、０．１～１００ｇ／Ｌが好ましく、１～５０ｇ／Ｌであるのがより好ましく、１～３０ｇ／Ｌであるのが更により好ましい。硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上の濃度が上記範囲内で良好な化成皮膜を形成でき、良好な耐食性及び耐傷性が得られる。硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上の濃度が０．１ｇ／Ｌより低下すると耐食性及び耐傷性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの観点から好ましくない。 The concentration of one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions is preferably 0.1 to 100 g/L, more preferably 1 to 50 g/L, and 1 to 30 g/L. Even more preferred is L. When the concentration of one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions is within the above range, a good chemical conversion film can be formed and good corrosion resistance and scratch resistance can be obtained. If the concentration of one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions decreases below 0.1 g/L, corrosion resistance and scratch resistance will decrease, and if it exceeds 100 g/L, it will reduce the cost advantage. undesirable.
＜その他の成分＞
本発明のコバルトフリーの化成皮膜処理液は、その他の成分として、Ｖ（例えば、酸化バナジウム（ＩＩＩ）、酸化バナジウム（ＩＶ）、酸化バナジウム（Ｖ）、塩化バナジウム（ＩＩＩ）、塩化バナジル（Ｖ）、硫酸バナジル、バナジン酸アンモン、または、バナジン酸カリウム等）、Ｃｅ（例えば、塩化セリウム、硫酸セリウム（ＩＩＩ）、硫酸セリウム（ＩＶ）、硝酸二アンモニウムセリウム、シュウ酸セリウム等）、Ｍｏ（例えば、三酸化モリブデン、モリブデン酸ナトリウム、七モリブデン酸六アンモニウム、または、モリブデン酸等）、Ｗ（例えば三酸化タングステン、タングステン酸カルシウム、タングステン酸ナトリウム、または、フッ化タングステン等）等を含有してもよい。Ｖ、Ｃｅ、Ｍｏ及びＷは耐食性及び耐傷性を向上させる。これらの成分の含有量は０．００１～１００ｇ／Ｌが好ましく、０．０１～５０ｇ／Ｌがより好ましい。
<Other ingredients>
The cobalt-free chemical conversion coating treatment solution of the present invention contains V (e.g., vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, vanadium (III) chloride, vanadyl (V) chloride) as other components. , vanadyl sulfate, ammonium vanadate, potassium vanadate, etc.), Ce (e.g., cerium chloride, cerium (III) sulfate, cerium (IV) sulfate, cerium diammonium nitrate, cerium oxalate, etc.), Mo (e.g., molybdenum trioxide, sodium molybdate, hexaammonium heptamolybdate, molybdic acid, etc.), W (for example, tungsten trioxide, calcium tungstate, sodium tungstate, tungsten fluoride, etc.), etc. . V, Ce, Mo and W improve corrosion resistance and scratch resistance. The content of these components is preferably 0.001 to 100 g/L, more preferably 0.01 to 50 g/L.
＜化成皮膜処理方法＞
次に、本発明のコバルトフリーの化成皮膜処理液を用いた化成皮膜処理方法について詳述する。本発明の化成皮膜の形成は、例えば表面にめっきが形成された金属基材（処理対象の金属）を化成皮膜処理液に浸漬させる。これにより、処理対象の金属の表面に化成皮膜処理液を接触させて、処理対象の金属の表面に化成皮膜を形成することができる。また、浸漬以外でもよく、例えば、化成皮膜処理液を用いた塗布や吹き付け工程によって、処理対象の金属の表面に化成皮膜処理液を接触させて、処理対象の金属の表面に化成皮膜を形成してもよい。
<Chemical film treatment method>
Next, a chemical conversion coating treatment method using the cobalt-free chemical conversion coating treatment liquid of the present invention will be described in detail. Formation of the chemical conversion film of the present invention involves, for example, immersing a metal base material (metal to be treated) whose surface is plated in a chemical conversion film treatment solution. Thereby, a chemical conversion coating can be formed on the surface of the metal to be treated by bringing the chemical conversion coating treatment liquid into contact with the surface of the metal to be treated. Alternatively, methods other than dipping may be used; for example, a chemical conversion coating may be formed on the surface of the metal to be treated by bringing the chemical conversion coating treatment liquid into contact with the surface of the metal to be treated through a coating or spraying process using the chemical conversion coating treatment liquid. It's okay.
化成皮膜処理液による処理温度は、１０～８０℃の範囲が好ましく、１０～５０℃の範囲がより好ましく、２０～５０℃の範囲が更により好ましい。処理温度が１０℃より低い場合は化成皮膜の反応速度が低下し、８０℃より高い場合は蒸発による処理液面の低下が生じるため好ましくない。 The treatment temperature with the chemical conversion coating treatment liquid is preferably in the range of 10 to 80°C, more preferably in the range of 10 to 50°C, and even more preferably in the range of 20 to 50°C. If the treatment temperature is lower than 10°C, the reaction rate of the chemical conversion coating will decrease, and if it is higher than 80°C, the level of the treatment liquid will drop due to evaporation, which is not preferable.
化成皮膜処理液による処理時間は、５～６００秒の範囲が好ましく、５～１２０秒の範囲がより好ましく、１０～１２０秒の範囲が更により好ましい。処理時間が５秒より短い場合は化成皮膜の形成が不十分となり、６００秒より長い場合は被処理金属の表面が白くボケるといった外観不良が発生しやすくなるため好ましくない。 The treatment time with the chemical conversion coating treatment liquid is preferably in the range of 5 to 600 seconds, more preferably in the range of 5 to 120 seconds, and even more preferably in the range of 10 to 120 seconds. If the treatment time is shorter than 5 seconds, the formation of the chemical conversion film will be insufficient, and if it is longer than 600 seconds, the surface of the metal to be treated will tend to have poor appearance such as white blurring, which is not preferable.
化成皮膜処理液のｐＨは、０．５～６．０の範囲が好ましく、０．５～５．０の範囲がより好ましく、１．５～５．０の範囲が更により好ましい。ｐＨが０．５より低い場合は被処理金属の表面が粗面化しやすく、６．０より高い場合は皮膜化成速度が低下するとともに処理液に沈殿が生じやすくなるため好ましくない。なお、化成皮膜処理液のｐＨ調整剤としては、塩酸、硫酸、硝酸の無機酸や、苛性ソーダ、苛性カリ、アンモニア水のアルカリを用いることができる。 The pH of the chemical conversion coating treatment solution is preferably in the range of 0.5 to 6.0, more preferably in the range of 0.5 to 5.0, and even more preferably in the range of 1.5 to 5.0. If the pH is lower than 0.5, the surface of the metal to be treated tends to be roughened, and if it is higher than 6.0, the rate of film formation decreases and precipitation tends to occur in the treatment solution, which is not preferred. As the pH adjuster for the chemical conversion coating treatment solution, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and alkalis such as caustic soda, caustic potash, and aqueous ammonia can be used.
化成皮膜処理を行う際、あらかじめ被処理金属の脱脂、活性化、表面調整を行うことで、被処理金属の外観、耐食性及び塗装密着性を向上させることが可能である。脱脂に関しては被処理金属により適した工程がある。亜鉛めっきや亜鉛合金めっきに関してはめっき後に硝酸活性、有機酸活性等、めっき後に必要に応じて適した活性処理を行い、その後、化成皮膜処理を行うことが適している。亜鉛ダイカストに関しては脱脂や必要に応じて活性処理を行い、その後に保護皮膜形成処理を行うことが適している。これらの前処理に関しては、各被処理金属に応じて適宜行うことで本発明における化成皮膜処理の性能を引き出すことが可能である。 When performing chemical conversion coating treatment, by degreasing, activating, and surface conditioning the metal to be treated in advance, it is possible to improve the appearance, corrosion resistance, and paint adhesion of the metal to be treated. Regarding degreasing, there are processes that are more suitable for the metal being treated. Regarding zinc plating or zinc alloy plating, it is suitable to perform a suitable activation treatment such as nitric acid activation or organic acid activation as necessary after plating, and then perform a chemical conversion coating treatment. Regarding zinc die casting, it is suitable to perform degreasing and, if necessary, activation treatment, and then perform protective film formation treatment. Regarding these pre-treatments, it is possible to bring out the performance of the chemical conversion coating treatment in the present invention by performing them appropriately depending on each metal to be treated.
化成皮膜処理後に、ケイ素、樹脂及びワックスからなる群のうちの一種以上を含有するコーティング剤にて後処理を行っても良い。これらコーティング剤に特に限定はなくアクリル樹脂、オレフィン樹脂、アルキド樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、フェノール樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド、ポリカーボネート等の樹脂類やケイ酸塩、コロイダルシリカ等を成分とするコーティング剤を用いても良い。これらの樹脂濃度は、０．０１～８００ｇ／Ｌが好ましいが、適切な濃度は樹脂の種類により異なる。コーティング剤としては、具体的には、コスマーコート（商品名、関西ペイント（株））、ハイシール２７２（商品名、日本表面化学（株））、ストロンＪコート（商品名、日本表面化学（株））、トライナーＴＲ－１７０（商品名、日本表面化学（株））、フィニガード（商品名、Coventya社）等が挙げられる。アクリル樹脂としては、具体的には、ヒロタイト（商品名、日立化成（株））、アロセット（（株）日本触媒）等があり、オレフィン樹脂については、フローセン（商品名、住友精化（株））、ＰＥＳ（商品名、日本ユニカー（株））、ケミパール（商品名、三井化学（株））、サンファイン（商品名、旭化成（株））等が挙げられる。 After the chemical conversion coating treatment, a post-treatment may be performed using a coating agent containing one or more of the group consisting of silicon, resin, and wax. These coating agents are not particularly limited, and include acrylic resin, olefin resin, alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, phenol resin, polyester resin, polyurethane, A coating agent containing resins such as polyamide and polycarbonate, silicate, colloidal silica, etc. may also be used. The concentration of these resins is preferably 0.01 to 800 g/L, but the appropriate concentration varies depending on the type of resin. Specific examples of coating agents include Cosmer Coat (product name, Kansai Paint Co., Ltd.), HiSeal 272 (product name, Nippon Surface Chemical Co., Ltd.), and Stron J Coat (product name, Nippon Surface Chemical Co., Ltd.). ), Trinar TR-170 (trade name, Nippon Kaimen Kagaku Co., Ltd.), Finigard (trade name, Coventya Co., Ltd.), and the like. Specific examples of acrylic resins include Hirotite (trade name, Hitachi Chemical Co., Ltd.) and Alloset (Nippon Shokubai Co., Ltd.), and examples of olefin resins include Frocene (trade name, Sumitomo Seika Chemical Co., Ltd.). ), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Chemicals Co., Ltd.), Sunfine (trade name, Asahi Kasei Co., Ltd.), and the like.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Examples of the present invention will be shown below, but these are provided for better understanding of the present invention, and are not intended to limit the present invention.
（実施例１～１５５、比較例１～１８）
試験片として、表１に記載の被処理金属を準備した。めっき膜厚はいずれのめっきも８～１０μｍとした。このうち、被処理金属Ｎｏ．１とＮｏ．３とは、めっき後に水洗、硝酸活性化（硝酸６７．５％を５ｍＬ/Ｌ、室温、５秒）の後、水洗した。被処理金属Ｎｏ．２は、めっき後に水洗、活性化（日本表面化学（株）製２Ｃ０７９を６ｍＬ/Ｌ、室温、５秒）の後、水洗した。
次に、当該被処理金属を表２－１～表２－６の液組成を有する化成皮膜処理液に浸漬し、化成処理後に水洗し、乾燥を行った。処理温度、処理ｐＨ及び処理時間を表３－１～表３－５に示す。ｐＨの調整は、硫酸、硝酸、塩酸から選択される適切な酸及び水酸化ナトリウムにより行った。
(Examples 1 to 155, Comparative Examples 1 to 18)
The metals to be treated listed in Table 1 were prepared as test pieces. The thickness of each plating was 8 to 10 μm. Among these, the metal to be treated No. 1 and no. 3 was washed with water after plating, activated with nitric acid (5 mL/L of 67.5% nitric acid, room temperature, 5 seconds), and then washed with water. Processed metal No. No. 2 was washed with water after plating, activated (2C079 manufactured by Nippon Surface Chemical Co., Ltd., 6 mL/L, room temperature, 5 seconds), and then washed with water.
Next, the metal to be treated was immersed in a chemical conversion coating solution having the liquid composition shown in Tables 2-1 to 2-6, and after the chemical conversion treatment, it was washed with water and dried. The treatment temperature, treatment pH, and treatment time are shown in Tables 3-1 to 3-5. Adjustment of pH was carried out with a suitable acid selected from sulfuric acid, nitric acid, hydrochloric acid and sodium hydroxide.
なお、実施例１５４及び１５５については、実施例３と同様にして化成皮膜を形成した後の被処理金属を水洗し、コーティング処理を行い、乾燥した。実施例１５４のコーティング処理にはハイシール２７２（日本表面化学（株）製、ポリアクリル樹脂型コーティング剤）、実施例１５５のコーティング処理にはストロンＪコート（日本表面化学（株）製、水分散型シリカ型コーティング剤）を使用した。 In Examples 154 and 155, the metal to be treated after forming the chemical conversion film in the same manner as in Example 3 was washed with water, subjected to coating treatment, and dried. For the coating treatment of Example 154, HiSeal 272 (manufactured by Nippon Surface Chemical Co., Ltd., polyacrylic resin type coating agent) was used, and for the coating treatment of Example 155, Stron J Coat (manufactured by Nippon Surface Chemical Co., Ltd., water dispersion type) was used. A silica-type coating agent) was used.
このようにして化成皮膜を形成した被処理金属について、以下のように耐食性試験、耐傷性試験、外観試験及び液安定性を実施した。
（耐食性試験）
耐食性試験は、化成皮膜を形成した被処理金属に対して、ＪＩＳ Ｚ ２７３１に従う塩水噴霧試験を行った。
Corrosion resistance tests, scratch resistance tests, appearance tests, and liquid stability tests were conducted on the metals to be treated on which chemical conversion films were formed as described below.
(Corrosion resistance test)
For the corrosion resistance test, a salt spray test according to JIS Z 2731 was conducted on the metal to be treated on which the chemical conversion film was formed.
（耐傷性試験）
耐傷性試験は、化成皮膜を形成した被処理金属に対して、まず、振とう培養機（高崎科学器機（株）製、回転速度１５０ｒｐｍ、５分間振とう）により被処理金属表面に傷をつけた後、ＪＩＳ Ｚ ２７３１に従う塩水噴霧試験を行った。
(Scratch resistance test)
In the scratch resistance test, the surface of the metal to be treated, on which a chemical conversion film has been formed, is first scratched using a shaking incubator (manufactured by Takasaki Scientific Instruments Co., Ltd., rotation speed 150 rpm, shaking for 5 minutes). After that, a salt spray test according to JIS Z 2731 was conducted.
耐食性試験及び耐傷性試験の評価は、それぞれ以下の基準による。
Ａ：３６０時間白錆発生無し
Ｂ：２４０時間白錆発生無し
Ｃ：１６８時間白錆発生無し
Ｄ：７２時間白錆発生無し
Ｅ：４８時間白錆発生
Ｆ：２４時間白錆発生
Evaluation of corrosion resistance test and scratch resistance test is based on the following criteria.
A: No white rust for 360 hours B: No white rust for 240 hours C: No white rust for 168 hours D: No white rust for 72 hours E: White rust for 48 hours F: White rust for 24 hours
（外観試験）
外観試験は、化成皮膜を形成した被処理金属に対して、目視により評価した。評価基準を以下に示す。
Ａ：均一な処理外観
Ｂ：やや不均一な外観
Ｃ：不均一な外観
(Appearance test)
In the appearance test, the treated metal on which the chemical conversion film was formed was visually evaluated. The evaluation criteria are shown below.
A: Uniform processed appearance B: Slightly uneven appearance C: Non-uniform appearance
（液安定性）
建浴後７２時間後の建浴液（化成皮膜処理液）の安定性を目視により評価した。評価基準を以下に示す。
Ａ：建浴時と比較し変化なし
Ｂ：やや濁りあり
Ｃ：濁りまたは沈殿あり
以上の試験について、評価結果を表３－１～表３－５に示す。
(liquid stability)
The stability of the bath preparation solution (chemical coating treatment solution) 72 hours after bath preparation was visually evaluated. The evaluation criteria are shown below.
A: No change compared to the time of bath preparation B: Slight turbidity C: Turbidity or precipitation The evaluation results for the above tests are shown in Tables 3-1 to 3-5.
以上の結果から、（Ａ）三価クロムイオン、（Ｂ）コロイダルシリカ、（Ｃ）本発明の実施形態に係る所定の二種類のカルボン酸化合物、（Ｄ）チタン化合物、及び、（Ｅ）硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上を含有するコバルトフリーの化成皮膜処理液により化成皮膜を形成することにより、優れた耐食性及び耐傷性、さらには良好な外観が得られることが確認された。また、当該コバルトフリーの化成皮膜処理液の液安定性が良好となることが確認された。
なお、比較例１、７、１３は、耐食性、耐傷性、外観、液安定性が良好であったが、硝酸コバルト６水和物を含有する液組成Ｎｏ．５２の化成皮膜処理液（すなわち、コバルトフリーではない化成皮膜処理液）を用いたものである。
From the above results, (A) trivalent chromium ion, (B) colloidal silica, (C) two types of predetermined carboxylic acid compounds according to the embodiment of the present invention, (D) titanium compound, and (E) sulfuric acid. By forming a chemical conversion film using a cobalt-free chemical conversion coating treatment solution containing one or more of the group consisting of ion, nitrate ion, and chloride ion, it has excellent corrosion resistance and scratch resistance, and also has a good appearance. It was confirmed that this was obtained. Furthermore, it was confirmed that the cobalt-free chemical conversion coating treatment liquid had good liquid stability.
Comparative Examples 1, 7, and 13 had good corrosion resistance, scratch resistance, appearance, and liquid stability, but liquid composition No. 1 containing cobalt nitrate hexahydrate had good corrosion resistance, scratch resistance, appearance, and liquid stability. No. 52 chemical conversion coating treatment solution (that is, a chemical conversion coating treatment solution that is not cobalt-free) was used.
Claims (6)
（Ｂ）コロイダルシリカ、
（Ｃ）下記（１）～（６）のいずれか一つに記載の二種類のカルボン酸イオン、
（１）シュウ酸イオンとマロン酸イオン、
（２）シュウ酸イオンと酒石酸イオン、
（３）シュウ酸イオンとリンゴ酸イオン、
（４）シュウ酸イオンと酢酸イオン、
（５）酒石酸イオンとクエン酸イオン、
（６）酒石酸イオンとマロン酸イオン、
（Ｄ）酸化チタン(ＩＶ)、塩化チタン(ＩＩＩ)、塩化チタン（ＩＶ）、フッ化チタン（ＩＩＩ）、フッ化チタン（ＩＶ）、硫酸チタン（ＩＩＩ）、硫酸チタン（ＩＶ）、チタンフッ化アンモニウム、チタンフッ化カリウム、チタンラクテート、シュウ酸チタンカリウムからなる群のうちの一種または二種以上、及び、
（Ｅ）硫酸イオン、硝酸イオン及び塩化物イオンからなる群のうちの一種または二種以上
を含有し、ジルコニウムイオンを含有しない、コバルトフリーの化成皮膜処理液。 (A) trivalent chromium ion,
(B) colloidal silica,
(C) two types of carboxylic acid ions described in any one of the following (1) to (6),
(1) Oxalate ion and malonate ion ,
(2) oxalate ion and tartrate ion ,
(3) oxalate ion and malate ion ,
(4) oxalate ion and acetate ion ,
(5) tartrate ion and citrate ion ,
(6) tartrate ion and malonate ion ,
(D) Titanium(IV) oxide, titanium(III) chloride, titanium(IV) chloride, titanium(III) fluoride, titanium(IV) fluoride, titanium(III) sulfate, titanium(IV) sulfate, titanium ammonium fluoride , one or more of the group consisting of potassium titanium fluoride, titanium lactate, potassium titanium oxalate, and
(E) A cobalt-free chemical conversion coating treatment solution that contains one or more of the group consisting of sulfate ions, nitrate ions, and chloride ions , but does not contain zirconium ions .
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| JP2005240068A (en) | 2004-02-24 | 2005-09-08 | Nippon Hyomen Kagaku Kk | Agent for forming hexavalent-chromium-free coating onto plated film of zinc or zinc-nickel alloy, and forming method therefor |
| JP2010150626A (en) | 2008-12-26 | 2010-07-08 | Nippon Parkerizing Co Ltd | Posttreatment agent for galvanization and galvanized material subjected to surface treatment using the same |
| WO2016104703A1 (en) | 2014-12-26 | 2016-06-30 | ディップソール株式会社 | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
| JP2016132785A (en) | 2015-01-16 | 2016-07-25 | 日本表面化学株式会社 | Trivalent chromium chemical conversion coating treatment solution and method for treating metal base material |
| JP2019515143A (en) | 2016-05-11 | 2019-06-06 | サーテック インターナショナル ゲーエムベーハー | Chemical conversion film for metal surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005240068A (en) | 2004-02-24 | 2005-09-08 | Nippon Hyomen Kagaku Kk | Agent for forming hexavalent-chromium-free coating onto plated film of zinc or zinc-nickel alloy, and forming method therefor |
| JP2010150626A (en) | 2008-12-26 | 2010-07-08 | Nippon Parkerizing Co Ltd | Posttreatment agent for galvanization and galvanized material subjected to surface treatment using the same |
| WO2016104703A1 (en) | 2014-12-26 | 2016-06-30 | ディップソール株式会社 | Trivalent chromium chemical conversion liquid for zinc or zinc alloy bases and chemical conversion coating film |
| JP2016132785A (en) | 2015-01-16 | 2016-07-25 | 日本表面化学株式会社 | Trivalent chromium chemical conversion coating treatment solution and method for treating metal base material |
| JP2019515143A (en) | 2016-05-11 | 2019-06-06 | サーテック インターナショナル ゲーエムベーハー | Chemical conversion film for metal surface |
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