WO2015152187A1 - 亜鉛めっき鋼材用の金属表面処理剤、被覆方法及び被覆鋼材 - Google Patents
亜鉛めっき鋼材用の金属表面処理剤、被覆方法及び被覆鋼材 Download PDFInfo
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- WO2015152187A1 WO2015152187A1 PCT/JP2015/060022 JP2015060022W WO2015152187A1 WO 2015152187 A1 WO2015152187 A1 WO 2015152187A1 JP 2015060022 W JP2015060022 W JP 2015060022W WO 2015152187 A1 WO2015152187 A1 WO 2015152187A1
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- mass
- metal surface
- surface treatment
- treatment agent
- galvanized steel
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- 150000008064 anhydrides Chemical class 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ICRFXIKCXYDMJD-UHFFFAOYSA-N n'-benzyl-n'-ethenyl-n-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 ICRFXIKCXYDMJD-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YTZVWGRNMGHDJE-UHFFFAOYSA-N tetralithium;silicate Chemical compound [Li+].[Li+].[Li+].[Li+].[O-][Si]([O-])([O-])[O-] YTZVWGRNMGHDJE-UHFFFAOYSA-N 0.000 description 1
- 150000003564 thiocarbonyl compounds Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
Definitions
- the present invention relates to a metal surface treatment agent for galvanized steel, a coating method using the metal surface treatment agent, and a coated steel material.
- galvanized steel materials have been widely subjected to anti-corrosion treatment with chromate using hexavalent chromate, etc., and coated with organic resin as necessary to provide fingerprint resistance, scratch resistance, etc. After that, various paints were overcoated.
- Patent Document 1 discloses that an average particle size of 20 to 100 nm, an ethylene-unsaturated carboxylic acid copolymer resin particle (A) containing a silanol group and / or an alkoxysilyl group, an average particle size of 5 to 50 nm.
- a coated steel sheet is described which is a film in which a certain silicon oxide particle (B) and an organic titanium compound (C) are combined, and the film amount is 0.5 to 3 g / m 2 .
- the above coating film is required to further improve the tape peel resistance although the substrate adhesion and press oil resistance are improved.
- Patent Document 2 discloses a treatment liquid in which an organic resin, a silane coupling agent, and a solid wetting agent are contained in a lithium silicate aqueous solution having a SiO 2 / Li 2 O ratio (molar ratio) of 18 to 33, a metal There is described a surface-treated metal plate characterized by being applied to the plate surface and then dried.
- the above metal plate has a problem of poor alkali resistance.
- Patent Document 3 discloses a surface-treated metal plate in which a surface-treated film is formed on a metal plate or a plated metal plate.
- the surface-treated film comprises Si and Li in a Si / Li (molar ratio) of 36 to 66.
- a surface-treated metal plate characterized by substantially not containing Cr is inferior.
- Patent Document 4 discloses a lithium silicate having an Si / Li molar ratio in the range of 1 to 4 in an aqueous medium, and 5 to 50 parts by mass of a silane coupling agent in an amount of 100 parts by mass of the lithium silicate. 0.2 to 10 parts by mass (as vanadium metal) vanadium compound, 0.2 to 10 parts by mass (as titanium metal) titanium compound, and 0.01 to 10 parts by mass wax.
- a surface treatment solution for zinc-based plated metal material is described. However, the surface treatment solution for zinc-based plated metal material has insufficient alkali resistance.
- the present invention is a metal surface treatment for galvanized steel materials with improved press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance. It is an object to provide an agent, a coating method using the metal surface treatment agent, and a coated steel material.
- tape-peeling resistance means that when steel strips or processed products are transported by sea, they are fixed with a highly adhesive tape and exposed to high temperature and high humidity conditions.
- the abrasion resistance indicates the resistance to abrasion scratches that may occur due to rubbing during transportation of steel coils and processed products.
- the inventors of the present invention obtained specific organic resin particles (A), silicon oxide particles (B), lithium silicate (C), organic titanium compounds (D), and epoxy group-containing compounds (E). It is a metal surface treating agent for galvanized steel materials to be contained, and the total amount of silicon contained in the silicon oxide particles (B) and the lithium silicate (C) is converted into SiO 2 equivalent mol of the lithium silicate (C 40 to 70 times the Li 2 O equivalent mole number of the lithium element contained in), and the mass of the lithium silicate (C) relative to the mass of the titanium element contained in the organotitanium compound (D)
- Metal surface treatment agent for galvanized steel with a ratio of 0.2 to 200 has excellent press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance sex It found that expression, thereby completing the present invention.
- the present invention provides the following [1] to [7].
- the organic resin particles (A) are resin particles obtained by modifying a base resin with a silane coupling agent (A-1) and a polyfunctional epoxy group-containing compound (A-2).
- the total amount of silicon elements contained in the silicon oxide particles (B) and the lithium silicate (C) is in terms of SiO 2
- the lithium silicate (C) The solid content mass of the organic resin particles (A) is 40 to 70 times the Li 2 O equivalent mole number of the lithium element contained in the metal surface treatment agent with respect to the total solid content mass of the metal surface treatment agent. 20 70 mass%, the silicon oxide particles (B) are 10 to 50 mass%, the lithium silicate (C) is 1 to 10 mass%, and the organotitanium compound (D) is in terms of titanium element.
- the epoxy group-containing compound (E) is 0.2 to 10% by mass
- the lithium silicate with respect to the mass of the titanium element contained in the organic titanium compound (D) A metal surface treatment agent for galvanized steel, wherein the mass ratio of C) is 0.2 to 200.
- the ratio of the total mass of the silane coupling agent (A-1) to the sum of the mass of titanium element and the mass of lithium silicate (C) contained in the organic titanium compound (D) is 0.
- the metal surface treating agent for galvanized steel materials according to any one of the above [1] to [4].
- the organic resin particles (A) are obtained by mixing and reacting the polyfunctional epoxy group-containing compound (A-2) in a proportion of 1 to 20% by mass with respect to the solid content mass of the base resin.
- the molar amount of SiO 2 in terms of the total amount of silicon elements contained in the silicon oxide particles (B) and the lithium silicate (C) is equal to the lithium element Li contained in the lithium silicate (C).
- a galvanized steel material characterized in that the surface treatment agent for galvanized steel material according to any one of [1] to [7] is applied to the surface of the galvanized steel material to form a film. Coating method.
- a metal surface treatment agent for galvanized steel material with improved press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance A coating method using a metal surface treatment agent and a coated steel material can be provided.
- the metal surface treatment agent for galvanized steel materials of the present invention includes organic resin particles (A), silicon oxide particles (B), lithium silicate (C), organic titanium compounds (D), and epoxy group-containing compounds (E).
- the organic resin particles (A) are modified with a silane coupling agent (A-1) and a polyfunctional epoxy group-containing compound (A-2).
- the solid content of the child (A) is 20 to 70% by mass
- the silicon oxide particles (B) are 10 to 50% by mass
- the lithium silicate (C) is 1 to 10% by mass
- the organic titanium compound (D) is 0.05 to 5% by mass in terms of titanium element
- the epoxy group-containing compound (E) is 0.2 to 10% by mass, and is contained in the organic titanium compound (D).
- a metal surface treatment agent for galvanized steel wherein the ratio of the mass of lithium silicate (C) to the mass of titanium element is 0.2 to 200.
- the metal surface treatment agent for galvanized steel material of the present invention is any of press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance. Excellent performance.
- the organic resin particles (A) used in the present invention are resin particles obtained by modifying a base resin with a silane coupling agent (A-1) and a polyfunctional epoxy group-containing compound (A-2). Or it is the resin particle which has an alkoxy silyl group.
- the base resin is not particularly limited.
- a copolymer resin of ethylene and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid or maleic anhydride (for example, ethylene-methacrylic acid copolymer) is hydroxylated.
- Water-dispersed acrylic resin neutralized with alkali metal hydroxides such as sodium and potassium hydroxide, aqueous ammonia and organic amines and dispersed in water, isocyanate group-containing compound and polyol, low molecular weight polyol, and active hydrogen group
- alkali metal hydroxides such as sodium and potassium hydroxide, aqueous ammonia and organic amines and dispersed in water, isocyanate group-containing compound and polyol, low molecular weight polyol, and active hydrogen group
- examples thereof include a water-dispersed polyurethane resin obtained by reacting a compound containing a hydrophilic group with a polyurethane prepolymer and then neutralizing the hydrophilic group with a neutralizing agent.
- organic resin particles (A) silanol groups and / or alkoxys obtained by allowing the silane coupling agent (A-1) and polyfunctional epoxy group-containing compound (A-2) described later to act on these dispersed resin liquids.
- acrylic resin particles having a silyl group examples thereof include acrylic resin particles having a silyl group, or polyurethane resin particles having a silanol group and / or an alkoxysilyl group.
- a silane coupling agent (A-1) and a polyfunctional epoxy group-containing compound (A-2) described later are allowed to act on an aqueous dispersion resin solution of an ethylene-methacrylic acid copolymer resin neutralized with a base.
- the acrylic resin particles obtained in this way are preferable in that they can be made fine and can form a high-performance film.
- the ethylene content may be 90 to 70% by mass and the methacrylic acid content may be 10 to 30% by mass. preferable. Moreover, although it may contain another monomer as needed, it is preferable that the usage-amount is 10 mass% or less.
- the ethylene-methacrylic acid copolymer resin it can be produced by a known method such as polymerization using a high-pressure low-density polyethylene production apparatus. As a compounding quantity, it is preferable to make base resin react with 80 mass% or more with respect to solid content mass of the said organic resin particle (A). More preferably, it is the range of 90 mass% or more.
- the organic resin particles (A) have silanol groups and / or alkoxysilyl groups.
- a reaction with the silicon oxide particles (B) and the organic titanium compound (D) can be caused to form a film, and the adhesion to the base material, resistance to press oil, etc. can be improved.
- the alkoxysilyl group in the alkoxysilyl group is not particularly limited, and examples thereof include a trimethoxysilyl group, a dimethoxysilyl group, a methoxysilyl group, a triethoxysilyl group, a diethoxysilyl group, and an ethoxysilyl group.
- the functional group can be obtained by reacting a silane coupling agent (A-1) described later with an aqueous dispersion of the base resin.
- silane coupling agent (A-1) examples of the silane coupling agent (A-1) used in the organic resin particles (A) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltriethoxy.
- the silane coupling agent (A-1) is blended and reacted at a ratio of 1 to 20% by mass with respect to 100% by mass of the solid content of the base resin. More preferably, it is in the range of 1 to 10% by mass.
- the blending amount is 1% by mass or more, the alkali resistance, solvent resistance, coating adhesion, etc. of the film formed on the steel material surface are good, and when it is 20% by mass or less, the hydrophilicity of the film becomes appropriate and the corrosion resistance. In some cases, and the liquid stability of the metal surface treatment agent used for forming a film may be good.
- the polyfunctional epoxy group-containing compound (A-2) used in the organic resin particles (A) includes sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, propylene glycol diglycidyl.
- examples include ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, bisphenol A glycidyl ether, hydrogenated bisphenol A diglycidyl ether, and the like. These may be used alone or in combination of two or more.
- the polyfunctional epoxy group-containing compound (A-2) When the polyfunctional epoxy group-containing compound (A-2) is used, the affinity with the organic resin is increased. Therefore, when a top coat is applied to the film, it may be advantageous for improving the adhesion of the film.
- the polyfunctional epoxy group-containing compound (A-2) does not include an epoxy group-containing silane compound.
- As a blending amount it is preferable to react 1 to 20% by mass of the polyfunctional epoxy group-containing compound (A-2) with respect to 100% by mass of the solid content of the base resin. More preferably, it is in the range of 1 to 10% by mass.
- the blending amount is 1% by mass or more, the alkali resistance, solvent resistance, coating adhesion, etc. of the film formed on the steel material surface are good, and when it is 20% by mass or less, the hydrophilicity of the film becomes appropriate and the corrosion resistance. In some cases, and the liquid stability of the metal surface treatment agent used for forming a film may be good.
- the resin particles of the organic resin particles (A) preferably have an average particle diameter of 20 to 100 nm.
- the average particle diameter can be measured by a particle diameter measuring apparatus using a dynamic light scattering method, for example, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
- the value of the average particle diameter is a cumulant average particle diameter obtained by diluting an aqueous dispersion of resin particles (A) with ion-exchanged water to a concentration suitable for measurement by the above apparatus and measuring at a liquid temperature of 25 ° C. is there.
- the average particle diameter by the above method is 20 nm or more, viscosity and hydrophilicity are appropriate, and workability, corrosion resistance, and the like are improved.
- the average particle size is 100 nm or less, the substrate adhesion, press oil resistance, and the like are favorable in terms of film performance.
- the organic resin particles (A) are contained at 20 to 70% by mass with respect to the total solid content of the metal surface treatment agent. If it is less than 20 mass%, sufficient coating film performance, especially processed part corrosion resistance cannot be obtained. Moreover, it is within 70 mass% from a viewpoint which adjusts balance with content of another component and exhibits the effect of this invention satisfactorily. From the same viewpoint, the content of the organic resin particles (A) is preferably 30 to 65% by mass, more preferably 40 to 60% by mass with respect to the total solid content of the metal surface treatment agent. . In addition, content of the said organic resin particle (A) can also be computed from the compounding quantity at the time of mix
- the silicon oxide particles (B) used in the present invention preferably have a primary particle number average particle size of 5 to 50 nm, more preferably 5 to 20 nm, and are appropriately selected from colloidal silica, fumed silica, or the like. be able to.
- the number average particle diameter of the primary particles of the silicon oxide particles (B) can be determined by observation with an electron microscope.
- Specific examples of the silicon oxide particles (B) include Snowtex N, Snowtex C (Nissan Chemical Industries), Adelite AT-20N, AT-20A (ADEKA), Cataloid S-20L, Cataloid SA (JGC) Catalytic Chemical Co., Ltd.). These may be used alone or in combination of two or more.
- the silicon oxide particles (B) are contained in an amount of 10 to 50% by mass with respect to the total solid mass of the metal surface treatment agent. If it is less than 10 mass%, sufficient coating film performance, especially substrate adhesion and tape peel resistance cannot be obtained. Moreover, it is 50 mass% or less from a viewpoint of adjusting the balance with content of another component and exhibiting the effect of this invention satisfactorily. From the same viewpoint, the content of the silicon oxide particles (B) is preferably 15 to 45% by mass, more preferably 20 to 40% by mass, based on the total solid mass of the metal surface treatment agent. . In addition, content of a silicon oxide particle (B) can also be computed from the compounding quantity at the time of mix
- the lithium silicate (C) used in the present invention is a salt composed of lithium oxide and silicon dioxide, and is represented by the general formula Li 2 O ⁇ nSiO 2 .
- n the molar ratio of lithium oxide to silicon dioxide
- the hydrate may be sufficient as lithium silicate (C), for example.
- the lithium silicate (C) can be used as, for example, an aqueous lithium silicate solution.
- the solid content concentration of the aqueous solution is, for example, 1 to 50% by mass, preferably 2 to 40% by mass. It is.
- lithium silicate (C) has different water solubility depending on the molar ratio n between lithium oxide and silicon dioxide. For example, lithium silicate having n of 2 to 5 is soluble in water. , N is 6 to 10 and is insoluble in water.
- lithium silicate 75 lithium silicate aqueous
- Lithium silicate (C) is contained in an amount of 1 to 10% by mass with respect to the total solid content of the metal surface treatment agent. If it is less than 1% by mass, the tape peel resistance is poor. Moreover, it is 10 mass% or less from a viewpoint of adjusting the balance with content of another component and exhibiting the effect of this invention satisfactorily. From the same viewpoint, the content of the lithium silicate (C) is preferably 1 to 7% by mass, more preferably 1 to 5% by mass with respect to the total solid content of the metal surface treatment agent. . In addition, content of lithium silicate (C) can also be computed from the compounding quantity at the time of mix
- the SiO 2 conversion mole number of the total amount of silicon elements contained in the silicon oxide particles (B) and the lithium silicate (C) is converted to Li 2 O of the lithium element contained in the lithium silicate (C). It is 40 to 70 times the number of moles (hereinafter, the SiO 2 molar ratio to Li 2 O is also simply referred to as 40 to 70). If the SiO 2 molar ratio to Li 2 O is less than 40, sufficient coating performance cannot be obtained, and particularly alkali resistance is lowered. On the other hand, if it exceeds 70, tape peel resistance is inferior. From the same viewpoint, the molar ratio of SiO 2 to Li 2 O is preferably 50 to 65, more preferably 50 to 60.
- the ratio of the mass of the lithium silicate (C) to the mass of the titanium element contained in the organotitanium compound (D) is 0.2. ⁇ 200.
- the ratio of the mass of the lithium silicate (C) to the mass of the titanium element contained in the organotitanium compound (D) is preferably 0.5 to 17, more preferably 1.5 to 17. It is.
- the metal surface treating agent for galvanized steel of the present invention is the silane coupling agent (for the sum of the mass of titanium element and the mass of lithium silicate (C) contained in the organotitanium compound (D)
- the mass ratio of A-1) is preferably 0.01 to 13.
- the ratio of the mass of the silane coupling agent (A-1) to the sum of the mass of titanium element and the mass of lithium silicate (C) contained in the organotitanium compound (D) is more Preferably it is 0.1 to 13, more preferably 0.35 to 0.65.
- Organic titanium compound (D) used in the present invention include dipropoxybis (triethanolaminato) titanium, dipropoxybis (diethanolaminato) titanium, dibutoxybis (triethanolaminato) titanium, dibutoxybis (diethanolamin).
- Nato titanium, dipropoxybis (acetylacetonato) titanium, dibutoxybis (acetylacetonato) titanium, dihydroxybis (lactato) titanium monoammonium salt, dihydroxybis (lactato) titanium diammonium salt, propanedioxytitanium bis (ethylacetoacetate) ), Oxotitanium bis (monoammonium oxalate), isopropyltri (N-amidoethyl / aminoethyl) titanate, and the like. These may be used alone or in combination of two or more.
- the organotitanium compound (D) is contained in an amount of 0.05 to 5% by mass in terms of titanium element with respect to the total solid content of the metal surface treatment agent. If it is less than 0.05 mass%, sufficient coating film performance cannot be obtained. Moreover, it is within 5 mass% from a viewpoint which adjusts balance with content of another component and exhibits the effect of this invention satisfactorily. From the same viewpoint, the content of the organotitanium compound (D) is more preferably 0.1 to 2% by mass, still more preferably relative to the total solid mass of the metal surface treatment agent in terms of titanium element. Is 0.3 to 1% by mass. In addition, content of an organic titanium compound (D) can also be computed from the compounding quantity at the time of mix
- the epoxy group-containing compound (E) used in the present invention is not particularly limited, but is a polyfunctional epoxy resin, and is more preferably polyfunctional from the viewpoint of reducing the amount of raw material used, preferably trifunctional or more, and more preferably Is tetrafunctional or higher. Further, from the viewpoint of adjusting the change in viscosity due to the reaction with the organic resin particles (A) and from the viewpoint of handling properties of the obtained metal treating agent, for example, it is preferably trifunctional to pentafunctional.
- the aforementioned polyfunctional epoxy group-containing compound (A-2) can be used as the epoxy group-containing compound.
- the epoxy group-containing compound (E) particularly improves the press oil resistance by forming a highly crosslinked film by crosslinking reaction with the organic resin particles (A) at the time of film formation.
- the epoxy group-containing compound (E) is contained at 0.2 to 10% by mass with respect to the total solid mass of the metal surface treatment agent. If it is less than 0.2% by mass, sufficient coating performance, particularly sufficient press oil resistance cannot be obtained. Moreover, it is 10 mass% or less from a viewpoint of adjusting the balance with content of another component and exhibiting the effect of this invention satisfactorily. From the same viewpoint, the content of the epoxy group-containing compound (E) is preferably 1 to 8% by mass, more preferably 2 to 7% by mass, based on the total solid content of the metal surface treatment agent. is there. In addition, content of an epoxy group containing compound (E) can also be computed from the compounding quantity at the time of mix
- the metal surface treating agent for galvanized steel material of the present invention preferably further contains a niobium compound (F) in addition to the above (A) to (E).
- the niobium compound (F) is preferably contained in an amount of 0.1 to 10% by mass with respect to the total solid content of the metal surface treatment agent. When the content is in the range of 0.1 to 10% by mass, the corrosion resistance of the processed part is excellent. From the same viewpoint, the content of the niobium compound (F) is more preferably 0.2 to 5% by mass, still more preferably 0.5 to 2%, based on the total solid mass of the metal surface treatment agent. % By mass.
- the niobium compound (F) is not particularly limited, and a conventionally known niobium-containing compound can be used, and examples thereof include niobium oxide, niobic acid and salts thereof, fluoroniobate, and fluorooxoniobate. Can do. Among these, niobium oxide is preferable from the viewpoint of improving corrosion resistance.
- the niobium oxide is preferably niobium oxide particles.
- membrane which compounded the niobium oxide particle can be formed, and corrosion resistance can be improved more.
- niobium oxide particles are particles in which oxides of niobium are dispersed in water in the form of fine particles.
- niobium oxide is not formed strictly, and the niobium oxide is in an intermediate state between niobium hydroxide and niobium oxide. It may be.
- Niobium oxide particles produced by a known method can be used as the niobium oxide particles added to the metal surface treatment agent used for forming the film.
- the niobium oxide particles are not particularly limited, and for example, those produced by known methods described in JP-A-6-321543, JP-A-8-143314, JP-A-8-325018, etc. Can be mentioned.
- niobium oxide sol and niobium oxide slurry marketed by Taki Chemical Co., Ltd. can also be used.
- the average particle diameter of the niobium oxide particles is preferably 2 nm to 10 ⁇ m, and more preferably 2 nm to 1 ⁇ m. A smaller average particle size is more preferable because a film containing niobium oxide that is more stable and dense can be formed, so that rust resistance can be stably imparted to the object to be treated.
- the average particle diameter of the niobium oxide particles is determined as a volume average particle diameter which is a particle diameter with a cumulative volume of 50% using a laser light diffraction / scattering type microtrack HRA particle size distribution meter (manufactured by HONEYWELL). Can do.
- the metal surface treating agent for galvanized steel of the present invention preferably further contains a phosphoric acid compound (G) in addition to the above (A) to (E) or the above (A) to (F).
- a phosphoric acid compound (G) include phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, trisodium phosphate, dihydrogen phosphate.
- phosphates such as sodium. These may be used alone or in combination of two or more.
- the phosphoric acid compound (G) is preferably contained in an amount of 0.1 to 10% by mass in terms of phosphorus element with respect to the total solid mass of the metal surface treatment agent.
- the content of the phosphoric acid compound (G) is more preferably 0.2 to 5% by mass, still more preferably based on the total solid content of the metal surface treatment agent in terms of phosphorus element. Is 0.5 to 2% by mass.
- content of a phosphoric acid compound (G) can also be computed from the compounding quantity at the time of mix
- the ratio of the phosphorus element equivalent mass of the phosphoric acid compound (G) to the mass of the niobium compound (F) is preferably 0.01 to 100, more preferably 0.03 to 10, still more preferably 0.03 to 4.
- the metal surface treating agent for galvanized steel of the present invention further contains water. May be.
- the metal surface treating agent for galvanized steel of the present invention may contain other components in addition to the above (A) to (G) and water.
- wax conventionally well-known waxes, such as hydrocarbon waxes, such as paraffin, microcrystalline, and polyolefin, these derivatives, can be used, for example.
- the derivative include carboxylated polyolefin and chlorinated polyolefin.
- lubricant for example, conventionally known lubricants such as fluorine-based, hydrocarbon-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and inorganic-based lubricants can be used.
- the pigment include titanium oxide (TiO 2 ), zinc oxide (ZnO), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon black, and iron oxide.
- An inorganic pigment such as (Fe 2 O 3 , Fe 3 O 4 ) or various colored pigments such as an organic pigment can be used.
- the thiocarbonyl compound and guanidine compound of patent 492295 can be used, for example.
- the metal surface treating agent for galvanized steel material of the present invention is obtained by mixing the silicon oxide particles (B), the lithium silicate (C), and the organic in an aqueous dispersion in which the resin particles of the organic resin particles (A) are dispersed.
- the metal surface treatment agent is prepared by blending the titanium compound (D) and the epoxy group-containing compound (E), and if necessary, the niobium compound (F), the phosphoric acid compound (G), water, It can manufacture by mix
- the coating method of the galvanized steel material of the present invention is characterized in that a coating is formed by applying the metal surface treatment agent for the galvanized steel material of the present invention to the surface of the galvanized steel material.
- the coating method of the galvanized steel material of the present invention has excellent performance in any of press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance.
- the film is a state in which the organic resin particles (A), silicon oxide particles (B), organic titanium compound (D), and epoxy group-containing compound (E) are bonded to each other. That is, the functional group of the organic resin particle (A), the functional group of the silicon oxide particle (B) surface, the organic titanium compound (D), and the functional group of the epoxy group-containing compound (E) form a bond and are combined. It is. Further, it is considered that the silicon oxide particles (B) and the lithium silicate (C) are quasi-crosslinked by ionic crosslinking in the film.
- the bonds mainly include Si—OR groups and / or Si—OH groups of the organic resin particles (A), Si—OH groups on the surface of the silicon oxide particles (B), and Ti—OR ′ groups of the organic titanium compound (D). And / or a bond formed by reaction of a Ti—OH group, which is considered to be a Si—O—Si bond, a Si—O—Ti—O—Si bond, or the like.
- These bonds provide an advantageous effect that the organic resin particles and the inorganic particles form chemically strong bonds.
- the carboxylic acid group of the organic resin particle (A) and the epoxy group of the epoxy group-containing compound (E) are cross-linked, so that a stronger film is formed and press oil resistance is improved. it is conceivable that.
- R is a substituent derived from the aforementioned silane coupling agent (A-1), and R ′ is a substituent derived from the aforementioned organic titanium compound (D).
- the silicon oxide particles (B) and the lithium silicate (C) are formed by pseudo-crosslinking by ionic crosslinking, so that it is considered that a film excellent in tape resistance is formed. Since the particle diameter of the organic resin particles (A) is within a specific range, the interparticle bonds are formed at a high density in the film, so that it is chemically stable and fine. It becomes a film with high visual homogeneity. For this reason, it is estimated that the metal surface treating agent for galvanized steel materials of the present invention is particularly effective. In producing a metal surface treatment agent for coating a galvanized steel material, the order of addition of the above components is not particularly limited. For example, the method for producing a metal surface treatment agent for galvanized steel material described above may be used. it can.
- a solvent or a leveling agent may be used in order to form a more uniform and smooth film.
- Solvents and leveling agents are not particularly limited as long as they are generally used in paints. Examples thereof include alcohol-based, ketone-based, ester-based, ether-based hydrophilic solvents and silicone-based leveling agents. be able to.
- the formation of the film by the metal surface treatment agent can be performed by applying the metal surface treatment agent to the surface of the steel material.
- the metal surface treatment agent is applied to an object to be degreased as necessary.
- the coating method is not particularly limited, and commonly used roll coat, air spray, airless spray, immersion, etc. can be appropriately employed.
- the steel sheet reached temperature (PMT) which is an index of the heating temperature of the object to be coated, is preferably 20 to 250 ° C, more preferably 50 to 220 ° C. When the heating temperature is 50 ° C.
- the metal surface treatment agent for galvanized steel material of the present invention has sufficiently excellent performance by evaporating water to dryness even under low temperature conditions near room temperature (20 ° C.). A film can be formed.
- the drying time in the case of heat drying after coating is preferably 1 second to 5 minutes.
- the coated steel material of the present invention is obtained by coating a steel material with the metal surface treatment agent for galvanized steel material of the present invention. Moreover, it obtains by the coating method of the galvanized steel material characterized by apply
- the coating amount is preferably 0.1 to 3 g / m 2 , more preferably 0.5 to 1.5 g / m 2 .
- the coating amount is 0.1 g / m 2 or more, the corrosion resistance is improved.
- the fall of base-material adhesiveness can be suppressed as the said film quantity is 3 g / m ⁇ 2 > or less.
- the coated steel material of the present invention can also be used by forming a coating film by applying a top coating on the coating film.
- the top coating include paints made of acrylic resin, acrylic-modified alkyd resin, epoxy resin, urethane resin, melamine resin, phthalic acid resin, amino resin, polyester resin, vinyl chloride resin, and the like.
- the film thickness of the coating film of the top coating is appropriately determined depending on the application of the rust-proof metal product, the type of top coating used, and the like, and is not particularly limited. Usually, it is 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m. Formation of the coating film of the top coating material can be carried out by applying the top coating material on the film formed by the metal surface treatment agent for the galvanized steel material, heating, drying and curing. The drying temperature and time are appropriately adjusted according to the type of top coat to be applied, the film thickness of the coating film, and the like. Usually, the drying temperature is preferably 50 to 250 ° C. The drying time is 5 minutes to 1 hour is preferred. As a method for applying the top coat, it can be performed by a conventionally known method according to the form of the paint.
- steel materials used in the present invention include galvanized steel materials, zinc-nickel plated steel materials, zinc-iron plated steel materials, zinc-chromium plated steel materials, zinc-aluminum plated steel materials, zinc-titanium plated steel materials, and zinc-magnesium plated steel materials.
- Zinc-plated steel materials such as zinc-manganese plated steel materials, zinc-aluminum-magnesium plated steel materials, zinc-aluminum-magnesium-silicon plated steel materials, as well as small amounts of different metal elements or impurities as cobalt, molybdenum, Includes those containing tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, etc., and dispersed inorganic substances such as silica, alumina, titania, etc. It is.
- the present invention can also be applied to multilayer plating in combination with the above plating and other types of plating such as iron plating, iron-phosphorus plating, nickel plating, cobalt plating and the like. Furthermore, it can be applied to aluminum or aluminum-based alloy plating.
- the plating method is not particularly limited, and any known method such as an electroplating method, a hot dipping method, a vapor deposition plating method, a dispersion plating method, and a vacuum plating method may be used.
- an aqueous dispersion of resin particles (a-2) having a solid content of 24% and having a silanol group and / or a methoxysilyl group was obtained.
- the average particle size of the resin particles (a-2) measured by a dynamic light scattering method particle size measuring apparatus FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
- an aqueous dispersion of resin particles (a-3) having a solid content of 24% and having silanol groups and / or methoxysilyl groups was obtained.
- the average particle size of the resin particles (a-3) measured by a particle size measuring apparatus by dynamic light scattering method, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
- an aqueous dispersion of resin particles (a-4) having a solid content of 24% and having silanol groups and / or methoxysilyl groups was obtained.
- the average particle diameter of the resin particles (a-4) measured by a dynamic light scattering method particle size measuring apparatus FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
- an aqueous dispersion of resin particles (a-5) having a solid content of 24% and having silanol groups and / or methoxysilyl groups was obtained.
- the average particle size of the resin particles (a-5) measured by a particle size measuring apparatus using a dynamic light scattering method, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
- aqueous dispersion of resin particles (a-7) having a solid content of 24% and having silanol groups and / or methoxysilyl groups.
- the average particle diameter of the resin particles (a-7) measured by a dynamic light scattering method FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 70 nm.
- sorbitol polyglycidyl ether product name: Denacol EX-614B, manufactured by Nagase ChemteX
- 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 1.15% was added and reacted at 85 ° C. for 2 hours to obtain an aqueous dispersion of resin particles (a-8) having a silanol group and / or methoxysilyl group having a solid content of 24%.
- the average particle diameter of the resin particles (a-8) measured by a dynamic light scattering method particle size measuring apparatus FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. was 70 nm.
- an aqueous dispersion of resin particles (b) having a solid content of 24% and having silanol groups and / or methoxysilyl groups was obtained.
- the average particle size of the resin particles (b) measured by a particle size measuring apparatus using a dynamic light scattering method, FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) was 100 nm.
- the resin particles obtained in Production Examples 1 to 10 are shown in Table 1 below.
- EG Electro-galvanized steel sheet “NS ZINCOAT (registered trademark)” manufactured by Nippon Steel & Sumikin Co., Ltd.
- GI hot-dip galvanized steel sheet
- GI zinc-aluminum-magnesium-silicon alloy plated steel sheet “Superdimer (registered trademark)” (hereinafter referred to as SD) manufactured by Nippon Steel & Sum
- Zinc-aluminum alloy plated steel sheet “Galbarium Steel Sheet (registered trademark)” (hereinafter referred to as GL), Zinc-Nickel Alloy Plated Steel Sheet “NS Zinclite (registered trademark)” manufactured by Nippon Steel & Sumitomo Metal Corporation (hereinafter referred to as ZL) Zinc-aluminum-magnesium alloy plated steel sheet “ZAM (registered trademark)” manufactured by Nisshin Steel Co., Ltd. was used as the original plate. The thickness of the original plate was 0.6 mm. The EG used had a plating adhesion amount of 20 g / m 2 on one side.
- GI, SD, GL, and ZAM used the thing with the plating adhesion amount of 60 g / m ⁇ 2 > on one side.
- the plating adhesion amount of ZL was 20 g / m 2 on one side, and the nickel amount in the plating layer was 12% by mass.
- Example 1> (Preparation of metal surface treatment agent for galvanized steel)
- An acid compound (G) was blended according to the formulation described in Table 2 to prepare a metal surface treating agent for galvanized steel.
- Each galvanized steel sheet was degreased by spraying at 60 ° C.
- Examples 2 to 32 and Comparative Examples 1 to 23 Preparation of metal surface treatment agent for galvanized steel materials in the same manner as in Example 1, using the composition of the metal surface treatment agent for galvanized steel materials listed in Table 2 and Table 3, the compounding conditions, and the preparation conditions of the test plate And a test plate was prepared.
- ⁇ Tape peel resistance> Filament tape (manufactured by Hitachi Maxell) was applied to the test plate and left for 2 weeks at 40 ° C. and humidity of 80%, and then the tape was forcibly peeled off. The film state was evaluated according to the following evaluation criteria. A: Almost no peeling B: Little peeling but tape marks remain C: Less than 50% peel area D: More than 50% peel area
- a melamine alkyd paint (trade name: Organo White, manufactured by Nippon Paint Co., Ltd.) was applied to the surface of the test plate with a bar coater to a dry film thickness of 20 ⁇ m, and baked at 130 ° C. for 15 minutes to prepare a coated plate. Next, the coated plate is immersed in boiling water for 30 minutes, taken out and left for 24 hours, and then the coated plate is extruded 7 mm with an elixir tester, and cello tape (registered trademark) (manufactured by Nichiban Co., Ltd.) is attached to the extruded portion.
- the film state after forced peeling was evaluated according to the following evaluation criteria.
- C peeling area less than 10% and less than 25%
- D peeling area 25% or more
- the test plate was extruded 7 mm with an elixir tester, the edges and back of the test plate were tape-sealed, and a salt spray test (SST) (JIS-Z-2371) was performed.
- SST salt spray test
- the occurrence of white rust after 72 hours was observed and evaluated according to the following criteria.
- D White rust occurrence area 30% or more
- ⁇ Abrasion resistance> A load of 10 g / cm 2 was applied to the test plate via corrugated paper, and an elliptical motion of 360 times / min was applied to generate abrasion (abrasion scratches) on the sliding portion. The state of the test plate surface after the test for 10 minutes was observed and evaluated according to the following criteria.
- D Black area is 30% or more of sliding part Conversion
- the metal surface treatment agent for galvanized steel materials of the present invention is resistant to press oil, adhesion to the substrate, Excellent effects were confirmed in all of tape peel resistance, paint adhesion, processed part corrosion resistance, alkali resistance, and abrasion resistance.
- the coating method using the metal surface treatment agent and the coated steel material press oil resistance, substrate adhesion, tape peel resistance, paint adhesion, processing It was confirmed that excellent performance was exhibited in all of the corrosion resistance, alkali resistance, and abrasion resistance.
- the metal surface treatment agent for galvanized steel material of the present invention, the coating method using the metal surface treatment agent and the coated steel material can be suitably used for automobiles, home appliances, building material products and the like.
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Abstract
Description
[1]有機樹脂粒子(A)、酸化ケイ素粒子(B)、ケイ酸リチウム(C)、有機チタン化合物(D)、及びエポキシ基含有化合物(E)を含む亜鉛めっき鋼材用の金属表面処理剤であって、前記有機樹脂粒子(A)は、シランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)とによって基体樹脂を変性させた樹脂粒子であり、シラノール基及び/又はアルコキシシリル基を有する樹脂粒子であり、前記酸化ケイ素粒子(B)及び前記ケイ酸リチウム(C)に含有されるケイ素元素の合計量のSiO2換算モル数が、前記ケイ酸リチウム(C)に含有されるリチウム元素のLi2O換算モル数に対して40~70倍であり、前記金属表面処理剤の固形分質量の合計に対して、前記有機樹脂粒子(A)の固形分質量が20~70質量%であり、前記酸化ケイ素粒子(B)が10~50質量%であり、前記ケイ酸リチウム(C)が1~10質量%であり、前記有機チタン化合物(D)がチタン元素換算として0.05~5質量%であり、前記エポキシ基含有化合物(E)が0.2~10質量%であり、前記有機チタン化合物(D)に含有されるチタン元素の質量に対する前記ケイ酸リチウム(C)の質量の比が0.2~200である、亜鉛めっき鋼材用の金属表面処理剤。
[2]前記有機チタン化合物(D)に含有されるチタン元素の質量とケイ酸リチウム(C)の質量との和に対する前記シランカップリング剤(A-1)の合計量の質量の比が0.01~13である、上記[1]に記載の亜鉛めっき鋼材用の金属表面処理剤。
[3]ニオブ化合物(F)を前記金属表面処理剤の固形分質量の合計に対して0.1~10質量%含む、上記[1]又は[2]に記載の亜鉛めっき鋼材用の金属表面処理剤。
[4]リン酸化合物(G)をリン元素換算として、前記金属表面処理剤の固形分質量の合計に対して0.1~10質量%含む、上記[1]~[3]のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
[5]有機樹脂粒子(A)は、シランカップリング剤(A-1)を前記基体樹脂の固形分質量に対して1~20質量%となる割合で配合し反応させて得られるものである、上記[1]~[4]のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
[6]有機樹脂粒子(A)は、多官能エポキシ基含有化合物(A-2)を前記基体樹脂の固形分質量に対して1~20質量%となる割合で配合し反応させて得られるものである、上記[1]~[5]のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
[7]前記酸化ケイ素粒子(B)及び前記ケイ酸リチウム(C)に含有されるケイ素元素の合計量のSiO2換算モル数が、前記ケイ酸リチウム(C)に含有されるリチウム元素のLi2O換算モル数に対して50~65倍である、上記[1]~[6]のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
[8]上記[1]~[7]のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤を、亜鉛めっき鋼材表面に塗布して皮膜を形成することを特徴とする、亜鉛めっき鋼材の被覆方法。
[9]上記[8]に記載の亜鉛めっき鋼材の被覆方法によって得られる被覆鋼材。
本発明の亜鉛めっき鋼材用の金属表面処理剤は、有機樹脂粒子(A)、酸化ケイ素粒子(B)、ケイ酸リチウム(C)、有機チタン化合物(D)、及びエポキシ基含有化合物(E)を含む亜鉛めっき鋼材用の金属表面処理剤であって、前記有機樹脂粒子(A)は、シランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)とによって変性させた樹脂粒子であり、シラノール基及び/又はアルコキシシリル基を有する樹脂粒子であり、前記酸化ケイ素粒子(B)及び前記ケイ酸リチウム(C)に含有されるケイ素元素の合計量のSiO2換算モル数が、前記ケイ酸リチウム(C)に含有されるリチウム元素のLi2O換算モル数に対して40~70倍であり、前記金属表面処理剤の固形分質量の合計に対して、前記有機樹脂粒子(A)の固形分質量が20~70質量%であり、前記酸化ケイ素粒子(B)が10~50質量%であり、前記ケイ酸リチウム(C)が1~10質量%であり、前記有機チタン化合物(D)がチタン元素換算として0.05~5質量%であり、前記エポキシ基含有化合物(E)が0.2~10質量%であり、前記有機チタン化合物(D)に含有されるチタン元素の質量に対する前記ケイ酸リチウム(C)の質量の比が0.2~200である、亜鉛めっき鋼材用の金属表面処理剤である。
これにより、本発明の亜鉛めっき鋼材用の金属表面処理剤は、耐プレス油性、基材密着性、耐テープ剥離性、塗装密着性、加工部耐食性、耐アルカリ性、及び耐アブレージョン性のいずれにおいても優れた性能を有する。
本発明で用いる有機樹脂粒子(A)は、シランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)とによって基体樹脂を変性させた樹脂粒子であり、シラノール基及び/又はアルコキシシリル基を有する樹脂粒子である。
前記基体樹脂としては、特に限定されないが、例えば、エチレンとアクリル酸、メタクリル酸又は無水マレイン酸等の不飽和カルボン酸との共重合樹脂(例えば、エチレン-メタクリル酸共重合体)を、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物やアンモニア水や有機アミン類で中和し水中に分散させた水分散アクリル樹脂、イソシアネート基含有化合物とポリオール、低分子量ポリオール、及び活性水素基と親水性基とを含有する化合物とを反応させてポリウレタンプレポリマーを製造し、次いで上記親水性基を中和剤により中和した水分散ポリウレタン樹脂等が挙げられる。
有機樹脂粒子(A)としては、これら分散樹脂液に、後述するシランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)を作用させて得られるシラノール基及び/又はアルコキシシリル基を有するアクリル樹脂粒子、又はシラノール基及び/又はアルコキシシリル基を有するポリウレタン樹脂粒子等を挙げることができる。なかでも、塩基で中和されたエチレン-メタクリル酸共重合樹脂の水分散樹脂液に、後述するシランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)等を作用させて得られるアクリル樹脂粒子が、微粒子化が可能で、かつ、高性能皮膜を形成しうるという点で好ましい。
また、必要に応じて、その他の単量体を含有するものであってもよいが、その使用量は10質量%以下であることが好ましい。上記エチレン-メタクリル酸共重合樹脂を用いる場合は、例えば、高圧法低密度ポリエチレンの製造装置による重合等の公知の方法によって製造することができる。
配合量としては、基体樹脂を、前記有機樹脂粒子(A)の固形分質量に対して、80質量%以上で反応させることが好ましい。より好ましくは90質量%以上の範囲である。
前記有機樹脂粒子(A)で用いるシランカップリング剤(A-1)は、例えば、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン等のエポキシ基含有シラン化合物、γ-(2-アミノエチル)アミノプロピルトリメトキシシラン、γ-(2-アミノエチル)アミノプロピルトリエトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジメトキシシラン、γ-(2-アミノエチル)アミノプロピルメチルジエトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルエトキシシラン、N-〔2-(ビニルベンジルアミノ)エチル〕-3-アミノプロピルトリメトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン等のアミノ基含有シラン化合物、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、γ-メルカプトプロピルトリエトキシシラン、γ-メルカプトプロピルメチルジエトキシシラン等のメルカプト基含有シラン化合物、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ-メタクリロキシプロピルメチルジメトキシシラン、γ-メタクリロキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルメチルジエトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン等を挙げることができ、エポキシ基含有シラン化合物であることが好ましい。これらは、単独で用いてもよく、2種以上を併用してもよい。
配合量としては、シランカップリング剤(A-1)を、前記基体樹脂の固形分100質量%に対して、1~20質量%となる割合で配合し反応させることが好ましい。より好ましくは1~10質量%の範囲である。この配合量が1質量%以上の場合、鋼材表面に形成される皮膜の耐アルカリ性、耐溶剤性、塗装密着性等が良好であり、20質量%以下であると皮膜の親水性が適切となり耐食性が良好となる、及び皮膜の形成に用いられる前記金属表面処理剤の液安定性が良好となる場合がある。
前記有機樹脂粒子(A)で用いる多官能エポキシ基含有化合物(A-2)としては、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、プロピレンレングリコールジグリシジルエーテル、トリグリシジルトリス(2-ヒドロキシエチル)イソシアヌレート、ビスフェノールAグリシジルエーテル、水素化ビスフェノールAジグリシジルエーテル等を挙げることができる。これらは、単独で用いてもよく、2種以上を併用してもよい。多官能エポキシ基含有化合物(A-2)を用いると、有機樹脂との親和性が高まるため、上記皮膜に上塗り塗料を塗布した場合に、塗膜密着性の向上に有利である場合がある。
ここで、多官能エポキシ基含有化合物(A-2)は、エポキシ基含有シラン化合物は含まない。
配合量としては、多官能エポキシ基含有化合物(A-2)を、前記基体樹脂の固形分100質量%に対して、1~20質量%反応させることが好ましい。より好ましくは1~10質量%の範囲である。この配合量が1質量%以上の場合、鋼材表面に形成される皮膜の耐アルカリ性、耐溶剤性、塗装密着性等が良好であり、20質量%以下であると皮膜の親水性が適切となり耐食性が良好となる、及び皮膜の形成に用いられる前記金属表面処理剤の液安定性が良好となる場合がある。
なお、前記有機樹脂粒子(A)の含有量は、各原料を配合する時の配合量から算出することもできる。
本発明で用いる酸化ケイ素粒子(B)は、一次粒子の数平均粒子径が5~50nmのものが好ましく、5~20nmのものがより好ましく、コロイダルシリカやヒュームドシリカ等から適宜選択して用いることができる。酸化ケイ素粒子(B)の一次粒子の数平均粒子径は電子顕微鏡観察により求めることができる。酸化ケイ素粒子(B)の具体例としては、スノーテックスN、スノーテックスC(日産化学工業社製)やアデライトAT-20N、AT-20A(ADEKA社製)やカタロイドS-20L、カタロイドSA(日揮触媒化成社製)などが挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。
酸化ケイ素粒子(B)は、前記金属表面処理剤の固形分質量の合計に対して、10~50質量%で含有する。10質量%未満であれば、十分な塗膜性能、特に基材密着性や耐テープ剥離性を得ることができない。また、他の成分の含有量とのバランスを調整して、本発明の効果を良好に発揮させる観点から50質量%以下である。同様の観点から、当該酸化ケイ素粒子(B)の含有量は、前記金属表面処理剤の固形分質量の合計に対して、好ましくは15~45質量%、より好ましくは20~40質量%である。
なお、酸化ケイ素粒子(B)の含有量は、各原料を配合する時の配合量から算出することもできる
本発明で用いるケイ酸リチウム(C)は、リチウム酸化物と二酸化ケイ素とからなる塩であって、一般式Li2O・nSiO2で表される。リチウム酸化物と二酸化ケイ素とのモル比を表すnの値によって、オルトケイ酸リチウム(Li4SiO4(Li2O・0.5SiO2:n=0.5))、メタケイ酸リチウム(Li2SiO3(Li2O・SiO2:n=1))、オルト二ケイ酸六リチウム(Li6Si2O7(Li2O・2/3SiO2:n=2/3))、Li4Si7O16(Li2O・3.5SiO2:n=3.5)、Li4Si9O20(Li2O・4.5SiO2:n=4.5)、Li4Si15O32(Li2O・7.5SiO2:n=7.5)などが挙げられる。また、ケイ酸リチウム(C)は、例えば、その水和物であってもよい。
さらに、珪酸リチウム(C)は、例えば、ケイ酸リチウム水溶液として用いることもでき、このような場合において、水溶液の固形分濃度は、例えば、1~50質量%、好ましくは、2~40質量%である。なお、ケイ酸リチウム(C)は、リチウム酸化物と二酸化ケイ素とのモル比nの値によって、その水溶性が異なり、例えば、nが2~5であるケイ酸リチウムは水に可溶であり、nが6~10であるケイ酸リチウムは、水に不溶である。
また、このようなケイ酸リチウム(C)としては、例えば、リチウムシリケート35(ケイ酸リチウム水溶液、SiO2/Li2O(モル比)=3.5)、リチウムシリケート45(ケイ酸リチウム水溶液、SiO2/Li2O(モル比)=4.5)、リチウムシリケート75(ケイ酸リチウム水溶液、SiO2/Li2O(モル比)=7.5)(いずれも、日産化学工業社製)などが挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。
ケイ酸リチウム(C)が、前記酸化ケイ素粒子(B)とイオン架橋によって、擬似架橋を形成することにより、耐テープ密着性に優れた皮膜が形成されていると考えられる。
ケイ酸リチウム(C)は、前記金属表面処理剤の固形分質量の合計に対して、1~10質量%で含有する。1質量%未満であれば、耐テープ剥離性が不良となる。また、他の成分の含有量とのバランスを調整して、本発明の効果を良好に発揮させる観点から10質量%以下である。同様の観点から、当該ケイ酸リチウム(C)の含有量は、前記金属表面処理剤の固形分質量の合計に対して、好ましくは1~7質量%、より好ましくは1~5質量%である。
なお、ケイ酸リチウム(C)の含有量は、各原料を配合する時の配合量から算出することもできる。
また、本発明の亜鉛めっき鋼材用の金属表面処理剤は、前記有機チタン化合物(D)に含有されるチタン元素の質量とケイ酸リチウム(C)の質量との和に対する前記シランカップリング剤(A-1)の質量の比が0.01~13であることが好ましい。上記質量比が0.01~13の範囲内であることにより、耐テープ剥離性、耐アルカリ性が改善され、かつ、耐プレス油性、加工部耐食性も改善される。同様の観点から、前記有機チタン化合物(D)に含有されるチタン元素の質量とケイ酸リチウム(C)の質量との和に対する前記シランカップリング剤(A-1)の質量の比は、より好ましくは0.1~13、さらに好ましくは0.35~0.65である。
本発明で用いる有機チタン化合物(D)として用いられる具体例としては、ジプロポキシビス(トリエタノールアミナト)チタン、ジプロポキシビス(ジエタノールアミナト)チタン、ジブトキシビス(トリエタノールアミナト)チタン、ジブトキシビス(ジエタノールアミナト)チタン、ジプロポキシビス(アセチルアセトナト)チタン、ジブトキシビス(アセチルアセトナト)チタン、ジヒドロキシビス(ラクタト)チタンモノアンモニウム塩、ジヒドロキシビス(ラクタト)チタンジアンモニウム塩、プロパンジオキシチタンビス(エチルアセトアセテート)、オキソチタンビス(モノアンモニウムオキサレート)、イソプロピルトリ(N-アミドエチル・アミノエチル)チタネート等を挙げることができる。これらは単独でもよく、2種以上を併用してもよい。
有機チタン化合物(D)は、チタン元素換算として、前記金属表面処理剤の固形分質量の合計に対して、0.05~5質量%で含有する。0.05質量%未満であれば、十分な塗膜性能を得ることができない。また、他の成分の含有量とのバランスを調整して、本発明の効果を良好に発揮させる観点から5質量%以内である。同様の観点から、当該有機チタン化合物(D)の含有量は、チタン元素換算として、前記金属表面処理剤の固形分質量の合計に対して、より好ましくは0.1~2質量%、更に好ましくは0.3~1質量%である。
なお、有機チタン化合物(D)の含有量は、各原料を配合する時の配合量から算出することもできる。
本発明で用いるエポキシ基含有化合物(E)は、特に限定されないが、多官能エポキシ樹脂であり、原料使用量を低減できる観点からはより多官能であるほど好ましく、好ましくは3官能以上、更に好ましくは4官能以上である。また、有機樹脂粒子(A)との反応による粘度変化を調整する観点、得られた金属処理剤のハンドリング性の観点からは、例えば、3~5官能であることが好ましい。具体例としては、例えば、前述の多官能エポキシ基含有化合物(A-2)をエポキシ基含有化合物として用いることができる。
エポキシ基含有化合物(E)は、皮膜形成時に前記有機樹脂粒子(A)と架橋反応して高架橋皮膜を形成することにより、特に耐プレス油性を向上させる。
エポキシ基含有化合物(E)は、前記金属表面処理剤の固形分質量の合計に対して、0.2~10質量%で含有する。0.2質量%未満であれば、十分な塗膜性能、特に十分な耐プレス油性を得ることができない。また、他の成分の含有量とのバランスを調整して、本発明の効果を良好に発揮させる観点から10質量%以下である。同様の観点から、当該エポキシ基含有化合物(E)の含有量は、前記金属表面処理剤の固形分質量の合計に対して、好ましくは1~8質量%、より好ましくは2~7質量%である。
なお、エポキシ基含有化合物(E)の含有量は、各原料を配合する時の配合量から算出することもできる。
本発明の亜鉛めっき鋼材用の金属表面処理剤は、前記(A)~(E)に加えて、更に、ニオブ化合物(F)を含有することが好ましい。
ニオブ化合物(F)は、前記金属表面処理剤の固形分質量の合計に対して、好ましくは0.1~10質量%で含有する。0.1~10質量%の範囲内であると、加工部耐食性に優れる。同様の観点から、当該ニオブ化合物(F)の含有量は、前記金属表面処理剤の固形分質量の合計に対して、より好ましくは0.2~5質量%、更に好ましくは0.5~2質量%である。
本発明の亜鉛めっき鋼材用の金属表面処理剤は、前記(A)~(E)又は前記(A)~(F)に加えて、更に、リン酸化合物(G)を含有することが好ましい。リン酸化合物(G)としては、オルトリン酸、メタリン酸、ピロリン酸、三リン酸、四リン酸等のリン酸類、リン酸三アンモニウム、リン酸水素二アンモニウム、リン酸三ナトリウム、リン酸水素二ナトリウム等のリン酸塩類等が挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。
リン酸化合物(G)を用いると、リン酸イオンが、金属素地表面にリン酸塩層を形成して不動態化させ、防錆性を向上させることができる。
リン酸化合物(G)は、リン元素換算として、前記金属表面処理剤の固形分質量の合計に対して、好ましくは0.1~10質量%で含有する。0.1~10質量%の範囲内であることで、加工部耐食性に優れる。同様の観点から、当該リン酸化合物(G)の含有量は、リン元素換算として、前記金属表面処理剤の固形分質量の合計に対して、より好ましくは0.2~5質量%、更に好ましくは0.5~2質量%である。
なお、リン酸化合物(G)の含有量は、各原料を配合する時の配合量から算出することもできる。
本発明の亜鉛めっき鋼材用の金属表面処理剤は、前記(A)~(E)、前記(A)~(F)又は前記(A)~(G)に加えて、更に、水を含有してもよい。
本発明の亜鉛めっき鋼材用の金属表面処理剤には上記(A)~(G)、及び水以外に、その他の成分を含有するものであってもよい。例えば、ワックス、潤滑剤、顔料を配合してもよい。前記ワックスとしては、例えば、パラフィン、マイクロクリスタリン、ポリオレフィン等の炭化水素系のワックス、これらの誘導体等従来公知のワックスを用いることができる。上記誘導体としては、カルボキシル化ポリオレフィン、塩素化ポリオレフィン等を挙げることができる。前記潤滑剤としては、例えば、フッ素系、炭化水素系、脂肪酸アミド系、エステル系、アルコール系、金属石鹸系及び無機系等の従来公知の潤滑剤を用いることができる。上記顔料としては、例えば、酸化チタン(TiO2)、酸化亜鉛(ZnO)、炭酸カルシウム(CaCO3)、硫酸バリウム(BaSO4)、アルミナ(Al2O3)、カオリンクレー、カーボンブラック、酸化鉄(Fe2O3、Fe3O4)等の無機顔料や、有機顔料等の各種着色顔料等を用いることができる。また、防錆剤として、例えば特許第492295号に記載のチオカルボニル化合物やグアニジン化合物を用いることができる。
本発明の亜鉛めっき鋼材用の金属表面処理剤は、前記有機樹脂粒子(A)の樹脂粒子が分散した水分散液に、前記酸化ケイ素粒子(B)、前記ケイ酸リチウム(C)、前記有機チタン化合物(D)、及び前記エポキシ基含有化合物(E)を配合して前記金属表面処理剤を調製し、更に、必要に応じて前記ニオブ化合物(F)前記リン酸化合物(G)、水、その他の成分から選ばれる1種以上を配合することにより製造できる。
本発明の亜鉛めっき鋼材の被覆方法は、本発明の亜鉛めっき鋼材用の金属表面処理剤を、亜鉛めっき鋼材表面に塗布して皮膜を形成することを特徴とする。これにより、本発明の亜鉛めっき鋼材の被覆方法は、耐プレス油性、基材密着性、耐テープ剥離性、塗装密着性、加工部耐食性、耐アルカリ性、及び耐アブレージョン性のいずれにおいても優れた性能を有する。
さらに、前記皮膜中では酸化ケイ素粒子(B)とケイ酸リチウム(C)とがイオン架橋によって、擬似架橋が形成されていると考えられる。
さらに、上述のとおり、酸化ケイ素粒子(B)とケイ酸リチウム(C)とがイオン架橋によって、擬似架橋を形成することにより、耐テープ密着性に優れた皮膜が形成されていると考えられる。
そして、有機樹脂粒子(A)の粒子径が特定の範囲内のものであることから、上記皮膜中には、上記の粒子間結合が高密度で形成されるため、化学的に安定で、微視的に均質性の高い皮膜となる。このため、本発明の亜鉛めっき鋼材用の金属表面処理剤は、特に顕著な効果が得られるものと推測される。
亜鉛めっき鋼材を被覆するための金属表面処理剤を製造するにあたって、上記各成分の添加順序としては特に限定されないが、例えば、前述の亜鉛めっき鋼材用の金属表面処理剤の製造方法を用いることができる。
また、本発明の亜鉛めっき鋼材用の金属表面処理剤は、室温(20℃)付近での低温条件下であっても、水分が蒸発して乾固することで、十分に優れた性能を有する皮膜を形成することができる。
コーティング後に熱乾燥させる場合の乾燥時間は1秒~5分が好ましい。
本発明の被覆鋼材は、本発明の亜鉛めっき鋼材用の金属表面処理剤によって、鋼材を被覆することにより得られる。また、本発明の亜鉛めっき鋼材用の金属表面処理剤を、亜鉛めっき鋼材表面に塗布して皮膜を形成することを特徴とする亜鉛めっき鋼材の被覆方法により得られる。これにより、本発明の被覆鋼材は、耐プレス油性、基材密着性、耐テープ剥離性、塗装密着性、加工部耐食性、耐アルカリ性、及び耐アブレージョン性のいずれにおいても優れた性能を有する。
(樹脂粒子(a-1)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル(製品名:SR-HBA、阪本薬品工業社製)0.69%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン(製品名:KBM-303、信越化学工業社製)1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-1)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-1)の平均粒子径は70nmであった。
(樹脂粒子(a-2)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.69%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン0.29%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-2)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-2)の平均粒子径は70nmであった。
(樹脂粒子(a-3)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.69%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン5.75%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-3)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-3)の平均粒子径は70nmであった。
(樹脂粒子(a-4)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.23%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-4)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-4)の平均粒子径は70nmであった。
(樹脂粒子(a-5)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル4.6%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-5)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-5)の平均粒子径は70nmであった。
(樹脂粒子(a-6)の製造)
反応容器に水系ウレタン樹脂(製品名:アデカボンタイターHUX-320、アデカ社製)(固形分30%)に、水素化ビスフェノールAジグリシジルエーテル0.90%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1.50%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-6)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-6)の平均粒子径は70nmであった。
(樹脂粒子(a-7)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.69%及びγ-グリシドキシプロピルトリメトキシシラン(製品名:KBM-403、信越化学工業社製)1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-7)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-7)の平均粒子径は70nmであった。
(樹脂粒子(a-8)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して5.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらにソルビトールポリグリシジルエーテル(製品名:デナコールEX-614B、ナガセケムテックス社製)0.69%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(a-8)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(a-8)の平均粒子径は70nmであった。
(樹脂粒子(b)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して4.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.69%及び2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン1.15%を加えて、85℃で2時間反応させることによって、固形分24%の、シラノール基及び/又はメトキシシリル基を有する樹脂粒子(b)の水分散液を得た。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(b)の平均粒子径は100nmであった。
(樹脂粒子(c)の製造)
反応容器にエチレン-メタクリル酸共重合樹脂(エチレンの含有量が80%、メタクリル酸の含有量が20%)、樹脂に対して4.6%の水酸化ナトリウム及び脱イオン水を加え、95℃で6時間攪拌することにより固形分23%の水分散樹脂液を得た。この水分散樹脂液に、さらに水素化ビスフェノールAジグリシジルエーテル0.69%を加えて、85℃で2時間反応させることによって、固形分24%の、樹脂粒子(c)の水分散液を得た。製造例10では、シランカップリング剤を加えていない。動的光散乱法による粒子径測定装置、FPAR-1000(大塚電子社製)によって測定した樹脂粒子(c)の平均粒子径は110nmであった。
酸化ケイ素粒子;製品名AT-20A、ADEKA社製、 平均粒子径12nm
ケイ酸リチウム;製品名珪酸リチウム35、日本化学工業社製
有機チタン化合物;製品名T-50、ジプロポキシビス(アセチルアセトナト)チタン日本曹達社製
エポキシ基含有化合物;製品名SR-HBA、阪本薬品工業社製
ニオブ化合物;製品名バイラールNb-G6000、多木化学社製、平均粒子径15nm
リン酸化合物;原料名 リン酸三ナトリウム(無水物)
その他原料;カルボジイミド(製品名カルボジライト SV-02、日清紡ケミカル社製)、メラミン樹脂(製品名サイメル385、日本サイテックインダストリーズ社製)、WAX(製品名ハイテックE-6000S、東邦化学工業社製、化合物名;ポリエチレンディスパージョン)
新日鐵住金株式会社製の電気亜鉛めっき鋼板「NSジンコート(登録商標)」(以降、EGと称する。)、新日鐵住金株式会社製の溶融亜鉛めっき鋼板「NSシルバージンク(登録商標)」(以降、GIと称する。)、新日鐵住金株式会社製の亜鉛-アルミニウム-マグネシウム-シリコン合金めっき鋼板「スーパーダイマ(登録商標)」(以降、SDと称する。)、日鉄住金鋼板社製の亜鉛-アルミニウム合金めっき鋼板「ガルバリウム鋼板(登録商標)」(以降、GLと称する。)、新日鐵住金株式会社製の亜鉛-ニッケル合金めっき鋼板「NSジンクライト(登録商標)」(以降、ZLと称する。)、日新製鋼株式会社製の亜鉛-アルミニウム―マグネシウム合金めっき鋼板「ZAM(登録商標)」を原板として使用した。原板の板厚は、0.6mmのものを使用した。EGは、めっき付着量が片面20g/m2のものを用いた。また、GI、SD、GL、ZAMは、めっき付着量が片面60g/m2のものを用いた。ZLのめっき付着量は片面20g/m2であり、めっき層中のニッケル量は12質量%であった。
(亜鉛めっき鋼材用の金属表面処理剤の調製)
上記樹脂粒子(a-1)の水分散体に、酸化ケイ素粒子(B)、ケイ酸リチウム(C)、有機チタン化合物(D)、エポキシ基含有化合物(E)、ニオブ化合物(F)及びリン酸化合物(G)を表2に記載の処方に従い配合して、亜鉛めっき鋼材用の金属表面処理剤を調製した。
(試験板の作製)
各亜鉛めっき鋼板を、アルカリ脱脂剤(サーフクリーナー155、日本ペイント社製)2%水溶液を用いて、60℃で2分間スプレー処理して脱脂し、水洗して温風乾燥させた。冷却後、この脱脂処理板に、上記金属表面処理剤をバーコーターで、乾燥皮膜量が1g/m2になるように塗布し、雰囲気温度が500℃の熱風乾燥炉を用いて鋼板到達温度(PMT)が150℃に、雰囲気温度が200℃の熱風乾燥炉を用いて鋼板到達温度(PMT)が50℃になるように焼き付けて試験板を作製した。
表2及び表3に記載の亜鉛めっき鋼材用の金属表面処理剤の配合、配合条件、並びに試験板の作製条件を用いて、実施例1と同様に亜鉛めっき鋼材用の金属表面処理剤の調製及び試験板を作製した。
以上のように作製した実施例1~32及び比較例1~23の試験板について、以下の評価を行った。評価結果を表2及び表3に示す。
試験板をプレス油(G6318SK、日本工作油社製)に室温下で24時間浸漬した後、試験板をヘキサンにて洗浄し、ラビングテスターに設置後、エタノールを含浸させた脱脂綿を用いて、0.5kgf/cm2の荷重で10往復擦った後の皮膜状態を、下記の評価基準で評価した。
A:擦り面に擦り跡が全くつかない
B:擦り面に擦り跡が僅かにつく
C:擦り面に白い擦り跡がつく
D:擦り面の一部が剥離している
塗装後1時間以内の試験板をエリクセンテスターにて8mm押し出し加工した後、押し出し部にセロテープ(登録商標)(ニチバン社製)を貼り、強制剥離した。剥離した後の試験板をメチルバイオレット染色液に30分浸漬した後の皮膜状態を、下記の評価基準で評価した。
A:剥離がほとんどなし
B:剥離面積10%未満
C:剥離面積10%以上25%未満
D:剥離面積25%以上
試験板にフィラメンテープ(日立マクセル社製)を貼り、40℃、湿度80%の条件で2週間放置した後、テープを強制剥離した。皮膜状態を、下記の評価基準で評価した。
A:剥離がほとんどなし
B:剥離がほとんどないが、テープ跡が残存
C:剥離面積50%未満
D:剥離面積50%以上
試験板表面にメラミンアルキッド塗料(商品名:オルガネオ ホワイト、日本ペイント社製)をバーコーターで乾燥膜厚20μmとなるように塗布し、130℃で15分間焼き付けて塗膜板を作製した。次に、塗膜板を沸騰水中に30分間浸漬し、取り出して24時間放置後、エリクセンテスターにて塗膜板を7mm押し出し、その押し出し部にセロテープ(登録商標)(ニチバン社製)を貼り、強制剥離した後の皮膜状態を、下記の評価基準で評価した。
A:剥離がほとんどなし
B:剥離面積10%未満
C:剥離面積10%以上25%未満
D:剥離面積25%以上
試験板をエリクセンテスターにて7mm押し出し加工し、試験板のエッジと裏面をテープシールし、塩水噴霧試験(SST)(JIS-Z-2371)を行った。72時間後の白錆発生状況を観察し下記基準で評価した。
A:白錆発生なし
B:白錆発生面積が10%未満
C:白錆発生面積が10%以上30%未満
D:白錆発生面積が30%以上
試験板を60℃のアルカリ脱脂剤(サーフクリーナー155、日本ペイント社製)2質量%水溶液(pH12.5)に攪拌しながら2分間浸漬した後、試験片のエッジと裏面をテープシールし、塩水噴霧試験(JIS-Z-2371)を行った。72時間後の白錆発生状況を観察し、下記基準で評価した。
A:白錆発生なし
B:白錆発生面積が10%未満
C:白錆発生面積が10%以上30%未満
D:白錆発生面積が30%以上
試験板に、段ボール紙を介して10g/cm2の荷重をかけ、360回/minの楕円運動を加えて摺動部にアブレージョン(摩耗傷)を発生させた。10分間試験を行った後の試験板表面の状態を観察し、下記基準で評価した。
A:黒化ほとんどなし
B:摺動部の10%未満の面積が黒化
C:摺動部の10%以上30%未満の面積が黒化
D:摺動部の30%以上の面積が黒化
本発明の亜鉛めっき鋼材用の金属表面処理剤、該金属表面処理剤を用いた被覆方法及び被覆鋼材を用いることで、耐プレス油性、基材密着性、耐テープ剥離性、塗装密着性、加工部耐食性、耐アルカリ性、及び耐アブレージョン性のいずれにおいても優れた性能が発現されることが確認された。
Claims (9)
- 有機樹脂粒子(A)、酸化ケイ素粒子(B)、ケイ酸リチウム(C)、有機チタン化合物(D)、及びエポキシ基含有化合物(E)を含む亜鉛めっき鋼材用の金属表面処理剤であって、
前記有機樹脂粒子(A)は、シランカップリング剤(A-1)と多官能エポキシ基含有化合物(A-2)とによって基体樹脂を変性させた樹脂粒子であり、シラノール基及び/又はアルコキシシリル基を有する樹脂粒子であり、前記酸化ケイ素粒子(B)及び前記ケイ酸リチウム(C)に含有されるケイ素元素の合計量のSiO2換算モル数が、前記ケイ酸リチウム(C)に含有されるリチウム元素のLi2O換算モル数に対して40~70倍であり、
前記金属表面処理剤の固形分質量の合計に対して、
前記有機樹脂粒子(A)の固形分質量が20~70質量%であり、
前記酸化ケイ素粒子(B)が10~50質量%であり、
前記ケイ酸リチウム(C)が1~10質量%であり、
前記有機チタン化合物(D)がチタン元素換算として0.05~5質量%であり、
前記エポキシ基含有化合物(E)が0.2~10質量%であり、
前記有機チタン化合物(D)に含有されるチタン元素の質量に対する前記ケイ酸リチウム(C)の質量の比が0.2~200である、
亜鉛めっき鋼材用の金属表面処理剤。 - 前記有機チタン化合物(D)に含有されるチタン元素の質量とケイ酸リチウム(C)の質量との和に対する前記シランカップリング剤(A-1)の質量の比が0.01~13である、請求項1に記載の亜鉛めっき鋼材用の金属表面処理剤。
- ニオブ化合物(F)を前記金属表面処理剤の固形分質量の合計に対して0.1~10質量%含む、請求項1又は2に記載の亜鉛めっき鋼材用の金属表面処理剤。
- リン酸化合物(G)をリン元素換算として、前記金属表面処理剤の固形分質量の合計に対して0.1~10質量%含む、請求項1~3のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
- 前記有機樹脂粒子(A)は、シランカップリング剤(A-1)を前記基体樹脂の固形分質量に対して1~20質量%となる割合で配合し反応させて得られるものである、請求項1~4のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
- 前記有機樹脂粒子(A)は、多官能エポキシ基含有化合物(A-2)を前記基体樹脂の固形分質量に対して1~20質量%となる割合で配合し反応させて得られるものである、請求項1~5のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
- 前記酸化ケイ素粒子(B)及び前記ケイ酸リチウム(C)に含有されるケイ素元素の合計量のSiO2換算モル数が、前記ケイ酸リチウム(C)に含有されるリチウム元素のLi2O換算モル数に対して50~65倍である、請求項1~6のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤。
- 請求項1~7のいずれかに記載の亜鉛めっき鋼材用の金属表面処理剤を、亜鉛めっき鋼材表面に塗布して皮膜を形成することを特徴とする、亜鉛めっき鋼材の被覆方法。
- 請求項8に記載の亜鉛めっき鋼材の被覆方法によって得られる被覆鋼材。
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