JP7169409B1 - Hexavalent chromium-free aqueous surface treatment liquid, surface treated metal and surface treatment method - Google Patents
Hexavalent chromium-free aqueous surface treatment liquid, surface treated metal and surface treatment method Download PDFInfo
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- JP7169409B1 JP7169409B1 JP2021130449A JP2021130449A JP7169409B1 JP 7169409 B1 JP7169409 B1 JP 7169409B1 JP 2021130449 A JP2021130449 A JP 2021130449A JP 2021130449 A JP2021130449 A JP 2021130449A JP 7169409 B1 JP7169409 B1 JP 7169409B1
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- hexavalent chromium
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 49
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000008119 colloidal silica Substances 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 13
- 239000004584 polyacrylic acid Substances 0.000 claims description 13
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 description 33
- 239000010959 steel Substances 0.000 description 33
- 239000003973 paint Substances 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 239000011651 chromium Substances 0.000 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 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 5
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000006115 industrial coating Substances 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- -1 zinc-aluminum-magnesium Chemical compound 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
-
- 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
-
- 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
- C23C22/07—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 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
- C23C22/06—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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
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
【課題】金属の耐食性および塗装密着性を向上させるとともに、無着色皮膜を形成することが可能な６価クロムフリー水性表面処理液を提供する。【解決手段】６価クロムフリー水性表面処理液は、金属の表面処理に用いられる。６価クロムフリー水性表面処理液は、３価クロムイオンと、リン酸イオンと、硫酸イオンと、コロイダルシリカと、を含み、３価クロムイオンに対するリン酸イオンのモル比が１．９以上３．２以下であり、３価クロムイオンに対する硫酸イオンのモル比が０．１０以上０．３０以下である。【選択図】なしAn object of the present invention is to provide a hexavalent chromium-free water-based surface treatment liquid capable of improving the corrosion resistance of metals and coating adhesion and forming a colorless film. A hexavalent chromium-free aqueous surface treatment liquid is used for metal surface treatment. The hexavalent chromium-free aqueous surface treatment liquid contains trivalent chromium ions, phosphate ions, sulfate ions, and colloidal silica, and the molar ratio of phosphate ions to trivalent chromium ions is 1.9 or more3. 2 or less, and the molar ratio of sulfate ions to trivalent chromium ions is 0.10 or more and 0.30 or less. [Selection figure] None
Description
本発明は、６価クロムフリー水性表面処理液、表面処理金属および表面処理方法に関する。 TECHNICAL FIELD The present invention relates to a hexavalent chromium-free aqueous surface treatment liquid, a surface treated metal, and a surface treatment method.
従来、金属の耐食性を向上させるために、６価クロムイオンを含む水性表面処理液で金属を表面処理する方法が知られている。 Conventionally, a method of surface-treating a metal with an aqueous surface-treating liquid containing hexavalent chromium ions is known in order to improve the corrosion resistance of the metal.
しかしながら、近年の環境規制の動向からすると、６価クロムイオンを含む水性表面処理液の使用が制限される可能性がある。 However, recent trends in environmental regulations may limit the use of aqueous surface treatment solutions containing hexavalent chromium ions.
そこで、６価クロムイオンを含まない６価クロムフリー水性表面処理液が種々開発されている。例えば、亜鉛系めっき鋼材の表面処理に用いられる６価クロムフリー水性表面処理液として、３価クロム化合物と、コバルト化合物と、キレート系性能のある有機酸と、リン酸と、硫酸と、を含む酸性水溶液が知られている（特許文献１参照）。 Therefore, various hexavalent chromium-free aqueous surface treatment liquids containing no hexavalent chromium ions have been developed. For example, a hexavalent chromium-free aqueous surface treatment liquid used for surface treatment of zinc-based plated steel contains a trivalent chromium compound, a cobalt compound, an organic acid with chelating properties, phosphoric acid, and sulfuric acid. An acidic aqueous solution is known (see Patent Document 1).
しかしながら、６価クロムフリー水性表面処理液中の酸成分の含有量が多いため、亜鉛系めっき鋼材の表面におけるエッチング反応が激しくなり、３価クロムイオンの付着量が多くなるため、無着色皮膜を形成することができない。また、６価クロムフリー水性表面処理液で表面処理することにより形成される皮膜の上に、塗膜を形成した場合の塗装密着性が低い。 However, since the acid component content in the hexavalent chromium-free aqueous surface treatment solution is large, the etching reaction on the surface of the zinc-based plated steel material becomes intense, and the amount of trivalent chromium ions adhered increases, resulting in a colorless film. cannot be formed. In addition, when a coating film is formed on a coating formed by surface treatment with a hexavalent chromium-free aqueous surface treatment liquid, the coating adhesion is low.
本発明は、金属の耐食性および塗装密着性を向上させるとともに、無着色皮膜を形成することが可能な６価クロムフリー水性表面処理液を提供することを目的とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide a hexavalent chromium-free aqueous surface treatment liquid capable of improving the corrosion resistance and coating adhesion of metals and forming a colorless film.
本発明の一態様は、金属の表面処理に用いられる６価クロムフリー水性表面処理液であって、３価クロムイオンと、リン酸イオンと、硫酸イオンと、コロイダルシリカと、を含み、前記３価クロムイオンに対する前記リン酸イオンのモル比が１．９以上３．２以下であり、前記３価クロムイオンに対する前記硫酸イオンのモル比が０．１０以上０．３０以下である。 One aspect of the present invention is a hexavalent chromium-free aqueous surface treatment liquid for use in metal surface treatment, comprising trivalent chromium ions, phosphate ions, sulfate ions, and colloidal silica. The molar ratio of the phosphate ions to the valent chromium ions is 1.9 or more and 3.2 or less, and the molar ratio of the sulfate ions to the trivalent chromium ions is 0.10 or more to 0.30 or less.
上記の６価クロムフリー水性表面処理液は、前記３価クロムイオンの含有量が０．５質量％以上１０．０質量％以下であってもよい。 The content of trivalent chromium ions in the hexavalent chromium-free aqueous surface treatment liquid may be 0.5% by mass or more and 10.0% by mass or less.
上記の６価クロムフリー水性表面処理液は、前記３価クロムイオンに対するＳｉＯ２換算した前記コロイダルシリカのモル比が０．３０以上２．００以下であってもよい。 In the hexavalent chromium-free aqueous surface treatment liquid, the molar ratio of the colloidal silica converted to SiO 2 to the trivalent chromium ion may be 0.30 or more and 2.00 or less.
上記の６価クロムフリー水性表面処理液は、ニッケルイオンをさらに含み、前記ニッケルイオンの含有量が０．０４質量％以上４．００質量％以下であってもよい。 The hexavalent chromium-free aqueous surface treatment liquid may further contain nickel ions, and the nickel ion content may be 0.04% by mass or more and 4.00% by mass or less.
上記の６価クロムフリー水性表面処理液は、ポリアクリル酸をさらに含み、前記ポリアクリル酸の含有量が０．５質量％以上３０．０質量％以下であってもよい。 The hexavalent chromium-free aqueous surface treatment liquid may further contain polyacrylic acid, and the polyacrylic acid content may be 0.5% by mass or more and 30.0% by mass or less.
上記の６価クロムフリー水性表面処理液は、オキサゾリン基含有ポリマーをさらに含み、前記オキサゾリン基含有ポリマーの含有量が０．５質量％以上５．０質量％以下であってもよい。 The hexavalent chromium-free aqueous surface treatment liquid may further include an oxazoline group-containing polymer, and the content of the oxazoline group-containing polymer may be 0.5% by mass or more and 5.0% by mass or less.
上記の６価クロムフリー水性表面処理液は、ｐＨが１．０以上４．０以下であってもよい。 The hexavalent chromium-free aqueous surface treatment liquid may have a pH of 1.0 or more and 4.0 or less.
本発明の他の一態様は、表面処理金属において、上記の６価クロムフリー水性表面処理液で金属を表面処理することにより形成される皮膜を有する。 Another aspect of the present invention is a surface-treated metal having a film formed by surface-treating the metal with the hexavalent chromium-free aqueous surface treatment liquid.
上記の表面処理金属は、前記皮膜の上に、塗膜をさらに有してもよい。 The above surface-treated metal may further have a coating on the coating.
本発明の他の一態様は、表面処理方法において、上記の６価クロムフリー水性表面処理液で金属を表面処理することにより皮膜を形成する皮膜形成工程を含む。 Another aspect of the present invention includes a surface treatment method including a film forming step of surface-treating a metal with the hexavalent chromium-free aqueous surface treatment liquid to form a film.
本発明によれば、金属の耐食性および塗装密着性を向上させるとともに、無着色皮膜を形成することが可能な６価クロムフリー水性表面処理液を提供することができる。 According to the present invention, it is possible to provide a hexavalent chromium-free aqueous surface treatment liquid capable of improving metal corrosion resistance and paint adhesion and forming a colorless film.
以下、本発明の実施形態について説明する。 Embodiments of the present invention will be described below.
［６価クロムフリー水性表面処理液］
本実施形態の６価クロムフリー水性表面処理液は、金属の表面処理、すなわち、金属を表面処理することにより形成される皮膜を有する表面処理金属の製造に用いられる。
[Hexavalent chromium-free aqueous surface treatment liquid]
The hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is used for surface treatment of metal, that is, for production of surface-treated metal having a film formed by surface treatment of metal.
金属としては、特に限定されないが、例えば、鉄、亜鉛、アルミニウム等が挙げられ、二種以上を併用してもよい。すなわち、金属は、合金であってもよいし、めっき処理されていてもよい。 Examples of metals include, but are not limited to, iron, zinc, and aluminum, and two or more of them may be used in combination. That is, the metal may be an alloy or plated.
本実施形態の６価クロムフリー水性表面処理液は、３価クロムイオン（Ｃｒ３＋）と、リン酸イオン（ＰＯ４ ３－）と、硫酸イオン（ＳＯ４ ２－）と、コロイダルシリカ（ＳｉＯ２）と、を含む。 The hexavalent chromium-free aqueous surface treatment liquid of the present embodiment contains trivalent chromium ions (Cr 3+ ), phosphate ions (PO 4 3− ), sulfate ions (SO 4 2− ), and colloidal silica (SiO 2 ). ) and including.
ここで、３価クロムイオンに対するリン酸イオンのモル比（ＰＯ４ ３－／Ｃｒ３＋）は、１．９以上３．２以下であり、２．２以上３．０以下であることが好ましい。３価クロムイオンに対するリン酸イオンのモル比が１．９未満である場合または３．２を超える場合は、表面処理金属の耐食性および塗装密着性が低下する。 Here, the molar ratio of phosphate ions to trivalent chromium ions (PO 4 3− /Cr 3+ ) is 1.9 or more and 3.2 or less, preferably 2.2 or more and 3.0 or less. If the molar ratio of phosphate ions to trivalent chromium ions is less than 1.9 or exceeds 3.2, the corrosion resistance and paint adhesion of the surface-treated metal are lowered.
また、３価クロムイオンに対する硫酸イオン（ＳＯ４ ２－／Ｃｒ３＋）のモル比は、０．１０以上０．３０以下であり、０．１５以上０．２５以下であることが好ましい。３価クロムイオンに対する硫酸イオンのモル比が０．１０未満であると、着色皮膜が形成されるとともに、６価クロムフリー水性表面処理液の貯蔵安定性が低下し、０．３０を超えると、表面処理金属の耐食性および塗装密着性が低下する。 Also, the molar ratio of sulfate ions (SO 4 2− /Cr 3+ ) to trivalent chromium ions is 0.10 or more and 0.30 or less, preferably 0.15 or more and 0.25 or less. When the molar ratio of sulfate ions to trivalent chromium ions is less than 0.10, a colored film is formed and the storage stability of the hexavalent chromium-free aqueous surface treatment solution is lowered. Corrosion resistance and paint adhesion of the surface-treated metal deteriorate.
本実施形態の６価クロムフリー水性表面処理液中の３価クロムイオンの含有量は、０．５質量％以上１０．０質量％以下であることが好ましく、１．５質量％以上７．０質量％以下であることがさらに好ましい。本実施形態の６価クロムフリー水性表面処理液中の３価クロムイオンの含有量が０．５質量％以上であると、表面処理金属の耐食性が向上し、１０．０質量％以下であると、表面処理金属の塗装密着性が向上する。 The content of trivalent chromium ions in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is preferably 0.5% by mass or more and 10.0% by mass or less, and more preferably 1.5% by mass or more and 7.0% by mass. % by mass or less is more preferable. When the trivalent chromium ion content in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is 0.5% by mass or more, the corrosion resistance of the surface-treated metal is improved, and when it is 10.0% by mass or less. , the coating adhesion of the surface-treated metal is improved.
３価クロムイオンに対するＳｉＯ２換算したコロイダルシリカのモル比（ＳｉＯ２／Ｃｒ３＋）は、０．３０以上２．００以下であることが好ましく、０．３５以上１．５０以下であることがさらに好ましい。３価クロムイオンに対するＳｉＯ２換算したコロイダルシリカのモル比が０．３０以上２．００以下であると、表面処理金属の耐食性が向上する。 The molar ratio (SiO 2 /Cr 3+ ) of colloidal silica in terms of SiO 2 to trivalent chromium ions is preferably 0.30 or more and 2.00 or less, more preferably 0.35 or more and 1.50 or less. preferable. When the molar ratio of colloidal silica converted to SiO 2 to trivalent chromium ions is 0.30 or more and 2.00 or less, the corrosion resistance of the surface-treated metal is improved.
本実施形態の６価クロムフリー水性表面処理液中の水の含有量は、特に限定されないが、例えば、１０質量％以上９９質量％以下である。 The water content in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but is, for example, 10% by mass or more and 99% by mass or less.
本実施形態の６価クロムフリー水性表面処理液は、ニッケルイオン（Ｎｉ２＋）をさらに含んでいてもよい。これにより、表面処理金属の耐食性が向上する。 The hexavalent chromium-free aqueous surface treatment liquid of the present embodiment may further contain nickel ions (Ni 2+ ). This improves the corrosion resistance of the surface-treated metal.
本実施形態の６価クロムフリー水性表面処理液中のニッケルイオンの含有量は、０．０４質量％以上４．００質量％以下であることが好ましく、０．０８質量％以上３．００質量％以下であることがさらに好ましい。本実施形態の６価クロムフリー水性表面処理液中のニッケルイオンの含有量が０．０４質量％以上４．００質量％以下であると、表面処理金属の耐食性が向上する。 The content of nickel ions in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is preferably 0.04% by mass or more and 4.00% by mass or less, and more preferably 0.08% by mass or more and 3.00% by mass. More preferably: When the content of nickel ions in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is 0.04% by mass or more and 4.00% by mass or less, the corrosion resistance of the surface-treated metal is improved.
本実施形態の６価クロムフリー水性表面処理液は、ポリアクリル酸をさらに含んでいてもよい。これにより、表面処理金属の塗装密着性が向上する。 The hexavalent chromium-free aqueous surface treatment liquid of the present embodiment may further contain polyacrylic acid. This improves the coating adhesion of the surface-treated metal.
本実施形態の６価クロムフリー水性表面処理液中のポリアクリル酸の含有量は、０．５質量％以上３０．０質量％以下であることが好ましく、１．０質量％以上１５．０質量％以下であることがさらに好ましい。本実施形態の６価クロムフリー水性表面処理液中のポリアクリル酸の含有量が０．５質量％以上３０．０質量％以下であると、表面処理金属の塗装密着性が向上する。 The content of polyacrylic acid in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is preferably 0.5% by mass or more and 30.0% by mass or less, and is preferably 1.0% by mass or more and 15.0% by mass. % or less. When the content of polyacrylic acid in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is 0.5% by mass or more and 30.0% by mass or less, the coating adhesion of the surface-treated metal is improved.
本実施形態の６価クロムフリー水性表面処理液は、ポリアクリル酸を含む場合に、オキサゾリン基含有ポリマーをさらに含んでいてもよい。これにより、表面処理金属の耐食性が向上する。ここで、オキサゾリン基含有ポリマーは、ポリアクリル酸の架橋剤として機能する。 When the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment contains polyacrylic acid, it may further contain an oxazoline group-containing polymer. This improves the corrosion resistance of the surface-treated metal. Here, the oxazoline group-containing polymer functions as a cross-linking agent for polyacrylic acid.
オキサゾリン基含有ポリマーの市販品としては、例えば、エポクロス（日本触媒製）等が挙げられる。 Examples of commercially available oxazoline group-containing polymers include Epocross (manufactured by Nippon Shokubai Co., Ltd.).
本実施形態の６価クロムフリー水性表面処理液中のオキサゾリン基含有ポリマーの含有量は、０．５質量％以上５．０質量％以下であることが好ましく、０．８質量％以上３．０質量％以下であることがさらに好ましい。本実施形態の６価クロムフリー水性表面処理液中のオキサゾリン基含有ポリマーの含有量が０．５質量％以上５．０質量％以下であると、表面処理金属の耐食性が向上する。 The content of the oxazoline group-containing polymer in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is preferably 0.5% by mass or more and 5.0% by mass or less, and 0.8% by mass or more and 3.0% by mass. % by mass or less is more preferable. When the content of the oxazoline group-containing polymer in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is 0.5% by mass or more and 5.0% by mass or less, the corrosion resistance of the surface-treated metal is improved.
本実施形態の６価クロムフリー水性表面処理液のｐＨは、１．０以上４．０以下であることが好ましく、１．３以上３．０以下であることがさらに好ましい。本実施形態の６価クロムフリー水性表面処理液のｐＨが１．０以上４．０以下であると、本実施形態の６価クロムフリー水性表面処理液の貯蔵安定性が向上する。 The pH of the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is preferably 1.0 or more and 4.0 or less, more preferably 1.3 or more and 3.0 or less. When the pH of the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is from 1.0 to 4.0, the storage stability of the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is improved.
本実施形態の６価クロムフリー水性表面処理液に含まれる３価クロムイオンの供給源としては、特に限定されないが、例えば、リン酸クロム、硝酸クロム、酢酸クロム、塩化クロム等の３価クロム塩が挙げられる。 The source of trivalent chromium ions contained in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but examples thereof include trivalent chromium salts such as chromium phosphate, chromium nitrate, chromium acetate, and chromium chloride. is mentioned.
本実施形態の６価クロムフリー水性表面処理液に含まれる硫酸イオンの供給源としては、特に限定されないが、例えば、硫酸、硫酸ニッケル等の金属硫酸塩等が挙げられる。 The source of sulfate ions contained in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but examples thereof include metal sulfates such as sulfuric acid and nickel sulfate.
本実施形態の６価クロムフリー水性表面処理液に含まれるリン酸イオンの供給源としては、特に限定されないが、例えば、リン酸、リン酸クロム等の金属リン酸塩等が挙げられる。 The source of phosphate ions contained in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but examples thereof include phosphoric acid and metal phosphates such as chromium phosphate.
本実施形態の６価クロムフリー水性表面処理液に含まれるニッケルイオンの供給源としては、特に限定されないが、例えば、炭酸ニッケル、硫酸ニッケル等のニッケル塩が挙げられる。 The supply source of nickel ions contained in the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but examples thereof include nickel salts such as nickel carbonate and nickel sulfate.
本実施形態の６価クロムフリー水性表面処理液は、上述した成分以外の成分（他の成分）をさらに含んでいてもよい。 The hexavalent chromium-free aqueous surface treatment liquid of the present embodiment may further contain components (other components) other than the components described above.
他の成分としては、オキサゾリン基含有ポリマー以外のポリアクリル酸の架橋剤、レベリング剤、消泡剤、ｐＨ調整剤等が挙げられる。 Other components include a cross-linking agent for polyacrylic acid other than the oxazoline group-containing polymer, a leveling agent, an antifoaming agent, a pH adjuster, and the like.
［表面処理金属］
本実施形態の表面処理金属は、本実施形態の６価クロムフリー水性表面処理液で金属を表面処理することにより形成される皮膜を有する。
[Surface treatment metal]
The surface-treated metal of this embodiment has a film formed by surface-treating a metal with the hexavalent chromium-free aqueous surface treatment liquid of this embodiment.
金属の形状としては、特に限定されないが、例えば、板状等が挙げられる。 Although the shape of the metal is not particularly limited, for example, it may be plate-like.
金属板としては、例えば、亜鉛めっき鋼板、亜鉛合金めっき鋼板等が挙げられる。 Examples of metal plates include galvanized steel sheets and zinc alloy plated steel sheets.
亜鉛合金めっき鋼板としては、例えば、亜鉛－ニッケルめっき鋼板、亜鉛－鉄めっき鋼板、亜鉛－クロムめっき鋼板、亜鉛－アルミニウムめっき鋼板、亜鉛－チタンめっき鋼板、亜鉛－マグネシウムめっき鋼板、亜鉛－アルミニウム－マグネシウム鋼板、亜鉛－マンガンめっき鋼板等が挙げられる。 Examples of zinc alloy plated steel sheets include zinc-nickel plated steel sheets, zinc-iron plated steel sheets, zinc-chromium plated steel sheets, zinc-aluminum plated steel sheets, zinc-titanium plated steel sheets, zinc-magnesium plated steel sheets, and zinc-aluminum-magnesium. A steel plate, a zinc-manganese plated steel plate, and the like can be mentioned.
めっきとしては、例えば、電気めっき、溶融めっき、蒸着めっき等が挙げられる。 Examples of plating include electroplating, hot dip plating, vapor deposition plating, and the like.
本実施形態の表面処理金属は、皮膜の上に、塗膜をさらに有していてもよい。 The surface-treated metal of this embodiment may further have a coating film on the film.
塗膜を形成する際に用いることができる塗料としては、特に限定されず、例えば、エポキシ系塗料、アクリル系塗料、ポリエステル系塗料、ウレタン系塗料、フッ素系塗料等が挙げられる。 The paint that can be used to form the coating film is not particularly limited, and examples thereof include epoxy-based paints, acrylic-based paints, polyester-based paints, urethane-based paints, fluorine-based paints, and the like.
塗膜は、単層膜であってもよいし、積層膜であってもよい。 The coating film may be a single layer film or a laminated film.
単層膜を形成する際に、１コート用塗料を用いることができる。 When forming a single layer film, a one-coat paint can be used.
１コート用塗料としては、例えば、アクリル・メラミン系塗料等が挙げられる。 Examples of one-coat paints include acrylic/melamine paints.
積層膜を形成する際に、プライマーおよびトップコートを用いることができる。 A primer and a topcoat can be used when forming the laminated film.
プライマーとしては、例えば、エポキシ・ポリエステル系プライマー、フェノール系プライマー等が挙げられる。 Examples of primers include epoxy/polyester primers and phenol primers.
トップコートとしては、例えば、ポリエステル系トップコート等が挙げられる。 Examples of topcoats include polyester-based topcoats.
［表面処理方法］
本実施形態の表面処理方法は、本実施形態の６価クロムフリー水性表面処理液で金属を表面処理することにより皮膜を形成する皮膜形成工程を含む。
[Surface treatment method]
The surface treatment method of the present embodiment includes a film forming step of surface-treating a metal with the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment to form a film.
皮膜形成工程は、例えば、本実施形態の６価クロムフリー水性表面処理液を金属の表面に塗布した後、乾燥させる。 In the film forming step, for example, the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is applied to the surface of the metal and then dried.
本実施形態の６価クロムフリー水性表面処理液を塗布する方法としては、特に限定されないが、例えば、ロールコーター塗装、刷毛塗り塗装、ローラー塗装、バーコーター塗装、流し塗り塗装等が挙げられる。 The method of applying the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment is not particularly limited, but examples thereof include roll coater coating, brush coating, roller coating, bar coater coating, flow coating, and the like.
乾燥方法としては、公知の方法を用いることができる。 As a drying method, a known method can be used.
乾燥させる際に、例えば、金属の表面の到達温度（ピークメタル温度）が６０℃以上９０℃以下であることが好ましい。 When drying, for example, it is preferable that the metal surface reaches a temperature (peak metal temperature) of 60° C. or more and 90° C. or less.
皮膜形成工程は、本実施形態の６価クロムフリー水性表面処理液を金属の表面に塗布しながら、乾燥させてもよい。例えば、本実施形態の６価クロムフリー水性表面処理液を、予熱しておいた金属の表面に塗布し、乾燥させてもよい。 In the film forming step, the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment may be dried while being applied to the surface of the metal. For example, the hexavalent chromium-free aqueous surface treatment liquid of the present embodiment may be applied to a preheated metal surface and dried.
皮膜形成工程における乾燥後の皮膜の形成量は、０．１ｍｇ／ｍ２以上５００ｍｇ／ｍ２以下であることが好ましく、１ｍｇ／ｍ２以上２５０ｍｇ／ｍ２以下であることがさらに好ましい。 The amount of the film formed after drying in the film forming step is preferably 0.1 mg/m 2 or more and 500 mg/m 2 or less, more preferably 1 mg/m 2 or more and 250 mg/m 2 or less.
本実施形態の表面処理方法は、皮膜の上に、塗膜を形成する塗膜形成工程をさらに含んでいてもよい。 The surface treatment method of the present embodiment may further include a coating film forming step of forming a coating film on the coating.
塗膜形成工程は、例えば、塗料を塗布した後、焼き付け乾燥させる。 In the coating film forming step, for example, the coating is applied and then baked and dried.
塗料としては、１コート用塗料を用いてもよいし、プライマーおよびトップコートを用いてもよい。 As the paint, a one-coat paint may be used, or a primer and a topcoat may be used.
なお、プライマーおよびトップコートを用いる場合は、プライマーおよびトップコートを塗布する毎に、焼き付け乾燥させてもよいし、プライマーおよびトップコートを塗布した後に、焼き付け乾燥させてもよい。 When the primer and topcoat are used, the substrate may be baked and dried each time the primer and topcoat are applied, or may be baked and dried after the primer and topcoat are applied.
以下、本発明の実施例を説明するが、本発明は、実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the examples.
［実施例１～３、５～７、９、１１～１８、比較例１、４～６］
表１に記載されている特性となるように、リン酸クロム（Ｃｒ（Ｈ１．５ＰＯ４）２）、リン酸（Ｈ３ＰＯ４）、硫酸（Ｈ２ＳＯ４）、コロイダルシリカ（ＳｉＯ２）、炭酸ニッケル（ＮｉＣＯ３）、ポリアクリル酸（ＰＡ）、オキサゾリン基含有ポリマー（ＯＸ）、ｐＨ調整剤およびイオン交換水を混合撹拌し、６価クロムフリー水性表面処理液を得た。
[Examples 1 to 3, 5 to 7, 9, 11 to 18, Comparative Examples 1, 4 to 6]
Chromium phosphate (Cr( H1.5PO4 ) 2 ), phosphoric acid ( H3PO4 ), sulfuric acid ( H2SO4), colloidal silica ( SiO 2 ), nickel carbonate (NiCO 3 ), polyacrylic acid (PA), oxazoline group-containing polymer (OX), pH adjuster and deionized water were mixed and stirred to obtain a hexavalent chromium-free aqueous surface treatment liquid.
ここで、使用した原料の詳細を以下に示す。
リン酸クロム：２Ｍ（日本化学工業製）
リン酸：８５質量％リン酸水溶液（日本化学工業製）
硫酸：７５質量％希硫酸水溶液（昭和電工製）
コロイダルシリカ：スノーテックス－Ｏ（日産化学製）
炭酸ニッケル：ｘＮｉＣＯ３／ｙＮｉ（ＯＨ）２・ｚＨ２Ｏ（日本化学産業製）
ポリアクリル酸：ジュリマーＡＣ－１０Ｌ（東亜合成製）
オキサゾリン基含有ポリマー：エポクロスＷＡ－５００（日本触媒製）
ｐＨ調整剤：アンモニア水（三井化学ファイン製）
Here, the details of the raw materials used are shown below.
Chromium phosphate: 2M (manufactured by Nippon Kagaku Kogyo)
Phosphoric acid: 85% by mass phosphoric acid aqueous solution (manufactured by Nippon Kagaku Kogyo)
Sulfuric acid: 75% by mass dilute sulfuric acid aqueous solution (manufactured by Showa Denko)
Colloidal silica: Snowtex-O (manufactured by Nissan Chemical)
Nickel carbonate: xNiCO3 / yNi (OH) 2.zH2O (manufactured by Nihon Kagaku Sangyo)
Polyacrylic acid: Jurimer AC-10L (manufactured by Toagosei Co., Ltd.)
Oxazoline group-containing polymer: Epocross WA-500 (manufactured by Nippon Shokubai)
pH adjuster: Ammonia water (manufactured by Mitsui Chemicals Fine)
［実施例４、８、１０、比較例２、３］
リン酸クロムの代わりに、硝酸クロム（Ｃｒ（ＮＯ３）３）を用いた以外は、上記と同様にして、６価クロムフリー水性表面処理液を得た。
[Examples 4, 8, 10, Comparative Examples 2, 3]
A hexavalent chromium-free aqueous surface treatment liquid was obtained in the same manner as above, except that chromium nitrate (Cr(NO 3 ) 3 ) was used instead of chromium phosphate.
ここで、使用した原料の詳細を以下に示す。
硝酸クロム：液体硝酸クロム（日本化学工業製）
Here, the details of the raw materials used are shown below.
Chromium nitrate: Liquid chromium nitrate (manufactured by Nippon Kagaku Kogyo)
４０℃のインキュベータで３か月間、６価クロムフリー水性表面処理液を静置した後、以下の判定基準で、貯蔵安定性を目視評価した。
３（合格）：６価クロムフリー水性表面処理液が白濁していない場合
２（不合格）：６価クロムフリー水性表面処理液がやや白濁している場合
１（不合格）：６価クロムフリー水性表面処理液が白濁している場合
［一次防錆処理（皮膜の形成）］
６価クロムフリー水性表面処理液で、板厚０．３５ｍｍの鋼板（表２参照）を表面処理することにより皮膜を形成した。具体的には、アルカリ脱脂剤であるサーフクリーナー１５５（日本ペイント・サーフケミカルズ製）を用いて、６０℃で１０秒間鋼板をスプレー脱脂した後、スプレー水洗し、乾燥させた。次に、バーコーター＃３を用いて、６価クロムフリー水性表面処理液を鋼板に塗布した後、ピークメタル温度８０℃で乾燥させた。
After allowing the hexavalent chromium-free aqueous surface treatment liquid to stand in an incubator at 40° C. for 3 months, the storage stability was visually evaluated according to the following criteria.
3 (Pass): When the hexavalent chromium-free aqueous surface treatment liquid is not cloudy 2 (Fail): When the hexavalent chromium-free aqueous surface treatment liquid is slightly cloudy 1 (Fail): Hexavalent chromium free When the water-based surface treatment liquid is cloudy [Primary rust prevention treatment (film formation)]
A film was formed by surface-treating a steel plate (see Table 2) having a thickness of 0.35 mm with a hexavalent chromium-free aqueous surface treatment liquid. Specifically, using Surf Cleaner 155 (manufactured by Nippon Paint Surf Chemicals), which is an alkaline degreasing agent, the steel plate was degreased by spraying at 60° C. for 10 seconds, then washed with spray water and dried. Next, using bar coater #3, the hexavalent chromium-free aqueous surface treatment liquid was applied to the steel sheet, and then dried at a peak metal temperature of 80°C.
ここで、使用した鋼板の詳細を以下に示す。
ＥＧ：電気亜鉛めっき鋼板
ＧＩ：溶融亜鉛めっき鋼板
ＧＬ：５５％アルミ亜鉛合金めっき鋼板
ＧＡ：鉄亜鉛合金めっき鋼板
Here, the details of the steel plate used are shown below.
EG: Electrogalvanized steel sheet GI: Hot dip galvanized steel sheet GL: 55% aluminum zinc alloy coated steel sheet GA: Iron zinc alloy coated steel sheet
［皮膜の着色］
鋼板に形成された皮膜の着色を目視評価した。
[Coloring of film]
Coloring of the film formed on the steel plate was visually evaluated.
［耐食性（ＳＳＴ）］
ＪＩＳ Ｚ２３７１に準拠して、皮膜が形成された鋼板の塩水噴霧試験（ＳＳＴ）を２４０時間実施し、表面の白錆が発生した面積の割合（白錆率）を目視評価し、以下の判定基準で、耐食性（ＳＳＴ）を評価した。
[Corrosion resistance (SST)]
In accordance with JIS Z2371, a salt spray test (SST) was performed on the coated steel sheet for 240 hours, and the ratio of the surface area where white rust occurred (white rust rate) was visually evaluated, and the following criteria were used. was evaluated for corrosion resistance (SST).
合格：白錆率が３０％以下である場合
不合格：白錆率が３０％を超える場合
Accepted: When the white rust rate is 30% or less Fail: When the white rust rate exceeds 30%
［二次防錆処理１（塗膜１の形成）］
皮膜が形成された鋼板に、エポキシ・ポリエステル系プライマーＮＳＣ５６１０ＮＣ ＰＲＩＭＥＲ（日本ペイント・インダストリアルコーティングス製）を乾燥膜厚が５μｍとなるようにバーコーターで塗装した後、ピークメタル温度２１５℃で焼き付け乾燥させた。次に、ポリエステル系トップコートＳ／Ｃ ４９０ＨＱ １Ｃ４６６１（日本ペイント・インダストリアルコーティングス製）を乾燥膜厚が１５μｍとなるようにバーコーターで塗装した後、ピークメタル温度２３０℃で焼き付け乾燥させ、塗膜１を形成した。
[Secondary rust prevention treatment 1 (formation of coating film 1)]
Epoxy/polyester primer NSC5610NC PRIMER (manufactured by Nippon Paint Industrial Coatings) was applied to the coated steel plate with a bar coater so that the dry film thickness was 5 μm, and then baked and dried at a peak metal temperature of 215°C. rice field. Next, a polyester top coat S/C 490HQ 1C4661 (manufactured by Nippon Paint Industrial Coatings) was applied with a bar coater so that the dry film thickness was 15 μm, and then baked and dried at a peak metal temperature of 230 ° C. to obtain a coating film. 1 was formed.
［二次防錆処理２（塗膜２の形成）］
皮膜が形成された鋼板に、フェノール系プライマーＮキノコート３８（日本ペイント・インダストリアルコーティングス製）を乾燥膜厚が５μｍとなるようにバーコーターで塗装した後、ピークメタル温度２２０℃で焼き付け乾燥させた以外は、塗膜１と同様にして、塗膜２を形成した。
[Secondary rust prevention treatment 2 (formation of coating film 2)]
Phenolic Primer N Kino Coat 38 (manufactured by Nippon Paint Industrial Coatings) was applied to the coated steel plate with a bar coater so that the dry film thickness was 5 μm, and then baked and dried at a peak metal temperature of 220 ° C. Coating film 2 was formed in the same manner as coating film 1 except for the above.
［二次防錆処理３（塗膜３の形成）］
皮膜が形成された鋼板に、１コート用アクリル・メラミン系塗料スーパーラック１００（日本ペイント・インダストリアルコーティングス製）を乾燥膜厚が２０μｍとなるようにバーコーターで塗装した後、１５０℃で２０分間焼き付け乾燥させ、塗膜３を形成した。
[Secondary rust prevention treatment 3 (formation of coating film 3)]
After coating the coated steel plate with one-coat acrylic/melamine paint Super Rack 100 (manufactured by Nippon Paint Industrial Coatings) with a bar coater so that the dry film thickness becomes 20 μm, the coating is performed at 150° C. for 20 minutes. A coating film 3 was formed by baking and drying.
［塗装密着性（２ＴＴ）］
２０℃の環境下で、塗膜が形成された鋼板を、スペーサとしての、板厚０．３５ｍｍのアルミニウム板２枚を間に挟んだ状態で１８０°折り曲げ加工した後、折り曲げ加工部を３回テープ剥離した。このとき、ＪＩＳ Ｚ０２３７：２００９に準拠して、テープ剥離試験を実施した。塗膜の剥離度合いを２０倍ルーペで観察し、以下の判定基準で、塗装密着性（２ＴＴ）を評価した。
５（合格）：塗膜の剥離度合いが０％である場合
４．５（合格）：塗膜の剥離度合いが１～１０％である場合
４（合格）：塗膜の剥離度合いが１１～２０％である場合
３．５（不合格）：塗膜の剥離度合いが２１～３０％である場合
３（不合格）：塗膜の剥離度合いが３１～４０％である場合
２．５（不合格）：塗膜の剥離度合いが４１～５０％である場合
２（不合格）：塗膜の剥離度合いが５１～６０％である場合
１．５（不合格）：塗膜の剥離度合いが６１～７０％である場合
１（不合格）：塗膜の剥離度合いが７１～８０％である場合
０．５（不合格）：塗膜の剥離度合いが８１～９０％である場合
０（不合格）：塗膜の剥離度合いが９１～１００％である場合
[Painting adhesion (2TT)]
In an environment of 20° C., the steel plate on which the coating film is formed is bent 180° with two aluminum plates having a thickness of 0.35 mm as spacers sandwiched between them, and then the bent portion is bent three times. Removed the tape. At this time, a tape peeling test was performed in accordance with JIS Z0237:2009. The degree of peeling of the paint film was observed with a 20x magnifying glass, and the paint adhesion (2TT) was evaluated according to the following criteria.
5 (Pass): When the degree of peeling of the coating film is 0% 4.5 (Pass): When the degree of peeling of the coating film is 1 to 10% 4 (Pass): The degree of peeling of the coating film is 11 to 20 % 3.5 (failed): When the degree of peeling of the coating film is 21 to 30% 3 (failed): When the degree of peeling of the coating film is 31 to 40% 2.5 (failed ): When the degree of peeling of the coating film is 41 to 50% 2 (failed): When the degree of peeling of the coating film is 51 to 60% 1.5 (failed): The degree of peeling of the coating film is 61 ~ If it is 70% 1 (failed): If the degree of peeling of the coating film is 71 to 80% 0.5 (failed): If the degree of peeling of the coating film is 81 to 90% 0 (failed) : When the peeling degree of the coating film is 91 to 100%
［塗装密着性（０ＴＴ）］
スペーサを間に挟まない状態で１８０°折り曲げ加工した以外は、塗装密着性（２ＴＴ）と同様にして、塗装密着性（０ＴＴ）を評価した。
[Painting adhesion (0TT)]
The coating adhesion (0TT) was evaluated in the same manner as the coating adhesion (2TT), except that the sample was bent 180° without a spacer interposed therebetween.
［耐食性（ＳＳＴ）］
ＪＩＳ Ｚ２３７１に準拠して、塗膜が形成された鋼板にクロスカットを入れた後、塩水噴霧試験（ＳＳＴ）を１０００時間実施し、カット傷からの片側の平均フクレ幅を測定し、以下の判定基準で、耐食性（ＳＳＴ）を評価した。
合格：平均フクレ幅が０．４５ｍｍ以下である場合
不合格：平均フクレ幅が０．４５ｍｍを超える場合
[Corrosion resistance (SST)]
In accordance with JIS Z2371, after cross-cutting the steel plate on which the coating film was formed, a salt spray test (SST) was performed for 1000 hours, and the average blister width on one side from the cut was measured, and the following judgments were made. Standards evaluated corrosion resistance (SST).
Pass: When the average blister width is 0.45 mm or less Fail: When the average blister width exceeds 0.45 mm
［耐食性（ＣＣＴ）］
ＪＩＳ Ｋ５６２１に準拠して、塗膜が形成された鋼板にクロスカットを入れた後、複合サイクル腐食試験（ＣＣＴ）を２０００時間実施し、カット傷からの片側の平均フクレ幅を測定し、以下の判定基準で、耐食性（ＣＣＴ）を評価した。
合格：平均フクレ幅が０．３ｍｍ以下である場合
不合格：平均フクレ幅が０．３ｍｍを超える場合
[Corrosion resistance (CCT)]
In accordance with JIS K5621, after cross-cutting the steel plate on which the coating film was formed, a combined cycle corrosion test (CCT) was performed for 2000 hours, and the average blister width on one side from the cut was measured. Criteria evaluated corrosion resistance (CCT).
Pass: When the average blister width is 0.3 mm or less Fail: When the average blister width exceeds 0.3 mm
表２に、６価クロムフリー水性表面処理液の特性および表面処理（一次防錆処理、二次防錆処理）後の鋼板の特性の評価結果を示す。なお、比較例２、５の６価クロムフリー水性表面処理液は、貯蔵安定性が不合格であったため、耐食性の評価を省略した。 Table 2 shows the evaluation results of the properties of the hexavalent chromium-free aqueous surface treatment liquid and the properties of the steel sheet after surface treatment (primary rust prevention treatment, secondary rust prevention treatment). Since the hexavalent chromium-free aqueous surface treatment liquids of Comparative Examples 2 and 5 failed in storage stability, evaluation of corrosion resistance was omitted.
これに対して、比較例１の６価クロムフリー水性表面処理液は、ＰＯ４ ３－／Ｃｒ３＋が４であるため、表面処理鋼板の耐食性および塗装密着性が低い。比較例３の６価クロムフリー水性表面処理液は、ＰＯ４ ３－を含まないため、表面処理鋼板の耐食性および塗装密着性が低い。比較例４の６価クロムフリー水性表面処理液は、ＳＯ４ ２－／Ｃｒ３＋が０．４であるため、表面処理鋼板の耐食性および塗装密着性が低い。比較例５の６価クロムフリー水性表面処理液は、ＳＯ４ ２－／Ｃｒ３＋が０．０６であるため、着色皮膜が形成される。比較例６の６価クロムフリー水性表面処理液は、ＳｉＯ２を含まないため、表面処理鋼板の耐食性および塗装密着性が低い。 On the other hand, the hexavalent chromium-free aqueous surface treatment liquid of Comparative Example 1 has a PO 4 3− /Cr 3+ of 4, so that the corrosion resistance and paint adhesion of the surface-treated steel sheet are low. Since the hexavalent chromium-free aqueous surface treatment liquid of Comparative Example 3 does not contain PO 4 3- , the corrosion resistance and paint adhesion of the surface-treated steel sheet are low. The hexavalent chromium-free water-based surface treatment liquid of Comparative Example 4 had SO 4 2− /Cr 3+ of 0.4, so that the corrosion resistance and paint adhesion of the surface-treated steel sheet were low. Since the hexavalent chromium-free aqueous surface treatment liquid of Comparative Example 5 has SO 4 2− /Cr 3+ of 0.06, a colored film is formed. Since the hexavalent chromium-free aqueous surface treatment liquid of Comparative Example 6 does not contain SiO 2 , the corrosion resistance and paint adhesion of the surface-treated steel sheet are low.
Claims (9)
３価クロムイオンと、リン酸イオンと、硫酸イオンと、コロイダルシリカと、を含み、
前記３価クロムイオンに対する前記リン酸イオンのモル比が１．９以上３．２以下であり、
前記３価クロムイオンに対する前記硫酸イオンのモル比が０．１０以上０．３０以下であり、
ｐＨが１．０以上４．０以下である、６価クロムフリー水性表面処理液。 A hexavalent chromium-free aqueous surface treatment liquid used for metal surface treatment,
containing trivalent chromium ions, phosphate ions, sulfate ions, and colloidal silica,
the molar ratio of the phosphate ions to the trivalent chromium ions is 1.9 or more and 3.2 or less;
the molar ratio of the sulfate ions to the trivalent chromium ions is 0.10 or more and 0.30 or less ;
A hexavalent chromium-free aqueous surface treatment liquid having a pH of 1.0 or more and 4.0 or less .
前記ニッケルイオンの含有量が０．０４質量％以上４.００質量％以下である、請求項１から３のいずれか一項に記載の６価クロムフリー水性表面処理液。 further comprising nickel ions,
The hexavalent chromium-free aqueous surface treatment liquid according to any one of claims 1 to 3, wherein the nickel ion content is 0.04% by mass or more and 4.00% by mass or less.
前記ポリアクリル酸の含有量が０．５質量％以上３０．０質量％以下である、請求項１から４のいずれか一項に記載の６価クロムフリー水性表面処理液。 further comprising polyacrylic acid,
The hexavalent chromium-free aqueous surface treatment liquid according to any one of claims 1 to 4, wherein the polyacrylic acid content is 0.5% by mass or more and 30.0% by mass or less.
前記オキサゾリン基含有ポリマーの含有量が０．５質量％以上５．０質量％以下である、請求項５に記載の６価クロムフリー水性表面処理液。 further comprising an oxazoline group-containing polymer,
6. The hexavalent chromium-free aqueous surface treatment liquid according to claim 5, wherein the content of said oxazoline group-containing polymer is 0.5% by mass or more and 5.0% by mass or less.
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| KR101111445B1 (en) * | 2009-09-25 | 2012-02-15 | 한양화학(공) | Aquous composition for forming trivalent chromium coating and method of forming black trivalent chromium coating using same |
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| JP2023025317A (en) | 2023-02-22 |
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