CN110698961B - Chromium-free metal surface treatment agent, metal surface treatment method and metal base material - Google Patents
Chromium-free metal surface treatment agent, metal surface treatment method and metal base material Download PDFInfo
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- CN110698961B CN110698961B CN201910557119.1A CN201910557119A CN110698961B CN 110698961 B CN110698961 B CN 110698961B CN 201910557119 A CN201910557119 A CN 201910557119A CN 110698961 B CN110698961 B CN 110698961B
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- surface treatment
- metal surface
- chromium
- component
- treatment agent
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 103
- 239000002184 metal Substances 0.000 title claims abstract description 103
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 55
- 238000004381 surface treatment Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims description 18
- 125000002091 cationic group Chemical group 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 15
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000077 silane Inorganic materials 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000003755 zirconium compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 abstract description 13
- 230000007797 corrosion Effects 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 22
- 239000000126 substance Substances 0.000 description 21
- 229910000831 Steel Inorganic materials 0.000 description 18
- 239000010959 steel Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- -1 zirconium ions Chemical class 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910001335 Galvanized steel Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000008397 galvanized steel Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002987 primer (paints) Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- OYWKBIVCHPPAOQ-UHFFFAOYSA-N 1-triethoxysilyl-n-(triethoxysilylmethyl)methanamine Chemical compound CCO[Si](OCC)(OCC)CNC[Si](OCC)(OCC)OCC OYWKBIVCHPPAOQ-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- RWLDCNACDPTRMY-UHFFFAOYSA-N 3-triethoxysilyl-n-(3-triethoxysilylpropyl)propan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCNCCC[Si](OCC)(OCC)OCC RWLDCNACDPTRMY-UHFFFAOYSA-N 0.000 description 1
- TZZGHGKTHXIOMN-UHFFFAOYSA-N 3-trimethoxysilyl-n-(3-trimethoxysilylpropyl)propan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCCC[Si](OC)(OC)OC TZZGHGKTHXIOMN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- MJUYLLSQJYPIDA-UHFFFAOYSA-N NC[N+](C(N(C)C)(NCC)NC)(C)N(CC)CC Chemical compound NC[N+](C(N(C)C)(NCC)NC)(C)N(CC)CC MJUYLLSQJYPIDA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910009257 Y—Si Inorganic materials 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- NRYWFNLVRORSCA-UHFFFAOYSA-N triethoxy(6-triethoxysilylhexyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCC[Si](OCC)(OCC)OCC NRYWFNLVRORSCA-UHFFFAOYSA-N 0.000 description 1
- OSAJVUUALHWJEM-UHFFFAOYSA-N triethoxy(8-triethoxysilyloctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCC[Si](OCC)(OCC)OCC OSAJVUUALHWJEM-UHFFFAOYSA-N 0.000 description 1
- XWPXMMSMCXBBGE-UHFFFAOYSA-N triethoxy(9-triethoxysilylnonyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCC[Si](OCC)(OCC)OCC XWPXMMSMCXBBGE-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 1
- GFKCWAROGHMSTC-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexyl)silane Chemical compound CO[Si](OC)(OC)CCCCCC[Si](OC)(OC)OC GFKCWAROGHMSTC-UHFFFAOYSA-N 0.000 description 1
- SHCGUUKICQTMGF-UHFFFAOYSA-N trimethoxy(8-trimethoxysilyloctyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCC[Si](OC)(OC)OC SHCGUUKICQTMGF-UHFFFAOYSA-N 0.000 description 1
- MBIWXZXQMMLFAB-UHFFFAOYSA-N trimethoxy(9-trimethoxysilylnonyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCC[Si](OC)(OC)OC MBIWXZXQMMLFAB-UHFFFAOYSA-N 0.000 description 1
- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
A chromium-free metal surface treatment agent comprising (A) a multi-silyl functional silane, (B) an amino group-containing silane coupling agent, (C) inorganic compound particles, and (D) at least one resin selected from the group consisting of aqueous cationic urethane resins and aqueous cationic acrylic resins, wherein the mass ratio of silicon in the component (A) and the component (B) to the resin solid content in the component (D) (resin solid content/silicon) is in the range of 1 to 5, a metal surface treatment method using the chromium-free metal surface treatment agent, and a metal substrate subjected to surface treatment.
Description
Technical Field
The invention relates to a chromium-free metal surface treatment agent, a metal surface treatment method and a metal substrate.
Background
Conventionally, chromium-based metal surface treatment agents such as chromate treatment agents and phosphoric acid-chromate treatment agents have been known as surface treatment agents for imparting corrosion resistance to metal substrates, and are still widely used at present. However, in view of the recent environmental restrictions, chromium may be used in limited ways in the future due to its toxicity, particularly carcinogenicity.
Therefore, various chromium-free metal surface treatment agents have been developed which exhibit corrosion resistance equivalent to that of chromium-based metal surface treatment agents.
For example, patent document 1 discloses a chromium-free metal surface treatment agent for precoated steel sheets (PCM), which comprises 1 liter of a metal surface treatment agent and, incorporated therein, 0.01 to 100g/L of a silane coupling agent and a hydrolysis condensate thereof, (b) 0.05 to 100g/L of water-dispersible silica (solid component), (c) 0.01 to 50g/L of a zirconium compound in terms of zirconium ions and/or 0.01 to 50g/L of a titanium compound in terms of titanium ions.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4393660
Disclosure of Invention
Problems to be solved by the invention
However, when a film is formed on a metal substrate using a chromium-free metal surface treatment agent, the formed film is required to have not only corrosion resistance but also adhesion to the metal substrate and top coat coating, chemical resistance, and the like. In particular, in the production of a precoated steel sheet (PCM), since a surface treatment is performed before the forming of a metal base material, the processed portion is required to exhibit corrosion resistance and adhesion.
However, the corrosion resistance, adhesion, and chemical resistance of a coating film formed by a conventional chromium-free metal surface treatment agent are not sufficient, and there is room for improvement.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a chromium-free metal surface treatment agent capable of forming a coating film excellent in corrosion resistance, adhesion, and chemical resistance on a metal base material. Further, the present invention aims to provide a metal surface treatment method using the chromium-free metal surface treatment agent and a metal substrate subjected to surface treatment.
Means for solving the problems
The present invention relates to a chromium-free metal surface treating agent comprising the following components (A), (B), (C) and (D);
(A) multi-silyl functional silanes
(B) Silane coupling agent containing amino group
(C) Inorganic compound particles
(D) At least one resin selected from the group consisting of water-based cationic urethane resins and water-based cationic acrylic resins,
the mass ratio of silicon in the components (A) and (B) to the resin solid in the component (D) (resin solid/silicon) is in the range of 1 to 5.
Preferably, the mass ratio of the component (a) to the component (B), (component (a)/(component B), is in the range of 0.2 to 8.7.
Preferably, the component (a) is 1, 2-bis (triethoxysilyl) -ethane.
Preferably, the component (B) is at least one selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane.
Preferably, the component (C) is at least one selected from the group consisting of particles of a zirconium compound and particles of a titanium compound.
The average particle diameter of the component (C) is preferably 1 μm or less.
The present invention also relates to a metal surface treatment method including the steps of: a step of applying the chromium-free metal surface treatment agent to the surface of a metal substrate; and a step of drying the chromium-free metal surface treatment agent applied to the metal base material to form a coating film.
The present invention also relates to a metal substrate having a coating film of the chromium-free metal surface treatment agent.
Effects of the invention
According to the present invention, a chromium-free metal surface treatment agent capable of forming a coating film excellent in corrosion resistance, adhesion, and chemical resistance on a metal base material can be provided. In addition, the present invention provides a metal surface treatment method using the chromium-free metal surface treatment agent and a metal substrate subjected to surface treatment.
Detailed Description
The chromium-free metal surface treatment agent, the metal surface treatment method, and the metal base material according to the present embodiment will be described in detail below.
< chromium-free Metal surface treating agent >
The chromium-free metal surface treatment agent according to the present embodiment contains the following components (a), (B), (C), and (D);
(A) multi-silyl functional silanes
(B) Silane coupling agent containing amino group
(C) Inorganic compound particles
(D) At least one resin selected from the group consisting of water-based cationic urethane resins and water-based cationic acrylic resins,
(A) the mass ratio of silicon in the component (B) and the resin solid in the component (D) (resin solid/silicon) is in the range of 1 to 5.
According to the chromium-free metal surface treatment agent of the present embodiment, a coating film having excellent corrosion resistance, adhesion, and chemical resistance can be formed on a metal base material. In particular, the coating film formed using the chromium-free metal surface treatment agent according to the present embodiment exhibits good corrosion resistance and adhesion even in the processed portion. Therefore, the chromium-free metal surface treatment agent according to the present embodiment is suitable as a coating base in producing a precoated steel sheet (PCM), for example.
[ (A) Polysilyl-functional silanes ]
The multi-silyl functional silane as the component (a) includes, for example, a compound having a plurality of silyl groups that can be hydrolyzed to form silanol groups. Preferred polysilyl-functional silanes include, for example, compounds represented by the following formula (I).
[ solution 1]
(X 1 ) 3-a-b (R 1 ) a (R 2 ) b Si-Y-Si(R 3 ) d (R 4 ) d (X 2 ) 3-c-d …(I)
In the above formula (I), R 1 、R 2 、R 3 And R 4 Each independently represents a hydrogen atom or a 1-valent organic group having 1 to 30 carbon atoms. As the 1-valent organic group, there may be mentioned: alkyl, alkenyl, cycloalkyl, aryl, and other hydrocarbon groups; and hydrocarbon groups having a functional group such as a hydroxyl group, an epoxy group, or an amino group, preferably alkyl groups having 1 to 4 carbon atoms such as methyl group or ethyl group.
In the formula (I), Y represents a 2-valent organic group or an amine. As the organic group having a valence of 2, there may be mentioned an alkylene group, an alkyleneoxy group, an alkylenethio group or a group containing these as a partial structure, with an alkylene group being preferred. The number of carbon atoms of the 2-valent organic group is preferably 2 to 30, more preferably 2 to 12.
In the above formula (I), X 1 And X 2 Each independently represents a hydrolyzable group. The hydrolyzable group includes an alkoxy group having 1 to 4 carbon atoms, and preferably a methoxy group or an ethoxy group.
In the formula (I), a and b independently represent an integer of 0 to 2, and a + b is not less than 0 and not more than 2. In addition, c and d independently represent an integer of 0 to 2, and c + d is 0. ltoreq. c + d. ltoreq.2. a + b and c + d are each preferably 0 or 1.
Specific examples of the polysilyl-functional silane represented by the above formula (I) include: bis (trimethoxysilyl) methane, 1, 2-bis (trimethoxysilyl) ethane, 1, 2-bis (triethoxysilyl) ethane, 1, 6-bis (trimethoxysilyl) hexane, 1, 6-bis (triethoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, 1, 8-bis (triethoxysilyl) octane, 1, 9-bis (trimethoxysilyl) nonane, 1, 9-bis (triethoxysilyl) nonane, bis (trimethoxysilyl) amine, bis (triethoxysilyl) amine, bis (trimethoxysilylmethyl) amine, bis (triethoxysilylmethyl) amine, bis (trimethoxysilylpropyl) amine, bis (triethoxysilylpropyl) amine, and the like. Among these, 1, 2-bis (triethoxysilyl) ethane is preferable from the viewpoint of safety in handling, corrosion resistance of the obtained coating film, and adhesion.
These multi-silyl functional silanes may be used singly or in combination of two or more. In addition, the polysilyl-functional silanes may also be partially hydrolytically condensed.
(A) The content of the component (b) is not particularly limited, but is preferably 0.4 to 2.4% by mass, more preferably 0.6 to 1.7% by mass, based on the total amount of the chromium-free metal surface treatment agent according to the present embodiment. When the content of the component (a) is 0.4% by mass or more, the corrosion resistance, adhesion to a metal substrate, and chemical resistance of the obtained coating film tend to be further improved. On the other hand, when the content of the component (a) is 2.4% by mass or less, the adhesion of the obtained coating film to the metal base material tends to be improved.
[ (B) silane coupling agent having amino group ]
As the silane coupling agent containing an amino group as the component (B), a conventionally known silane coupling agent having an amino group can be used without particular limitation. Specific examples of the amino group-containing silane coupling agent include: 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like. Of these, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane are preferable.
These amino group-containing silane coupling agents may be used alone or in combination of two or more. In addition, the silane coupling agent containing an amino group may be partially subjected to hydrolytic condensation.
(B) The content ratio of the component (A) to the component (B) is not particularly limited, and the mass ratio of the component (A) to the component (B), (component (A)/(component B)), is preferably in the range of 0.2 to 8.7, and more preferably in the range of 0.5 to 3.0. When the mass ratio ((a) component/(B) component) is 0.2 or more, the corrosion resistance, adhesion to a metal substrate, and chemical resistance of the obtained coating film tend to be further improved. On the other hand, when the mass ratio ((a) component/(B) component) is 8.7 or less, the adhesion of the obtained coating film to the top coat coating tends to be further improved.
[ (C) particles of an inorganic Compound ]
Examples of the inorganic compound particles as the component (C) include zirconium compound particles and titanium compound particles. By containing the particulate inorganic compound, the corrosion resistance and chemical resistance of the obtained coating film tend to be improved as compared with the case where the coating film contains a non-particulate inorganic compound.
Examples of the zirconium compound include zirconium oxide. Examples of the titanium compound include titanium oxide. These inorganic compound particles may be used alone or in combination of two or more.
The average particle diameter (D50) of the inorganic compound particles is preferably 1 μm or less, and more preferably 10 to 300 nm.
Commercially available inorganic compound particles may be used. Examples of commercially available zirconium compound particles include "ZSL-20N", "ZSL-10A", "ZSL-10T", "EP zirconia", "UEP zirconia" and "UEP-100 zirconia" (manufactured by first Dilute elements chemical Co., Ltd.). Further, as commercially available products of titanium compound particles, there can be mentioned: "CSB", "CSB-M", "SSP-25", "SSP-20", "SSP-M", "STA-100A" (made by Sakai chemical industry Co., Ltd.); "DC-Ti", "DCN-Ti" and "DCB-Ti" (manufactured by Fuji titanium industries Co., Ltd.).
(C) The content of the component is not particularly limited, and is preferably 9.0 to 16.0 mass% based on the total solid content of the chromium-free metal surface treatment agent according to the present embodiment. When the content of the component (C) is 9.0 mass% or more, the chemical resistance of the obtained coating film tends to be improved. On the other hand, when the content of the component (C) is 16.0 mass% or less, the corrosion resistance and adhesion to the metal base material of the obtained coating film tend to be improved.
[ (D) at least one resin selected from the group consisting of aqueous cationic urethane resins and aqueous cationic acrylic resins ]
The aqueous cationic urethane resin and the aqueous cationic acrylic resin as the component (D) have cationic functional groups that can be cationized in an aqueous medium, such as primary to tertiary amino groups, ammonium groups, sulfonium groups, and phosphonium groups, in their molecular structures. Specific examples of the cationic functional group include: amino, methylamino, ethylamino, dimethylamino, diethylamino, trimethylammonium, triethylammonium, and the like.
The water-based cationic urethane resin and the water-based cationic acrylic resin are preferably added to the chromium-free metal surface treatment agent in the form of a finely dispersed emulsion in water.
Examples of the aqueous cationic urethane resin include: in urethane resins obtained by polymerizing a polyol such as a polyether polyol, a polyester polyol, a polycarbonate polyol, a polycaprolactone polyol, or a castor oil polyol with an aliphatic, alicyclic, or aromatic polyisocyanate, a polyol obtained by replacing a part of the polyol with a cationic functional group such as a primary to tertiary amino group or an ammonium group is used.
As the aqueous cationic urethane resin, a commercially available product can be used. Examples of commercially available products of the aqueous cationic urethane resin include "F-2667D" and "SUPERFLEX 650" (manufactured by first Industrial pharmaceutical Co., Ltd.); "テックコート WH-1515" (manufactured by Kanji Kabushiki Kaisha K.K.).
Examples of the aqueous cationic acrylic resin include copolymers of a (meth) acrylate having a cationic functional group such as an amino group-containing (meth) acrylate or a quaternary ammonium group-containing (meth) acrylate and other polymerizable unsaturated monomers. Examples of the amino group-containing (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N-dimethylaminopropyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N-methylaminopropyl (meth) acrylate. Examples of the (meth) acrylate containing a quaternary ammonium group include (meth) acryloyloxyethyltrimethyl ammonium chloride.
As the aqueous cationic acrylic resin, commercially available products can be used. As a commercially available product of the aqueous cationic acrylic resin, there can be mentioned: "UW-550 CS" and "UW-600" (manufactured by Dachen Fine chemical Co., Ltd.); "ACE-6" (manufactured by chemical research in Yam, village, K.K.) and the like.
Among the water-based cationic urethane resin and the water-based cationic acrylic resin, a water-based cationic urethane resin having a double bond in the structure is preferable. Since the aqueous cationic urethane resin having a double bond in the molecular structure has high hydrophobicity, the corrosion resistance of the obtained coating film, the adhesion to the top coat coating, and the like tend to be further improved.
The commercially available product of the aqueous cationic urethane resin having a double bond in its structure includes "F-2667D" (manufactured by first Industrial pharmaceutical Co., Ltd.).
The component (D) is contained in an amount such that the mass ratio of silicon in the components (A) and (B) to the resin solid in the component (D) (resin solid/silicon) is in the range of 1 to 5. When the mass ratio (resin solid content/silicon) is 1 or more, the corrosion resistance, adhesion, and chemical resistance (particularly alkali resistance) of the obtained coating film tend to be further improved. On the other hand, when the mass ratio (resin solid content/silicon) is 5 or less, the chemical resistance (particularly, acid resistance) of the obtained coating film tends to be further improved.
The chromium-free metal surface treatment agent according to the present embodiment may further contain a resin other than the water-based cationic urethane resin and the water-based cationic acrylic resin. The content of the other resin is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 0% by mass, based on the total amount of the resin.
[ other ingredients ]
The chromium-free metal surface treatment agent according to the present embodiment may further contain other components in addition to the above components. Examples of the other components include a resin crosslinking agent for accelerating the curing of the resin, a surface conditioner for leveling purposes, and a defoaming agent for foam suppressing purposes.
[ pH of chromium-free Metal surface treatment agent ]
The pH of the chromium-free metal surface treatment agent according to the present embodiment is preferably 7 or less, and more preferably 4 to 7. When the pH of the chromium-free metal surface treatment agent is 7 or less, the storage stability is further improved, and the chemical resistance (particularly, alkali resistance) of the obtained coating film tends to be further improved.
< method for treating metal surface >
The metal surface treatment method according to the present embodiment includes the steps of: a step of applying the chromium-free metal surface treatment agent according to the present embodiment to the surface of the metal base material (hereinafter, also referred to as "applying step"); and a step of drying the chromium-free metal surface treatment agent applied to the metal base material to form a coating film (hereinafter also referred to as "drying step").
In the applying step, the chromium-free metal surface treatment agent according to the present embodiment described above is applied to a metal substrate.
Examples of the metal base include a hot dip galvanized steel material, a galvanized steel material, an aluminum-zinc alloy-plated steel material, an aluminum material, and stainless steel.
The method for applying the chromium-free metal surface treatment agent to the metal material is not particularly limited, and examples thereof include roll coater coating, brush coating, roll coating, bar coater coating, flow coating, and the like.
In the drying step, the chromium-free metal surface treatment agent applied to the metal base material is dried to form a coating film.
The drying temperature is, for example, preferably 50 to 150 ℃, more preferably 60 to 100 ℃.
The imparting step and the drying step may be performed simultaneously and in parallel. For example, a chromium-free metal surface treatment agent may be applied to a metal substrate heated in advance, and the chromium-free metal surface treatment agent may be dried by using waste heat.
The amount of the coating film to be adhered is preferably, for example, 0.01 to 1.0g/m 2 More preferably 0.04 to 0.6/m 2 . By setting the amount of adhesion to 0.01g/m 2 As described above, the corrosion resistance and chemical resistance tend to be further improved. Further, the amount of the deposit was set to 1.0g/m 2 Hereinafter, corrosion resistance (particularly corrosion resistance of a processed portion) and adhesion tend to be further improved.
In the production of a precoated steel sheet (PCM), for example, a primer coating may be applied to the formed coating film, and then a topcoat coating may be applied. As both the primer coating and the topcoat coating, a chromium-free coating is preferable.
< Metal substrate >
The metal substrate according to the present embodiment has a coating film of the chromium-free metal surface treatment agent according to the present embodiment. The metal substrate according to the present embodiment can be obtained by the metal surface treatment method according to the present embodiment described above.
[ examples ]
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
< preparation of chromium-free Metal surface treating agent >
Examples 1 to 17, 24 to 33 and comparative examples 1 to 14
The component (A) was mixed with 100g of ion-exchanged water in the types and amounts (unit: g) shown in tables 1 and 2, and the pH was adjusted to 6 with acetic acid. The resulting solution was mixed with component (B), component (C) and component (D) in this order and stirred to obtain chromium-free metal surface treatment agents of examples 1 to 17, 24 to 33 and comparative examples 1 to 14.
[ examples 18 to 23]
The component (A) was mixed with 100g of ion-exchanged water in the type and amount (unit: g) shown in Table 1, and the pH was adjusted to 6 with acetic acid. The resulting solution was mixed with component (B), component (C) and component (D) in this order and stirred. Further, the pH was adjusted to the pH shown in Table 1 with acetic acid or 25 mass% aqueous ammonia to obtain each of the chromium-free metal surface treatment agents of examples 18 to 23.
[ Table 1]
[ Table 2]
The abbreviations in tables 1 and 2 have the following meanings.
(Polysilyl-functional silanes)
A1: 1, 2-bis (triethoxysilyl) ethane (manufactured by shin-Etsu chemical Co., Ltd., "KBE-3026")
A2: vinyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd., "KBM-1003")
(silane coupling agent)
B1: 3-aminopropyltriethoxysilane (KBE-903, product of shin-Etsu chemical Co., Ltd.)
B2: 3-aminopropyltrimethoxysilane (product of shin-Etsu chemical Co., Ltd., "KBM-903")
B3: n-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, product of shin-Etsu chemical Co., Ltd.)
B4: n-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd., "KBM-602")
B5: vinyltrimethoxysilane (manufactured by shin-Etsu chemical Co., Ltd., "KBM-1003")
B6: 3-glycidoxypropyltrimethoxysilane (KBM-403, product of shin-Etsu chemical Co., Ltd.)
(inorganic Compound)
C1: zirconium compound particles (ZSL-20N, product of first Dilute elements Chemicals Co., Ltd., "ZSL-20N", particle diameter: 60 to 105nm, solid content concentration: 20% by mass)
C2: titanium compound particles (made by Sakai chemical industry Co., Ltd., "CSB-M", particle diameter: 7nm, solid concentration: 30% by mass)
C3: zirconium compound particles (EP zirconia, first rare element chemical Co., Ltd., "EP zirconia", average particle diameter: 1.5 to 2.5 μm, solid content concentration: 100% by mass)
C4: zirconium Compound (first Dilute element chemical Co., Ltd., "ZIRCOZOLE AC-7", solid content concentration: 20% by mass)
C5: silica particles (manufactured by ADEKA, "ADELITE AT-20A", manufactured by K.K.; particle diameter: 10-20 nm, solid content concentration: 20% by mass)
(resin)
D1: aqueous cationic urethane resin (first Industrial pharmaceutical Co., Ltd., "F-2667D", solid content concentration: 25% by mass)
D2: aqueous cationic urethane resin (first Industrial pharmaceutical Co., Ltd., "SUPERFLEX 650", solid content concentration: 26% by mass)
D3: water-based cationic acrylic resin (available from Dacheng Fine chemical Co., Ltd., "UW-550 CS", solid content concentration: 34% by mass)
D4: aqueous anionic urethane resin (manufactured by ADEKA, Inc.; "HUX-320", solid content concentration: 32% by mass)
D5: aqueous nonionic urethane resin (first Industrial pharmaceutical Co., Ltd., "SUPERFLEX 500M", solid content concentration: 45% by mass)
D6: water-based anionic acrylic resin (available from SAIDEN chemical Co., Ltd., "AD-7", solid content concentration: 39% by mass)
< evaluation >
The chromium-free metal surface treatment agents of examples 1 to 33 and comparative examples 1 to 14 were used to evaluate corrosion resistance, adhesion, chemical resistance and storage stability as described below. The results are shown in tables 3 and 4.
[ production of test plate ]
The steel sheets shown in tables 3 and 4 were degreased by spraying an alkali degreaser (manufactured by Nippon Paint Surf Chemical, "Surf cleaner 155") at 60 ℃ for 1 minute. The degreased steel plate is washed with water and then dried. Then, the chromium-free metal surface treatment agents of examples 1 to 33 and comparative examples 1 to 14 were applied to the surface of the steel sheet by a bar coater so that the amount of the coating film adhered was the value shown in tables 1 and 2, and were baked and dried until the arrival temperature of the steel sheet became 90 ℃. Next, a chromium-free primer coating and a chromium-free topcoat coating (both manufactured by Nippon Paint Industrial Coatings Co., Ltd.) were applied to the steel sheet, respectively, to obtain a coated steel sheet.
[ evaluation of Corrosion resistance ]
A salt solution of 35 ℃ and 5 w/v% was sprayed on the coated surface of the coated steel sheet. After 1000 hours from the start of the salt solution spray, the proportion (%) of the area where white rust was generated was visually observed to evaluate the corrosion resistance. Two points, namely a plane part and a bending part, are evaluated, wherein the bending part is formed by folding 2 plates in half and performing bending processing (2T processing).
The evaluation criteria are as follows. If the score is 3 or more based on the evaluation criterion, the product is qualified.
Evaluation criteria-
And 4, dividing: no white rust generation
And 3, dividing: the area generating white rust is less than 10 percent
And 2, dividing: the area of white rust is more than 10% and less than 30%
1 minute: the area of white rust generation is more than 30%
[ evaluation of adhesion ]
The coated steel sheet was subjected to 180 ° bending (0T processing). Then, after the adhesive tape was adhered to the coated surface of the folded portion, the tape was peeled off, and the ratio (%) of the area where the coating was peeled off was visually observed to evaluate the adhesion.
The evaluation criteria are as follows. If the score is 3 or more based on the evaluation criterion, the product is qualified.
Evaluation criteria-
And 4, dividing: without peeling
And 3, dividing: the area of stripping is less than 25 percent
And 2, dividing: the stripping area is more than 26% and less than 50%
1 minute: the peeled area is more than 50%
[ evaluation of chemical resistance ]
a) Evaluation of acid resistance
The coated steel sheet was immersed in a 5 w/v% sulfuric acid aqueous solution at 25 ℃ for 24 hours, and the acid resistance was evaluated by visually checking the ratio (%) of the area of the coating film in which swelling occurred.
The evaluation criteria are as follows. If the score is 3 or more based on the evaluation criterion, the product is qualified.
Evaluation criteria-
And 4, dividing: without expansion
And 3, dividing: the area generating the expansion is less than 25 percent
And 2, dividing: the area of the expansion is more than 25 percent and less than 50 percent
1 minute: the area of expansion is 50% or more
b) Evaluation of alkali resistance
The coated steel sheet was immersed in a 5 w/v% aqueous solution of sodium hydroxide at 25 ℃ for 24 hours, and the alkali resistance was evaluated by visually checking the ratio (%) of the area of the coating film in which swelling occurred.
The evaluation criteria are as follows. If the score is 3 or more based on the evaluation criterion, the product is qualified.
Evaluation criteria-
And 4, dividing: without expansion
And 3, dividing: the area generating the expansion is less than 25 percent
And 2, dividing: the area of the expansion is more than 25 percent and less than 50 percent
1 minute: the area of expansion is 50% or more
[ evaluation of storage stability ]
The chromium-free metal surface treatment agents of examples 1 to 33 and comparative examples 1 to 14 were stored in a thermostatic apparatus at 40 ℃ for 3 months, and the storage stability was evaluated by visually observing the states of gelation and precipitation.
The evaluation criteria are as follows. If the rating is 2 points, the product is qualified.
Evaluation criteria-
And 2, dividing: no gelation and precipitation were observed
1 minute: gelation or precipitation was confirmed
[ Table 3]
[ Table 4]
The abbreviations in tables 3 and 4 have the following meanings.
(Steel plate)
GL: aluminum-zinc alloy plated steel sheet (Al: 55 mass%)
GI: hot dip galvanized steel sheet
GF: aluminum-zinc alloy plated steel sheet (Al: 5 mass%)
EG: galvanized steel sheet
SUS: stainless steel plate
AL: aluminium plate
As shown in tables 3 and 4, examples 1 to 33 used chromium-free metal surface treatment agents containing (a) a multi-silyl functional silane, (B) an amino group-containing silane coupling agent, (C) inorganic compound particles, and (D) at least one selected from the group consisting of aqueous cationic urethane resins and aqueous cationic acrylic resins, and having a mass ratio of silicon in the component (a) and the component (B) to a resin solid in the component (D) (resin solid/silicon) in the range of 1 to 5, and were excellent in corrosion resistance, adhesion, chemical resistance, and storage stability. In contrast, comparative examples 1 to 14 using chromium-free metal surface treatment agents that do not satisfy some of the conditions were inferior to examples 1 to 33 in the evaluation of at least 1 of corrosion resistance, adhesion, chemical resistance, and storage stability.
Claims (6)
1. A chromium-free metal surface treating agent comprising the following components (A), (B), (C) and (D);
(A) a multi-silyl-functional silane,
(B) A silane coupling agent containing amino,
(C) Inorganic compound particles,
(D) At least one resin selected from the group consisting of water-based cationic urethane resins and water-based cationic acrylic resins,
the ratio of the mass of the resin solid component in the component (D) to the total mass of the silicon in the components (A) and (B) is in the range of 1 to 5,
the component (C) is at least one selected from zirconium compound particles and titanium compound particles, and has an average particle diameter of 10 to 300nm,
the content of the component (C) is 9.0-16.0 mass% of the total solid content of the chromium-free metal surface treatment agent.
2. The chromium-free metal surface treatment agent according to claim 1, wherein the ratio of the mass of the component (A) to the mass of the component (B) is in the range of 0.2 to 8.7.
3. The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the component (a) is 1, 2-bis (triethoxysilyl) ethane.
4. The chromium-free metal surface treatment agent according to claim 1 or 2, wherein the component (B) is at least one selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane.
5. A metal surface treatment method comprises the following steps: a step of applying the chromium-free metal surface treatment agent according to any one of claims 1 to 4 to the surface of a metal substrate; and
and a step of drying the chromium-free metal surface treatment agent applied to the metal base material to form a coating film.
6. A metal substrate having a coating film of the chromium-free metal surface treatment agent according to any one of claims 1 to 4.
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| TW202006186A (en) | 2020-02-01 |
| TWI835814B (en) | 2024-03-21 |
| CN110698961A (en) | 2020-01-17 |
| JP7101066B2 (en) | 2022-07-14 |
| JP2020007617A (en) | 2020-01-16 |
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