JP2004218070A - Pretreatment method for coating - Google Patents
Pretreatment method for coating Download PDFInfo
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- JP2004218070A JP2004218070A JP2003403688A JP2003403688A JP2004218070A JP 2004218070 A JP2004218070 A JP 2004218070A JP 2003403688 A JP2003403688 A JP 2003403688A JP 2003403688 A JP2003403688 A JP 2003403688A JP 2004218070 A JP2004218070 A JP 2004218070A
- Authority
- JP
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- Prior art keywords
- chemical conversion
- coating
- group
- agent
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000576 coating method Methods 0.000 title claims abstract description 88
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 238000002203 pretreatment Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 99
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 125000003277 amino group Chemical group 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 33
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 13
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 94
- 238000005260 corrosion Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- -1 aluminum ions Chemical class 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 229910001449 indium ion Inorganic materials 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052742 iron Inorganic materials 0.000 abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 16
- 239000011701 zinc Substances 0.000 abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- 150000002739 metals Chemical class 0.000 abstract description 5
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 34
- 239000000758 substrate Substances 0.000 description 31
- 239000002585 base Substances 0.000 description 21
- 238000004070 electrodeposition Methods 0.000 description 21
- 125000002091 cationic group Chemical group 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000003973 paint Substances 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 12
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 12
- 229910000165 zinc phosphate Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005238 degreasing Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000012756 surface treatment agent Substances 0.000 description 5
- 150000003755 zirconium compounds Chemical class 0.000 description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- 239000013527 degreasing agent Substances 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- RMBYJMVHGICGMN-UHFFFAOYSA-N n',n'-bis(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCN(CCN)CCC[Si](OC)(OC)OC RMBYJMVHGICGMN-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- OKWYEBJNFREPEV-UHFFFAOYSA-N 3-[dimethoxy(phenylmethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](OC)(OC)OCC1=CC=CC=C1 OKWYEBJNFREPEV-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000316887 Saissetia oleae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910007992 ZrF Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- QHEDSQMUHIMDOL-UHFFFAOYSA-J hafnium(4+);tetrafluoride Chemical compound F[Hf](F)(F)F QHEDSQMUHIMDOL-UHFFFAOYSA-J 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004761 hexafluorosilicates Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-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
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
Description
本発明は、塗装前処理方法に関する。 The present invention relates to a coating pretreatment method.
金属材料表面にカチオン電着塗装、粉体塗装等を施す場合、通常、耐食性、塗膜密着性等の性質を向上させる目的で、化成処理が施されている。塗膜の密着性や耐食性をより向上させることができる観点から化成処理において用いられてきたクロメート処理は、近年、クロムの有害性が指摘されるようになっており、クロムを含まない化成処理剤の開発が必要とされてきた。このような化成処理としては、リン酸亜鉛による処理が広く行われている（例えば、特許文献１参照）。 When a surface of a metal material is subjected to cationic electrodeposition coating, powder coating, or the like, a chemical conversion treatment is usually performed for the purpose of improving properties such as corrosion resistance and coating film adhesion. Chromate treatment, which has been used in chemical conversion treatment from the viewpoint of further improving the adhesion and corrosion resistance of the coating film, has recently been pointed out to be harmful to chromium, and a chemical treatment agent containing no chromium The development of has been required. As such a chemical conversion treatment, treatment with zinc phosphate is widely performed (for example, see Patent Document 1).
しかし、リン酸亜鉛系処理剤は、金属イオン及び酸濃度が高く非常に反応性の強い処理剤であるため、排水処理における経済性、作業性が良好でない。更に、リン酸亜鉛系処理剤による金属表面処理に伴って、水に不溶な塩類が生成して沈殿となって析出する。このような沈殿物は、一般にスラッジと呼ばれ、このようなスラッジを除去し、廃棄することによるコストの発生等が問題とされている。また、リン酸イオンは、富栄養化によって環境に対して負荷を与えるおそれがあるため、廃液の処理に際して労力を要し、使用しないことが好ましい。更に、リン酸亜鉛系処理剤による金属表面処理においては、表面調整を行うことが必要とされており、工程が長くなるという問題もある。 However, the zinc phosphate-based treating agent is a highly reactive treating agent having a high concentration of metal ions and acid, and therefore has poor economic efficiency and workability in wastewater treatment. Further, with the metal surface treatment with the zinc phosphate-based treating agent, salts insoluble in water are formed and precipitate as precipitates. Such a precipitate is generally called sludge, and there is a problem in that such sludge is removed and discarded, which results in cost. In addition, phosphate ions may exert a load on the environment due to eutrophication. Therefore, labor is required in treating waste liquid, and it is preferable that phosphate ions are not used. Furthermore, in the metal surface treatment using a zinc phosphate-based treating agent, it is necessary to adjust the surface, and there is a problem that the process becomes long.
このようなリン酸亜鉛系処理剤又はクロメート化成処理剤以外の金属表面処理剤として、ジルコニウム化合物からなる金属表面処理剤が知られている（例えば、特許文献２参照）。このようなジルコニウム化合物からなる金属表面処理剤は、スラッジの発生が抑制される点で上述したようなリン酸亜鉛系化成処理剤に比べて優れた性質を有している。 As a metal surface treatment agent other than such a zinc phosphate treatment agent or a chromate conversion treatment agent, a metal surface treatment agent comprising a zirconium compound is known (for example, see Patent Document 2). Such a metal surface treating agent comprising a zirconium compound has properties superior to the above-mentioned zinc phosphate chemical conversion treating agent in that generation of sludge is suppressed.
しかし、ジルコニウム化合物からなる金属表面処理剤によって得られた化成皮膜は、特にカチオン電着塗装により得られる塗膜との密着性が悪く、通常、カチオン電着塗装の前処理工程として使用されることは少なかった。このようなジルコニウム化合物からなる金属表面処理剤においては、リン酸イオン等の成分を併用することによって、密着性の向上や耐食性を改善することが行われている。しかし、リン酸イオンを併用した場合、上述したような富栄養化という問題が生じる。また、このような金属表面処理剤による処理を、カチオン電着塗装等の各種塗装の前処理方法として使用することについての検討は一切なされていない。また、このような金属表面処理剤によって鉄系基材を処理する場合、充分な塗膜の密着性や塗装後の耐食性が得られないという問題があった。 However, a chemical conversion coating obtained by a metal surface treatment agent comprising a zirconium compound has poor adhesion to a coating obtained particularly by cationic electrodeposition coating, and is usually used as a pretreatment step of cationic electrodeposition coating. Was few. In such a metal surface treating agent comprising a zirconium compound, an improvement in adhesion and an improvement in corrosion resistance have been carried out by using components such as phosphate ions in combination. However, when phosphate ions are used in combination, the problem of eutrophication occurs as described above. Further, there is no study on using such a treatment with a metal surface treating agent as a pretreatment method for various kinds of coating such as cationic electrodeposition coating. Further, when treating an iron-based substrate with such a metal surface treating agent, there is a problem that sufficient adhesion of a coating film and corrosion resistance after coating cannot be obtained.
ジルコニウム化合物及びアミノ基含有シランカップリング剤からなるノンクロメート金属表面処理剤も知られている（例えば、特許文献３参照。）。しかし、このようなノンクロメート金属表面処理剤はいわゆるコイルコーティング分野用途の塗布型処理剤であり、これを用いた表面処理は、処理後水洗が不可能であって、さらに、複雑な形状を有する被処理物を想定したものではなかった。 A non-chromate metal surface treatment agent comprising a zirconium compound and an amino group-containing silane coupling agent is also known (for example, see Patent Document 3). However, such a non-chromate metal surface treatment agent is a coating-type treatment agent for so-called coil coating applications, and the surface treatment using the same cannot be washed with water after the treatment and has a complicated shape. It was not supposed to be processed.
更に、自動車車体や部品等の鉄、亜鉛、アルミニウム等の種々の金属素材からなる物品に対して一回の処理ですべての金属の表面処理を行わなければならない場合もあり、このような場合であっても問題なく化成処理を施すことができる塗装前処理方法の開発が望まれている。他方、粉体塗料、溶剤塗料、水性塗料等によるカチオン電着塗装以外の塗装においても、上述のような問題を生じることなく化成処理を行うことができる前処理方法の開発も望まれている。 Further, in some cases, it is necessary to perform surface treatment of all metals in a single treatment on articles made of various metal materials such as iron, zinc, and aluminum such as automobile bodies and parts. It is desired to develop a coating pretreatment method that can perform a chemical conversion treatment without any problem. On the other hand, in coatings other than the cationic electrodeposition coating using a powder coating, a solvent coating, a water-based coating, and the like, it is also desired to develop a pretreatment method capable of performing a chemical conversion treatment without causing the above-described problems.
本発明は、上記に鑑み、塗装方法が限定されず、環境への負荷が少なく、かつ、鉄、亜鉛、アルミニウム等のすべての金属に対して良好な化成処理を行うことができる塗装前処理方法を提供することを目的とするものである。 In view of the above, the present invention is not limited to a coating method, has a low environmental load, and is capable of performing a good chemical conversion treatment on all metals such as iron, zinc, and aluminum. The purpose is to provide.
本発明は、化成処理剤によって被処理物を処理し、化成皮膜を形成する塗装前処理方法であって、上記化成処理剤は、ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種、フッ素、並びに、アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種からなることを特徴とする塗装前処理方法である。 The present invention is a pre-coating method for treating an object to be treated with a chemical conversion treatment agent to form a chemical conversion film, wherein the chemical conversion treatment agent is at least one selected from the group consisting of zirconium, titanium and hafnium, fluorine, A coating pretreatment method comprising at least one selected from the group consisting of an amino group-containing silane coupling agent, a hydrolyzate thereof, and a polymer thereof.
上記アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種の含有量は、固形分濃度で５〜５０００ｐｐｍであることが好ましい。
上記化成処理剤は、金属換算で２０〜１００００ｐｐｍのジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種を含有し、ｐＨが１．５〜６．５であることが好ましい。
上記化成処理剤は、更に、マグネシウムイオン、亜鉛イオン、カルシウムイオン、アルミニウムイオン、ガリウムイオン、インジウムイオン及び銅イオンからなる群より選ばれる少なくとも一種の密着性及び耐食性付与剤を含有することが好ましい。
以下、本発明を詳細に説明する。
The content of at least one selected from the group consisting of the amino group-containing silane coupling agent, its hydrolyzate, and its polymer is preferably from 5 to 5,000 ppm in terms of solid content.
The chemical conversion treating agent contains at least one selected from the group consisting of zirconium, titanium and hafnium in an amount of 20 to 10000 ppm in terms of metal, and preferably has a pH of 1.5 to 6.5.
The chemical conversion treatment agent preferably further contains at least one adhesion and corrosion resistance imparting agent selected from the group consisting of magnesium ions, zinc ions, calcium ions, aluminum ions, gallium ions, indium ions, and copper ions.
Hereinafter, the present invention will be described in detail.
本発明は、ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種、並びに、フッ素を含有し、リン酸イオンや、有害な重金属イオンを実質的に含有しない化成処理剤を用いて化成処理を行なう塗装前処理方法である。化成処理方法として汎用されているリン酸亜鉛処理に代えて、従来のジルコニウム等からなる化成処理剤により被処理物を処理すると、特に鉄系基材においては充分な塗膜密着性が得られない等の問題が生じる。本発明は、上記のような問題を解決し、ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種、並びに、フッ素からなる化成処理剤を用いて、鉄系基材に対しても充分な塗膜密着性を有する化成皮膜を形成する塗装前処理方法である。 The present invention performs chemical conversion treatment using at least one selected from the group consisting of zirconium, titanium, and hafnium, and a chemical conversion treatment agent that contains fluorine, and contains substantially no phosphate ions or harmful heavy metal ions. This is a pre-painting treatment method. When the object to be treated is treated with a conventional chemical conversion treatment agent composed of zirconium or the like instead of zinc phosphate treatment, which is widely used as a chemical conversion treatment method, sufficient coating film adhesion cannot be obtained, particularly in an iron-based substrate. And the like. The present invention solves the above-mentioned problems, and uses a chemical conversion treating agent comprising at least one selected from the group consisting of zirconium, titanium, and hafnium, and a fluorine-containing chemical conversion treatment agent, to sufficiently coat an iron-based substrate. This is a coating pretreatment method for forming a chemical conversion film having film adhesion.
上記化成処理剤に含まれるジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種は、化成皮膜形成成分であり、基材にジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種を含む化成皮膜が形成されることにより、基材の耐食性や耐磨耗性を向上させ、更に、塗膜との密着性を高めることができる。 At least one selected from the group consisting of zirconium, titanium, and hafnium contained in the chemical conversion treatment agent is a chemical conversion film-forming component, and the substrate has a chemical conversion film containing at least one selected from the group consisting of zirconium, titanium, and hafnium. By being formed, the corrosion resistance and abrasion resistance of the base material can be improved, and further, the adhesion to the coating film can be improved.
例えば、ジルコニウムを含有する化成処理剤を用いて金属基材の表面処理を行うと、金属の溶解反応により化成処理剤中に溶出した金属イオンがＺｒＦ６ ２−のフッ素を引き抜くことにより、又、界面ｐＨの上昇により、ジルコニウムの水酸化物又は酸化物が生成され、このジルコニウムの水酸化物又は酸化物が基材表面に析出していると考えられる。上述のように、本発明における化成処理剤は反応型化成処理剤であるため、複雑な形状を有する被処理物の浸漬処理にも用いることができる。また、上記化成処理剤を用いて表面処理を行うと、化学反応により強固に被処理物に付着した化成皮膜が得られるため、処理後水洗を行うこともできる。 For example, when the surface treatment of the metal substrate using a chemical conversion treatment agent containing zirconium, by metal ions eluted into the chemical conversion treatment agent by dissolution reaction of the metal pulls the ZrF 6 2-fluorine, and, It is considered that a zirconium hydroxide or oxide is generated due to the increase in the interface pH, and the zirconium hydroxide or oxide is deposited on the surface of the base material. As described above, since the chemical conversion treatment agent in the present invention is a reaction type chemical conversion treatment agent, it can also be used for immersion treatment of an object having a complicated shape. In addition, when the surface treatment is performed using the above-mentioned chemical conversion treatment agent, a chemical conversion film firmly adhered to the object to be treated by a chemical reaction can be obtained, and therefore, water washing can be performed after the treatment.
上記ジルコニウムの供給源としては特に限定されず、例えば、Ｋ２ＺｒＦ６等のアルカリ金属フルオロジルコネート；（ＮＨ４）２ＺｒＦ６等のフルオロジルコネート；Ｈ２ＺｒＦ６等のフルオロジルコネート酸等の可溶性フルオロジルコネート等；フッ化ジルコニウム；酸化ジルコニウム等を挙げることができる。 The source of the zirconium is not particularly limited. For example, alkali metal fluorozirconates such as K 2 ZrF 6 ; fluorozirconates such as (NH 4 ) 2 ZrF 6 ; fluorozirconates such as H 2 ZrF 6 Soluble zirconium fluoride; zirconium fluoride; zirconium oxide and the like.
上記チタンの供給源としては特に限定されず、例えば、アルカリ金属フルオロチタネート、（ＮＨ４）２ＴｉＦ６等のフルオロチタネート；Ｈ２ＴｉＦ６等のフルオロチタネート酸等の可溶性フルオロチタネート等；フッ化チタン；酸化チタン等を挙げることができる。 The source of the titanium is not particularly limited. For example, alkali metal fluorotitanate, fluorotitanate such as (NH 4 ) 2 TiF 6 ; soluble fluorotitanate such as fluorotitanate acid such as H 2 TiF 6 ; titanium fluoride A titanium oxide and the like.
上記ハフニウムの供給源としては特に限定されず、例えば、Ｈ２ＨｆＦ６等のフルオロハフネート酸；フッ化ハフニウム等を挙げることができる。
上記ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種の供給源としては、皮膜形成能が高いことからＺｒＦ６ ２−、ＴｉＦ６ ２−、ＨｆＦ６ ２−からなる群より選ばれる少なくとも一種を有する化合物が好ましい。
The source of the hafnium is not particularly limited, and examples thereof include a fluorohafnate acid such as H 2 HfF 6 and hafnium fluoride.
The zirconium, the at least one source of selected from the group consisting of titanium and hafnium, ZrF 6 2-due to its high film-forming ability, TiF 6 2-, at least one selected from the group consisting of HfF 6 2- Is preferred.
上記化成処理剤に含まれるジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種の含有量は、金属換算で下限２０ｐｐｍ、上限１００００ｐｐｍの範囲内であることが好ましい。上記下限未満であると得られる化成皮膜の性能が不充分であり、上記上限を超えると、それ以上の効果は望めず経済的に不利である。上記下限は５０ｐｐｍがより好ましく、上記上限は２０００ｐｐｍがより好ましい。 The content of at least one selected from the group consisting of zirconium, titanium and hafnium contained in the chemical conversion treatment agent is preferably in the range of a lower limit of 20 ppm and an upper limit of 10,000 ppm in terms of metal. If the amount is less than the above lower limit, the performance of the resulting chemical conversion film is insufficient. If the amount exceeds the above upper limit, no further effect can be expected and it is economically disadvantageous. The lower limit is more preferably 50 ppm, and the upper limit is more preferably 2000 ppm.
上記化成処理剤に含まれるフッ素は、基材のエッチング剤としての役割を果たすものである。上記フッ素の供給源としては特に限定されず、例えば、フッ化水素酸、フッ化アンモニウム、フッ化ホウ素酸、フッ化水素アンモニウム、フッ化ナトリウム、フッ化水素ナトリウム等のフッ化物を挙げることができる。また、錯フッ化物としては、例えば、ヘキサフルオロケイ酸塩が挙げられ、その具体例としてケイフッ化水素酸、ケイフッ化水素酸亜鉛、ケイフッ化水素酸マンガン、ケイフッ化水素酸マグネシウム、ケイフッ化水素酸ニッケル、ケイフッ化水素酸鉄、ケイフッ化水素酸カルシウム等を挙げることができる。 The fluorine contained in the chemical conversion treating agent plays a role as an etching agent for the base material. The source of the fluorine is not particularly limited, and examples thereof include fluorides such as hydrofluoric acid, ammonium fluoride, boron fluoride, ammonium hydrogen fluoride, sodium fluoride, and sodium hydrogen fluoride. . Examples of the complex fluoride include hexafluorosilicate, and specific examples thereof include hydrofluorosilicic acid, zinc hydrofluorosilicate, manganese hydrofluorosilicate, magnesium hydrofluorosilicate, and hydrofluorosilicic acid. Nickel, iron hydrofluorosilicate, calcium hydrofluorosilicate and the like can be mentioned.
上記化成処理剤は、アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種を含有するものである。上記アミノ基含有シランカップリング剤は、分子中に少なくとも１つのアミノ基を有し、かつ、シロキサン結合を有する化合物である。上記アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種が化成皮膜と塗膜の双方に作用することにより、両者の密着性が向上される。 The chemical conversion treating agent contains at least one selected from the group consisting of an amino group-containing silane coupling agent, a hydrolyzate thereof, and a polymer thereof. The amino group-containing silane coupling agent is a compound having at least one amino group in a molecule and having a siloxane bond. When at least one selected from the group consisting of the amino group-containing silane coupling agent, a hydrolyzate thereof, and a polymer thereof acts on both the chemical conversion film and the coating film, the adhesion between them is improved.
このような効果は、加水分解してシラノールを生成する基が加水分解され金属基材の表面と水素結合的に吸着すること、及び、アミノ基の作用により化成皮膜と金属基材の密着性が高まるために生じると推測される。上述したように化成皮膜に含まれるアミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種が、金属基材及び塗膜の両方に働きかけることによって、相互の密着性を向上させる作用を有すると考えられる。 This effect is due to the fact that the group that generates silanol by hydrolysis is hydrolyzed and adsorbed to the surface of the metal substrate by hydrogen bonding, and the adhesion between the chemical conversion film and the metal substrate is caused by the action of the amino group. It is presumed to occur because of the increase. As described above, the amino group-containing silane coupling agent contained in the chemical conversion film, at least one selected from the group consisting of a hydrolyzate and a polymer thereof, acts on both the metal base material and the coating film, thereby causing mutual interaction. It is considered to have the effect of improving the adhesion.
上記アミノ基含有シランカップリング剤としては特に限定されず、例えば、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ，Ｎ−ビス〔３−（トリメトキシシリル）プロピル〕エチレンジアミン等の公知のシランカップリング剤等を挙げることができる。市販されているアミノ基含有シランカップリング剤であるＫＢＭ−６０２、ＫＢＭ−６０３、ＫＢＥ−６０３、ＫＢＭ−９０３、ＫＢＥ−９１０３、ＫＢＭ−５７３（以上信越化学工業株式会社製）、ＸＳ１００３（チッソ株式会社製）等も使用することができる。 The amino group-containing silane coupling agent is not particularly limited. For example, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (Aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- Known silane coupling agents such as phenyl-3-aminopropyltrimethoxysilane and N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine can be used. Commercially available amino group-containing silane coupling agents KBM-602, KBM-603, KBE-603, KBM-903, KBE-9103, KBM-573 (all manufactured by Shin-Etsu Chemical Co., Ltd.), XS1003 (Chisso Corporation) Can be used.
上記アミノ基含有シランカップリング剤の加水分解物は、従来公知の方法、例えば、上記アミノ基含有シランカップリング剤をイオン交換水に溶解し、任意の酸で酸性に調整する方法等により製造することができる。上記アミノ基含有シランカップリング剤の加水分解物としては、ＫＢＰ−９０（信越化学工業株式会社製：有効成分３２％）等の市販の製品を使用することもできる。 The hydrolyzate of the amino group-containing silane coupling agent is produced by a conventionally known method, for example, by dissolving the amino group-containing silane coupling agent in ion-exchanged water and adjusting the acidity with an arbitrary acid. be able to. As the hydrolyzate of the amino group-containing silane coupling agent, a commercially available product such as KBP-90 (manufactured by Shin-Etsu Chemical Co., Ltd .: active ingredient 32%) can be used.
上記アミノ基含有シランカップリング剤の重合物としては特に限定されず、例えば、サイラエースＳ−３３０（γ−アミノプロピルトリエトキシシラン；チッソ株式会社製）、サイラエースＳ−３２０（Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン；チッソ株式会社製）等の市販の製品を挙げることができる。 The polymer of the amino group-containing silane coupling agent is not particularly limited. For example, Silaace S-330 (γ-aminopropyltriethoxysilane; manufactured by Chisso Corporation), Silaace S-320 (N- (2-amino) Commercially available products such as ethyl) -3-aminopropyltrimethoxysilane (manufactured by Chisso Corporation).
上記アミノ基含有シランカップリング剤及びその加水分解物は、特にカチオン電着塗料による塗装の前処理を行う際に好適に使用される。また、上記アミノ基含有シランカップリング剤の重合物は、上記カチオン電着塗料だけでなく、溶剤塗料、水性塗料、粉体塗料等を用いた塗装の前処理を行う際に好適に使用することができる。 The amino group-containing silane coupling agent and the hydrolyzate thereof are preferably used particularly when performing pretreatment for coating with a cationic electrodeposition paint. In addition, the polymer of the amino group-containing silane coupling agent is preferably used not only in the cationic electrodeposition coating, but also in pretreatment of coating using a solvent coating, an aqueous coating, a powder coating, or the like. Can be.
上記化成処理剤における上記アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種の配合量は、固形分濃度で下限５ｐｐｍ、上限５０００ｐｐｍの範囲内であることが好ましい。５ｐｐｍ未満であると、充分な塗膜密着性を得ることができない。５０００ｐｐｍを超えると、それ以上の効果は望めず、経済的に不利である。上記下限は、１０ｐｐｍがより好ましく、５０ｐｐｍが更に好ましい。上記上限は、１０００ｐｐｍがより好ましく、５００ｐｐｍが更に好ましい。 The amount of at least one compound selected from the group consisting of the amino group-containing silane coupling agent, the hydrolyzate thereof, and the polymer thereof in the chemical conversion treatment agent is in the range of a lower limit of 5 ppm and an upper limit of 5000 ppm in solid content concentration. Is preferred. If it is less than 5 ppm, sufficient coating film adhesion cannot be obtained. If it exceeds 5000 ppm, no further effect can be expected, which is economically disadvantageous. The lower limit is more preferably 10 ppm, and still more preferably 50 ppm. The upper limit is more preferably 1000 ppm, and still more preferably 500 ppm.
上記化成処理剤は、実質的にリン酸イオンを含有しないものであることが好ましい。実質的にリン酸イオンを含まないとは、リン酸イオンが化成処理剤中の成分として作用する程含まれていないことを意味し、本発明において使用する化成処理剤は、実質的にリン酸イオンを含まないことから、環境負荷の原因となるリンを実質的に使用することがなく、リン酸亜鉛系処理剤を使用する場合に発生するリン酸鉄、リン酸亜鉛等のようなスラッジの発生を抑制することができる。 It is preferable that the chemical conversion treatment agent does not substantially contain phosphate ions. The phrase “substantially free of phosphate ions” means that phosphate ions are not contained so much as to act as a component in the chemical conversion treatment agent. Since it does not contain ions, it does not substantially use phosphorus, which causes environmental load, and generates sludge such as iron phosphate and zinc phosphate generated when using a zinc phosphate treatment agent. Generation can be suppressed.
上記化成処理剤は、ｐＨが下限１．５、上限６．５の範囲内であることが好ましい。１．５未満であると、エッチング過剰となり充分な皮膜形成ができなくなる。６．５を超えると、エッチングが不充分となり良好な皮膜が得られない。上記下限は、２．０がより好ましく、上記上限は、５．５がより好ましい。上記下限は、２．５が更に好ましく、上記上限は、５．０が更に好ましい。上記化成処理剤のｐＨを調整するために、硝酸、硫酸等の酸性化合物、及び、水酸化ナトリウム、水酸化カリウム、アンモニア等の塩基性化合物を使用することができる。 The chemical conversion treating agent preferably has a pH in the range of a lower limit of 1.5 and an upper limit of 6.5. If the ratio is less than 1.5, the etching becomes excessive and a sufficient film cannot be formed. If it exceeds 6.5, the etching becomes insufficient and a good film cannot be obtained. The lower limit is more preferably 2.0, and the upper limit is more preferably 5.5. The lower limit is more preferably 2.5, and the upper limit is more preferably 5.0. In order to adjust the pH of the chemical conversion treating agent, acidic compounds such as nitric acid and sulfuric acid, and basic compounds such as sodium hydroxide, potassium hydroxide and ammonia can be used.
上記化成処理剤は、更に、密着性及び耐食性付与剤としてマグネシウムイオン、亜鉛イオン、カルシウムイオン、アルミニウムイオン、ガリウムイオン、インジウムイオン及び銅イオンからなる群より選ばれる少なくとも一種を含有することが好ましい。上記密着性及び耐食性付与剤を含有することにより、より良好な密着性及び耐食性を有する化成皮膜を得ることができる。 It is preferable that the chemical conversion treatment agent further contains at least one selected from the group consisting of magnesium ions, zinc ions, calcium ions, aluminum ions, gallium ions, indium ions, and copper ions as an agent for imparting adhesion and corrosion resistance. By containing the above-mentioned agent for imparting adhesion and corrosion resistance, a chemical conversion film having better adhesion and corrosion resistance can be obtained.
上記化成処理剤における上記マグネシウムイオン、亜鉛イオン、カルシウムイオン、アルミニウムイオン、ガリウムイオン、インジウムイオン及び銅イオンからなる群より選ばれる少なくとも一種の含有量は、下限１ｐｐｍ、上限５０００ｐｐｍの範囲内であることが好ましい。上記含有量が上記下限未満であると、充分な効果が得られず好ましくない。上記含有量が上記上限を超えると、それ以上の効果の向上はみられず経済的に不利であり、塗装後密着性が低下する場合もある。上記下限は、２５ｐｐｍがより好ましく、上記上限は、３０００ｐｐｍがより好ましい。 The content of at least one selected from the group consisting of the magnesium ion, zinc ion, calcium ion, aluminum ion, gallium ion, indium ion, and copper ion in the chemical conversion treatment agent is within a range of a lower limit of 1 ppm and an upper limit of 5000 ppm. Is preferred. If the content is less than the lower limit, a sufficient effect cannot be obtained, which is not preferable. When the content exceeds the upper limit, no further improvement in the effect is observed, which is economically disadvantageous, and the adhesion after coating may decrease. The lower limit is more preferably 25 ppm, and the upper limit is more preferably 3000 ppm.
上記化成処理剤は、上記成分の他に必要に応じて、任意の成分を併用するものであってもよい。使用することができる成分としては、シリカ等を挙げることができる。このような成分を添加することで、塗装後耐食性を向上させることが可能である。 The above-mentioned chemical conversion treating agent may be used in combination with an optional component, if necessary, in addition to the above-mentioned component. Examples of components that can be used include silica and the like. By adding such components, it is possible to improve the corrosion resistance after painting.
本発明の塗装前処理方法における化成処理は、特に限定されるものではなく、通常の処理条件によって化成処理剤と金属表面とを接触させることによって行うことができる。上記化成処理における処理温度は、下限２０℃、上限７０℃の範囲内であることが好ましい。上記下限は３０℃であることがより好ましく、上記上限は５０℃であることがより好ましい。上記化成処理における化成時間は、下限５秒、上限１２００秒の範囲内であることが好ましい。上記下限は３０秒がより好ましく、上記上限は１２０秒がより好ましい。化成処理方法としては特に限定されず、例えば、浸漬法、スプレー法、ロールコート法等を挙げることができる。 The chemical conversion treatment in the coating pretreatment method of the present invention is not particularly limited, and can be performed by bringing the chemical conversion agent into contact with the metal surface under ordinary processing conditions. The treatment temperature in the chemical conversion treatment is preferably within a range of a lower limit of 20 ° C and an upper limit of 70 ° C. The lower limit is more preferably 30 ° C., and the upper limit is more preferably 50 ° C. The chemical conversion time in the chemical conversion treatment is preferably within a range of a lower limit of 5 seconds and an upper limit of 1200 seconds. The lower limit is more preferably 30 seconds, and the upper limit is more preferably 120 seconds. The chemical conversion treatment method is not particularly limited, and examples thereof include a dipping method, a spray method, and a roll coating method.
本発明の塗装前処理方法においては、上記化成処理を行う前に、金属基材の表面に対して脱脂処理、脱脂後水洗処理を行い、上記化成処理後に化成後水洗処理を行うことが好ましい。
上記脱脂処理は、基材表面に付着している油分や汚れを除去するために行われるものであり、無リン・無窒素脱脂洗浄液等の脱脂剤により、通常３０〜５５℃において数分間程度の浸漬処理がなされる。所望により、脱脂処理の前に、予備脱脂処理を行うことも可能である。
In the pre-coating treatment method of the present invention, it is preferable that the surface of the metal substrate is subjected to a degreasing treatment, a degreasing and a rinsing treatment before the chemical conversion treatment, and a post-chemical rinsing treatment after the chemical conversion treatment.
The degreasing treatment is performed to remove oil and dirt attached to the surface of the base material, and is usually performed at a temperature of 30 to 55 ° C. for several minutes by a degreasing agent such as a phosphorus-free and nitrogen-free degreasing cleaning solution. An immersion process is performed. If desired, a preliminary degreasing treatment can be performed before the degreasing treatment.
上記脱脂後水洗処理は、脱脂処理後の脱脂剤を水洗するために、大量の水洗水によって１回又はそれ以上スプレー処理を行うことにより行われるものである。
上記化成後水洗処理は、その後の各種塗装後の密着性、耐食性等に悪影響を及ぼさないようにするために、１回又はそれ以上により行われるものである。この場合、最終の水洗は、純水で行われることが適当である。この化成後水洗処理においては、スプレー水洗又は浸漬水洗のどちらでもよく、これらの方法を組み合わせて水洗することもできる。
上記化成後水洗処理の後は、公知の方法に従って、必要に応じて乾燥され、その後、各種塗装を行うことができる。
The post-degreasing water washing treatment is performed by spraying once or more with a large amount of washing water in order to wash the degreasing agent after the degreasing treatment with water.
The post-chemical conversion washing treatment is performed once or more so as not to adversely affect the adhesion, corrosion resistance, and the like after the subsequent coating. In this case, it is appropriate that the final washing is performed with pure water. In the post-chemical water washing treatment, either spray water washing or immersion water washing may be used, and water washing may be performed by combining these methods.
After the above-mentioned post-formation water-washing treatment, it is dried if necessary according to a known method, and thereafter, various coatings can be performed.
本発明の塗装前処理方法は、従来より実用化されているリン酸亜鉛系化成処理剤を用いて処理する方法において、必要となっている表面調整処理を行わなくてもよいため、より少ない工程で金属基材の化成処理を行うことが可能である。 The coating pretreatment method of the present invention is a method of treating with a zinc phosphate-based chemical conversion treatment agent that has been conventionally practically used. It is possible to carry out a chemical conversion treatment of the metal base material.
本発明において処理される金属基材は、鉄系基材、アルミニウム系基材、及び、亜鉛系基材等を挙げることができる。鉄、アルミニウム、及び、亜鉛系基材とは、基材が鉄及び／又はその合金からなる鉄系基材、基材がアルミニウム及び／又はその合金からなるアルミニウム基材、基材が亜鉛及び／又はその合金からなる亜鉛系基材を意味する。本発明の塗装前処理方法は、鉄系基材、アルミニウム系基材、及び、亜鉛系基材のうちの複数の金属基材からなる被処理物に対しても適用することができる。 Examples of the metal substrate treated in the present invention include an iron-based substrate, an aluminum-based substrate, and a zinc-based substrate. Iron, aluminum, and a zinc-based substrate are an iron-based substrate whose base is made of iron and / or an alloy thereof, an aluminum base whose base is made of aluminum and / or an alloy thereof, and zinc and / or Or a zinc-based substrate made of an alloy thereof. The coating pretreatment method of the present invention can be applied to an object to be processed composed of a plurality of metal substrates among an iron-based substrate, an aluminum-based substrate, and a zinc-based substrate.
本発明の塗装前処理方法は、通常のジルコニウム等からなる化成処理剤による処理によって充分な塗膜密着性を得ることが困難であった鉄系基材に対しても、充分な塗膜密着性を付与することができる点で好ましく、このため、特に少なくとも一部に鉄系基材を含む被処理物の処理にも適用することができる点で優れた性質を有するものである。 The coating pretreatment method of the present invention has a sufficient coating film adhesion to an iron-based substrate, which has been difficult to obtain sufficient coating film adhesion by a treatment with a chemical conversion treatment agent composed of ordinary zirconium or the like. Therefore, it has excellent properties in that it can be applied particularly to the treatment of an object to be treated containing an iron-based substrate at least in part.
上記鉄系基材としては特に限定されず、例えば、冷延鋼板、熱延鋼板等を挙げることができる。上記アルミニウム系基材としては特に限定されず、例えば、５０００番系アルミニウム合金、６０００番系アルミニウム合金等を挙げることができる。上記亜鉛系基材としては特に限定されず、例えば、亜鉛めっき鋼板、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−マンガンめっき鋼板等の亜鉛系の電気めっき、溶融めっき、蒸着めっき鋼板等の亜鉛又は亜鉛系合金めっき鋼板等を挙げることができる。本発明においては、鉄、アルミニウム及び亜鉛系基材を同時に化成処理することができる。 The iron-based substrate is not particularly limited, and examples thereof include a cold-rolled steel sheet and a hot-rolled steel sheet. The aluminum-based substrate is not particularly limited, and examples thereof include a 5000-th aluminum alloy and a 6000-th aluminum alloy. The zinc-based substrate is not particularly limited. For example, a zinc-coated steel sheet, a zinc-nickel-coated steel sheet, a zinc-iron-plated steel sheet, a zinc-chromium-plated steel sheet, a zinc-aluminum-plated steel sheet, a zinc-titanium-plated steel sheet, zinc- Examples thereof include zinc-based electroplated steel sheets such as magnesium-plated steel sheets and zinc-manganese-plated steel sheets, hot-dip coated steel sheets, and zinc- or zinc-based alloy-plated steel sheets such as vapor-deposited plated steel sheets. In the present invention, iron, aluminum and zinc-based substrates can be subjected to chemical conversion treatment at the same time.
本発明の塗装前処理方法により得られる化成皮膜は、皮膜量が化成処理剤に含まれる金属の合計量で下限０．１ｍｇ／ｍ２、上限５００ｍｇ／ｍ２の範囲内であることが好ましい。０．１ｍｇ／ｍ２未満であると、均一な化成皮膜が得られず好ましくない。５００ｍｇ／ｍ２を超えると、それ以上の効果は得られず、経済的に不利である。上記下限は、５ｍｇ／ｍ２がより好ましく、上記上限は、２００ｍｇ／ｍ２がより好ましい。 Conversion coating obtained by painting pretreatment method of the present invention, the lower limit 0.1 mg / m 2 in a total amount of metal coating weight is comprised chemical conversion treatment agent is preferably in the range of the upper limit 500 mg / m 2. If it is less than 0.1 mg / m 2 , a uniform chemical conversion film cannot be obtained, which is not preferable. If it exceeds 500 mg / m 2 , no further effect can be obtained, which is economically disadvantageous. The lower limit is more preferably 5 mg / m 2 , and the upper limit is more preferably 200 mg / m 2 .
本発明の塗装前処理方法により処理された金属基材に対して行うことができる塗装としては特に限定されず、カチオン電着塗料、溶剤塗料、水性塗料、粉体塗料等の従来公知の塗料を用いた塗装を行うことができる。例えば、上記カチオン電着塗料としては特に限定されず、アミノ化エポキシ樹脂、アミノ化アクリル樹脂、スルホニウム化エポキシ樹脂等からなる従来公知のカチオン電着塗料を塗布することができる。なかでも、化成処理剤にアミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種を配合することから、電着塗膜と化成皮膜の密着性をより高めるために、アミノ基との反応性又は相溶性を示す官能基を有する樹脂からなるカチオン電着塗料が好ましい。 The coating that can be performed on the metal substrate treated by the coating pretreatment method of the present invention is not particularly limited, and a conventionally known coating such as a cationic electrodeposition coating, a solvent coating, a water-based coating, or a powder coating can be used. The coating used can be performed. For example, the above-mentioned cationic electrodeposition paint is not particularly limited, and a conventionally known cationic electrodeposition paint composed of an aminated epoxy resin, an aminated acrylic resin, a sulfonium epoxy resin, or the like can be applied. Above all, since the chemical conversion treating agent contains at least one selected from the group consisting of an amino group-containing silane coupling agent, a hydrolyzate thereof and a polymer thereof, the adhesion between the electrodeposition coating film and the chemical conversion film is further improved. For this reason, a cationic electrodeposition coating composed of a resin having a functional group that is reactive or compatible with an amino group is preferable.
本発明の塗装前処理方法は、ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種を化成皮膜形成成分として、更に、アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種を含有する化成処理剤を用いることで、従来リン酸亜鉛系処理剤による化成処理が一般的であった塗装前処理を好適に行うことができる。更に、従来ジルコニウム等からなる化成処理剤での前処理が不適であった鉄系基材に対しても塗膜密着性に優れた化成皮膜を形成することができるものである。
又、本発明で使用する化成処理剤は、リン酸イオンを実質的に含まないため、環境に対する負荷が少なく、スラッジも発生しない。更に、本発明の塗装前処理方法は、表面調整工程を必要としないため、より少ない工程で金属基材の化成処理を行うことが可能である。
The coating pretreatment method of the present invention comprises, as a chemical conversion film-forming component, at least one selected from the group consisting of zirconium, titanium, and hafnium, further comprising an amino group-containing silane coupling agent, a hydrolyzate thereof, and a polymer thereof. By using a chemical conversion treatment agent containing at least one selected from the group, it is possible to suitably perform a pre-coating treatment in which conversion treatment with a zinc phosphate-based treatment agent has conventionally been common. Further, it is possible to form a chemical conversion film having excellent coating film adhesion even on an iron-based substrate, which was conventionally unsuitable for pretreatment with a chemical conversion treatment agent composed of zirconium or the like.
Further, since the chemical conversion treatment agent used in the present invention does not substantially contain phosphate ions, the load on the environment is small and sludge is not generated. Furthermore, since the method for pre-coating treatment of the present invention does not require a surface conditioning step, it is possible to carry out the chemical conversion treatment of the metal base material in fewer steps.
以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.
実施例１
市販の冷間圧延鋼板（ＳＰＣＣ−ＳＤ、日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）を基材として、下記の条件で塗装前処理を施した。
（１）塗装前処理
脱脂処理：２質量％「サーフクリーナー５３」（日本ペイント社製脱脂剤）で４０℃、２分間浸漬処理した。
脱脂後水洗処理：水道水で３０秒間スプレー処理した。
化成処理：ジルコンフッ化水素酸及びアミノ基含有シランカップリング剤としてＫＢＭ−６０３（Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン：有効濃度１００％：信越化学工業株式会社製）を使用し、ジルコニウム濃度１００ｐｐｍ、固形分としてアミノ基含有シランカップリング剤濃度１００ｐｐｍの化成処理剤を調製した。ｐＨは、水酸化ナトリウムを用いて４に調整した。化成処理剤の温度を４０℃に調整し、基材を６０秒間浸漬処理した。処理の初期段階における皮膜量は、１０ｍｇ／ｍ２であった。
Example 1
Using a commercially available cold-rolled steel plate (SPCC-SD, manufactured by Nippon Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm) as a base material, pre-coating treatment was performed under the following conditions.
(1) Pre-coating treatment Degreasing treatment: 2% by mass of “Surf Cleaner 53” (degreasing agent manufactured by Nippon Paint Co., Ltd.) at 40 ° C. for 2 minutes.
Rinsing treatment after degreasing: spray treatment with tap water for 30 seconds.
Chemical conversion treatment: KBM-603 (N-2 (aminoethyl) 3-aminopropyltrimethoxysilane: effective concentration 100%: manufactured by Shin-Etsu Chemical Co., Ltd.) is used as zircon hydrofluoric acid and an amino group-containing silane coupling agent. A chemical conversion treating agent having a zirconium concentration of 100 ppm and an amino group-containing silane coupling agent concentration of 100 ppm as a solid content was prepared. The pH was adjusted to 4 using sodium hydroxide. The temperature of the chemical conversion treatment agent was adjusted to 40 ° C., and the substrate was dipped for 60 seconds. The coating amount at the initial stage of the treatment was 10 mg / m 2 .
化成後水洗処理：水道水で３０秒間スプレー処理した。更にイオン交換水で１０秒間スプレー処理した。その後、ウェットな状態で電着塗装を行った。
なお、皮膜量は、水洗処理後の冷延鋼板を電気乾燥炉において、８０℃で５分間乾燥したうえで「ＸＲＦ１７００」（島津製作所製蛍光Ｘ線分析装置）を用いて、化成処理剤に含まれる金属の合計量として分析した。
Rinse treatment after chemical formation: spray treatment with tap water for 30 seconds. Further, spray treatment was performed with ion exchanged water for 10 seconds. Thereafter, electrodeposition coating was performed in a wet state.
The amount of the coating was included in the chemical conversion treatment agent after drying the cold-rolled steel sheet after the water-washing treatment in an electric drying oven at 80 ° C. for 5 minutes and using “XRF1700” (Shimadzu X-ray fluorescence analyzer). And analyzed as the total amount of metals.
（２）塗装
化成処理剤１Ｌ当たり１ｍ２の冷間圧延鋼板を処理した後に、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）を用いて乾燥膜厚２０μｍになるように電着塗装し、水洗後、１７０℃で２０分間加熱して焼き付け、試験板を作成した。
(2) After treating a cold-rolled steel sheet of 1 m 2 per 1 L of a coating chemical conversion treatment agent, electrodeposition coating was performed using “Powernics 110” (a cationic electrodeposition coating product manufactured by Nippon Paint Co., Ltd.) so as to have a dry film thickness of 20 μm. After washing with water, the plate was heated at 170 ° C. for 20 minutes and baked to prepare a test plate.
評価試験
〈スラッジ観察〉
化成処理剤１Ｌ当たり１ｍ２の金属基材を処理した後、化成処理剤中の濁りを目視観察した。
〇：濁りなし
×：濁りあり
Evaluation test <Sludge observation>
After treating 1 m 2 of the metal substrate per 1 L of the chemical conversion treatment agent, turbidity in the chemical conversion treatment agent was visually observed.
〇: No cloudiness ×: Cloudy
〈二次密着性試験（ＳＤＴ）〉
得られた試験板に、素地まで達する縦平行カットを２本入れた後、５％ＮａＣｌ水溶液中において５０℃で４８０時間浸漬した。その後、カット部をテープ剥離し、塗料の剥離を観察した。
◎：剥離なし
〇：若干剥離
×：剥離幅３ｍｍ以上
<Secondary adhesion test (SDT)>
Two vertical parallel cuts reaching the substrate were placed in the obtained test plate, and then immersed in a 5% NaCl aqueous solution at 50 ° C. for 480 hours. Thereafter, the cut portion was tape-peeled, and the peeling of the paint was observed.
◎: No peeling〇: Slight peeling ×: Peeling width 3 mm or more
〈ＳＳＴ〉
得られた試験板に、素地まで達するクロスカットをいれた後、３５℃に保たれた塩水噴霧試験器中で５％ＮａＣｌ水溶液を２４０時間連続噴霧した。その後、カット部からのふくれ幅を測定した。
<SST>
After the obtained test plate was subjected to a cross cut reaching the substrate, a 5% NaCl aqueous solution was continuously sprayed for 240 hours in a salt spray tester maintained at 35 ° C. Thereafter, the blister width from the cut portion was measured.
〈耐湿試験〉
得られた試験板を恒温恒湿試験機（湿度９５％、温度５０℃）に２４０時間放置した。次に、試験板を大気中で１時間放置後、クロスカット（１ｍｍ角×１００個）をいれ、テープ剥離し、塗膜残存数を測定して塗膜密着性の指標とした。
<Moisture resistance test>
The obtained test plate was left for 240 hours in a thermo-hygrostat (humidity 95%, temperature 50 ° C.). Next, after leaving the test plate in the air for 1 hour, a cross cut (1 mm square × 100 pieces) was inserted, the tape was peeled off, and the number of remaining coating films was measured to obtain an index of coating film adhesion.
実施例２
アミノ基含有シランカップリング剤として、ＫＢＭ−９０３（３−アミノプロピルトリメトキシシラン：有効濃度１００％：信越化学工業株式会社製）を用いたこと以外は、実施例１と同様にして試験板を作製した。
Example 2
A test plate was prepared in the same manner as in Example 1 except that KBM-903 (3-aminopropyltrimethoxysilane: effective concentration 100%: manufactured by Shin-Etsu Chemical Co., Ltd.) was used as an amino group-containing silane coupling agent. Produced.
実施例３
アミノ基含有シランカップリング剤として、ＫＢＥ−９０３（３−アミノプロピルトリエトキシシラン：有効濃度１００％：信越化学工業株式会社製）を用いたこと以外は、実施例１と同様にして試験板を作製した。
Example 3
A test plate was prepared in the same manner as in Example 1 except that KBE-903 (3-aminopropyltriethoxysilane: effective concentration 100%: manufactured by Shin-Etsu Chemical Co., Ltd.) was used as an amino group-containing silane coupling agent. Produced.
実施例４
アミノ基含有シランカップリング剤の加水分解物として、ＫＢＰ−９０（３−アミノプロピルトリメトキシシラン加水分解物：有効濃度３２％：信越化学工業株式会社製）を用いたこと以外は、実施例１と同様にして試験板を作製した。
Example 4
Example 1 except that KBP-90 (3-aminopropyltrimethoxysilane hydrolyzate: effective concentration 32%: manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the hydrolyzate of the amino group-containing silane coupling agent. A test plate was prepared in the same manner as described above.
実施例５
アミノ基含有シランカップリング剤の加水分解物として、ＸＳ−１００３（Ｎ，Ｎ−ビス［３−（トリメトキシシリル）プロピル］エチレンジアミンのメタノール溶液：有効濃度５０％：チッソ株式会社製）を用いたこと以外は、実施例１と同様にして試験板を作製した。
Example 5
As a hydrolyzate of the amino group-containing silane coupling agent, XS-1003 (methanol solution of N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine: effective concentration 50%: manufactured by Chisso Corporation) was used. Except for this, a test plate was produced in the same manner as in Example 1.
実施例６
アミノ基含有シランカップリング剤の濃度を５ｐｐｍに変更したこと以外は、実施例２と同様にして試験板を作製した。
Example 6
A test plate was prepared in the same manner as in Example 2, except that the concentration of the amino group-containing silane coupling agent was changed to 5 ppm.
実施例７
アミノ基含有シランカップリング剤の濃度を５０００ｐｐｍに変更したこと以外は、実施例２と同様にして試験板を作製した。
Example 7
A test plate was prepared in the same manner as in Example 2, except that the concentration of the amino group-containing silane coupling agent was changed to 5000 ppm.
実施例８
金属基材を、亜鉛系めっき鋼板（ＧＡ鋼板、日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）に変更したこと以外は、実施例２と同様にして試験板を作製した。
Example 8
A test plate was prepared in the same manner as in Example 2 except that the metal base material was changed to a galvanized steel plate (GA steel plate, manufactured by Nippon Test Panel Co., Ltd., 70 mm × 150 mm × 0.8 mm).
実施例９
金属基材を、５０００系アルミニウム（日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）に変更したこと以外は、実施例２と同様にして試験板を作製した。
Example 9
A test plate was produced in the same manner as in Example 2 except that the metal base material was changed to 5000 series aluminum (70 mm x 150 mm x 0.8 mm, manufactured by Nippon Test Panel Co., Ltd.).
実施例１０〜３５
密着性及び耐食性付与剤として硝酸マグネシウム及び硝酸亜鉛を使用し、アミノ基含有シランカップリング剤の重合物としてサイラエースＳ−３３０又はサイラエースＳ−３２０（いずれもチッソ株式会社製）を使用して表１及び２に示した組成を有する化成処理剤を調製し、基材として溶融亜鉛めっき鋼板（ＧＩ、日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）、電気めっき亜鉛鋼板（ＥＧ、日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）、黒皮鋼板（ＳＳ４００、日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）又は６０００系アルミニウム（日本テストパネル社製、７０ｍｍ×１５０ｍｍ×０．８ｍｍ）を使用したこと以外は実施例１と同様にして試験板を作製した。
Examples 10 to 35
Using magnesium nitrate and zinc nitrate as adhesion and corrosion resistance imparting agents, and using Silaace S-330 or Silaace S-320 (both manufactured by Chisso Corporation) as a polymer of an amino group-containing silane coupling agent, Table 1 And a chemical conversion treatment agent having the composition shown in Table 2 was prepared, and as a base material, a hot-dip galvanized steel sheet (GI, manufactured by Nippon Test Panel Co., 70 mm × 150 mm × 0.8 mm), an electroplated zinc steel sheet (EG, Nippon Test Panel) 70 mm x 150 mm x 0.8 mm), black scale steel plate (SS400, Nippon Test Panel, 70 mm x 150 mm x 0.8 mm) or 6000 series aluminum (Nippon Test Panel, 70 mm x 150 mm x 0.8 mm) A test plate was prepared in the same manner as in Example 1 except that (1) was used.
比較例１
アミノ基含有シランカップリング剤を配合しなかったこと以外は、実施例１と同様にして試験板を作製した。
Comparative Example 1
A test plate was prepared in the same manner as in Example 1, except that the amino group-containing silane coupling agent was not blended.
比較例２
ジルコンフッ化水素酸を配合しなかったこと以外は、実施例１と同様にして試験板を作製した。
Comparative Example 2
A test plate was prepared in the same manner as in Example 1 except that zircon hydrofluoric acid was not blended.
比較例３
ジルコンフッ化水素酸を配合せず、アミノ基含有シランカップリング剤としてサイラエースＳ−３３０を使用したこと以外は、実施例１と同様にして試験板を作製した。
Comparative Example 3
A test plate was prepared in the same manner as in Example 1, except that zircon hydrofluoric acid was not used and Silaace S-330 was used as an amino group-containing silane coupling agent.
比較例４〜８
表２に示した基材を使用して、脱脂後水洗処理の後にサーフファイン５Ｎ−８Ｍ（日本ペイント社製）を用いて室温で３０秒間表面調整を行い、サーフダインＳＤ−６３５０（日本ペイント社製リン酸亜鉛系化成処理剤）を用いて３５℃で２分間浸漬処理を行うことで化成処理を施したこと以外は実施例１と同様にして試験板を得た。
Comparative Examples 4 to 8
Using the base material shown in Table 2, after degreasing and rinsing, the surface was adjusted at room temperature for 30 seconds using Surffine 5N-8M (manufactured by Nippon Paint Co., Ltd.), and Surfdyne SD-6350 (Nippon Paint Co., Ltd.) was used. A test plate was obtained in the same manner as in Example 1 except that a chemical conversion treatment was performed by performing a soaking treatment at 35 ° C. for 2 minutes using a zinc phosphate-based chemical conversion treating agent.
実施例３６〜４０
表３に示した組成を有する化成処理剤及び基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「オルガセレクトＯＴＳ９００ホワイト」（日本ペイント社製溶剤塗料）を乾燥膜厚３５±２μｍになるように塗装し、１４０℃で３０分間加熱して焼き付けたこと以外は、実施例１と同様にして試験板を得た。
Examples 36 to 40
Using a chemical conversion treatment agent and a base material having the compositions shown in Table 3, "Orga Select OTS900 White" (solvent paint manufactured by Nippon Paint Co., Ltd.) instead of "Powernics 110" (cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.) Was coated in a dry film thickness of 35 ± 2 μm and baked by heating at 140 ° C. for 30 minutes in the same manner as in Example 1 to obtain a test plate.
比較例９〜１３
表３に示した基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「オルガセレクトＯＴＳ９００ホワイト」（日本ペイント社製溶剤塗料）を乾燥膜厚３５±２μｍになるように塗装し、１４０℃で３０分間加熱して焼き付けたこと以外は、比較例４と同様にして試験板を得た。
Comparative Examples 9 to 13
Using the base material shown in Table 3, "Olga Select OTS900 White" (solvent paint made by Nippon Paint Co.) was used instead of "Powernics 110" (cationic electrodeposition paint made by Nippon Paint Co.) in a dry film thickness of 35 ± 2 μm. , And baked by heating at 140 ° C. for 30 minutes to obtain a test plate in the same manner as in Comparative Example 4.
実施例４１〜４５
表３に示した組成を有する化成処理剤及び基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「オーデエコラインＯＥＬ１００」（日本ペイント社製水性塗料）を乾燥膜厚３５±２μｍになるように塗装し、１４０℃で３０分間加熱して焼き付けたこと以外は、実施例１と同様にして試験板を得た。
Examples 41 to 45
Using a chemical conversion treating agent and a base material having the compositions shown in Table 3, instead of "Powernics 110" (cationic electrodeposition paint made by Nippon Paint Co., Ltd.), "Audeko Line OEL100" (water paint made by Nippon Paint Co., Ltd.) Was coated in a dry film thickness of 35 ± 2 μm and baked by heating at 140 ° C. for 30 minutes in the same manner as in Example 1 to obtain a test plate.
比較例１４〜１８
表３に示した基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「オーデエコラインＯＥＬ１００」（日本ペイント社製水性塗料）を乾燥膜厚３５±２μｍになるように塗装し、１４０℃で３０分間加熱して焼き付けたこと以外は、比較例４と同様にして試験板を得た。
Comparative Examples 14 to 18
Using the base material shown in Table 3, "Ode Ecoline OEL100" (a water-based paint manufactured by Nippon Paint Co., Ltd.) was used instead of "Powernics 110" (a cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.) in a dry film thickness of 35 ± 2 μm. , And baked by heating at 140 ° C. for 30 minutes to obtain a test plate in the same manner as in Comparative Example 4.
実施例４６〜５０
表３に示した組成を有する化成処理剤及び基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「パウダックスＰ１００」（日本ペイント社製粉体塗料）を乾燥膜厚１００±５μｍになるように塗装し、１８０℃で２０分間加熱して焼き付けたこと以外は、実施例１と同様にして試験板を得た。
Examples 46 to 50
Using a chemical conversion treating agent and a base material having the compositions shown in Table 3, "Powax P100" (powder paint manufactured by Nippon Paint Co., Ltd.) was used instead of "Powernics 110" (cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.). A test plate was obtained in the same manner as in Example 1 except that the coating was performed so as to have a dry film thickness of 100 ± 5 μm, and the coating was heated and baked at 180 ° C. for 20 minutes.
比較例１９〜２３
表３に示した基材を使用し、「パワーニクス１１０」（日本ペイント社製カチオン電着塗料）に代えて「パウダックスＰ１００」（日本ペイント社製粉体塗料）を乾燥膜厚１００±５μｍになるように塗装し、１８０℃で２０分間加熱して焼き付けたこと以外は、比較例４と同様にして試験板を得た。
Comparative Examples 19 to 23
Using the base material shown in Table 3, "Powax P100" (powder paint manufactured by Nippon Paint Co., Ltd.) was used instead of "Powernics 110" (cationic electrodeposition paint manufactured by Nippon Paint Co., Ltd.) to a dry film thickness of 100 ± 5 μm. A test plate was obtained in the same manner as in Comparative Example 4, except that the coating was performed as described above, and baking was performed by heating at 180 ° C. for 20 minutes.
表１〜３より実施例で使用した化成処理剤中にスラッジは発生しないことが示された。更に、本発明の塗装前処理方法により得られた化成皮膜は、各種塗装による塗膜との良好な密着性を有することが示された。一方、比較例においては、化成処理剤中のスラッジの発生を抑え、かつ、塗膜との密着性に優れる化成皮膜を得ることはできなかった。 From Tables 1 to 3, it was shown that no sludge was generated in the chemical conversion treatment agents used in the examples. Furthermore, it was shown that the chemical conversion coating obtained by the coating pretreatment method of the present invention had good adhesion to coatings by various coatings. On the other hand, in the comparative example, the formation of sludge in the chemical conversion treatment agent was suppressed, and a chemical conversion film excellent in adhesion to the coating film could not be obtained.
本発明により、環境に対する負荷が少なく、鉄、亜鉛、アルミニウム等のすべての金属に良好な化成処理を行なうことができる塗装前処理方法を得ることができた。また、本発明の塗装前処理方法は、表面調整を行わなくても良好な化成皮膜を形成することができることから、作業性及びコストの面でも優れている。 ADVANTAGE OF THE INVENTION According to this invention, the load to environment was small and the coating pretreatment method which can perform favorable chemical conversion treatment to all metals, such as iron, zinc, and aluminum, was able to be obtained. Further, the coating pretreatment method of the present invention is excellent in workability and cost since a good chemical conversion film can be formed without performing surface adjustment.
Claims (4)
前記化成処理剤は、ジルコニウム、チタン及びハフニウムからなる群より選ばれる少なくとも一種、フッ素、並びに、アミノ基含有シランカップリング剤、その加水分解物及びその重合物からなる群より選ばれる少なくとも一種からなる
ことを特徴とする塗装前処理方法。 A coating pretreatment method for treating an object to be treated with a chemical conversion treatment agent to form a chemical conversion film,
The chemical conversion treatment agent is at least one selected from the group consisting of zirconium, titanium and hafnium, fluorine, and at least one selected from the group consisting of amino group-containing silane coupling agents, hydrolysates thereof, and polymers thereof. A coating pretreatment method characterized by the following.
Priority Applications (11)
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| JP2003403688A JP4989842B2 (en) | 2002-12-24 | 2003-12-02 | Pre-painting method |
| CA2454042A CA2454042C (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| KR1020030095382A KR20040058039A (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| PT03293300T PT1433877E (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| ES03293300T ES2316706T3 (en) | 2002-12-24 | 2003-12-23 | METHOD OF PRE-TREATMENT TO COVER. |
| EP03293300A EP1433877B1 (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| TW092136468A TW200420754A (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| AT03293300T ATE412073T1 (en) | 2002-12-24 | 2003-12-23 | METHOD FOR PRE-TREATMENT BEFORE COATING |
| DE60324245T DE60324245D1 (en) | 2002-12-24 | 2003-12-23 | Pretreatment process prior to coating |
| US10/743,387 US8075708B2 (en) | 2002-12-24 | 2003-12-23 | Pretreatment method for coating |
| CN200310113012A CN100575552C (en) | 2002-12-24 | 2003-12-24 | The pretreatment process that is used to apply |
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