EP3662024A1 - Härtbare oberflächenschutzbeschichtungszusammensetzung, verfahren zu ihrer herstellung und anwendung auf einem metallischen substrat und daraus resultierendes beschichtetes metallisches substrat - Google Patents
Härtbare oberflächenschutzbeschichtungszusammensetzung, verfahren zu ihrer herstellung und anwendung auf einem metallischen substrat und daraus resultierendes beschichtetes metallisches substratInfo
- Publication number
- EP3662024A1 EP3662024A1 EP18750574.8A EP18750574A EP3662024A1 EP 3662024 A1 EP3662024 A1 EP 3662024A1 EP 18750574 A EP18750574 A EP 18750574A EP 3662024 A1 EP3662024 A1 EP 3662024A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- forming composition
- coating forming
- group
- coating
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims description 39
- 230000008569 process Effects 0.000 title claims description 18
- 239000011253 protective coating Substances 0.000 title abstract description 14
- 239000000758 substrate Substances 0.000 title description 25
- 238000002360 preparation method Methods 0.000 title description 5
- 238000000576 coating method Methods 0.000 claims abstract description 186
- 239000011248 coating agent Substances 0.000 claims abstract description 175
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 87
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 94
- 239000003054 catalyst Substances 0.000 claims description 65
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000009833 condensation Methods 0.000 claims description 30
- 230000005494 condensation Effects 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- -1 glycidoxy Chemical group 0.000 claims description 24
- 230000007797 corrosion Effects 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005299 abrasion Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 14
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- LJOODBDWMQKMFB-UHFFFAOYSA-N cyclohexylacetic acid Chemical compound OC(=O)CC1CCCCC1 LJOODBDWMQKMFB-UHFFFAOYSA-N 0.000 claims description 8
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 8
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005639 Lauric acid Substances 0.000 claims description 7
- 235000021314 Palmitic acid Nutrition 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- STGNLGBPLOVYMA-UHFFFAOYSA-N C(C=C/C(=O)O)(=O)O.C(C=CC(=O)O)(=O)O Chemical compound C(C=C/C(=O)O)(=O)O.C(C=CC(=O)O)(=O)O STGNLGBPLOVYMA-UHFFFAOYSA-N 0.000 claims description 4
- NMEZJSDUZQOPFE-UHFFFAOYSA-N Cyclohex-1-enecarboxylic acid Chemical compound OC(=O)C1=CCCCC1 NMEZJSDUZQOPFE-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 4
- 235000001014 amino acid Nutrition 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims description 4
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 claims description 4
- JLRBNGCMXSGALP-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O.CCCCCCC(O)=O JLRBNGCMXSGALP-UHFFFAOYSA-N 0.000 claims description 4
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 claims description 4
- ZILMEHNWSRQIEH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O.CCCCCC(O)=O ZILMEHNWSRQIEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 229960003424 phenylacetic acid Drugs 0.000 claims description 4
- HJSRRUNWOFLQRG-UHFFFAOYSA-N propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)CC(O)=O HJSRRUNWOFLQRG-UHFFFAOYSA-N 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 3
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 3
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 3
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 claims description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 3
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 claims description 3
- HILHCDFHSDUYNX-UHFFFAOYSA-N trimethoxy(pentyl)silane Chemical compound CCCCC[Si](OC)(OC)OC HILHCDFHSDUYNX-UHFFFAOYSA-N 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 claims description 3
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 claims description 3
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Chemical group 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical group CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 claims description 2
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 2
- DIBHLCJAJIKHGB-UHFFFAOYSA-N dec-5-ene Chemical compound [CH2]CCCC=CCCCC DIBHLCJAJIKHGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012990 dithiocarbamate Substances 0.000 claims description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
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Classifications
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1212—Zeolites, glasses
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
Definitions
- This invention relates to the field of surface-protective coating compositions, e.g., conversion and passivation coatings, and more particularly to curable coating compositions derived from alkoxysilanes and to processes for coating metallic substrates therewith.
- a curable surface- protective coating forming composition for application to protect the surface of a substrate such as one of metal, metal alloy, metallized part, metal or metallized part possessing one or more protective layers, the coating forming composition comprising: at least one alkoxysilane selected from the group consisting of Formulas A and B:
- X is an organofunctional group, more specifically a mercapto, acyloxy, glycidoxy, epoxy, epoxycyclohexyl, epoxycyclohexylethyl, hydroxy, episulfide, acrylate, methacrylate, ureido, thioureido, vinyl, allyl, -NHCOOR 4 or -NHCOSR 4 group in which R 4 is a monovalent hydrocarbyl group containing from 1 to about 12 carbon atoms, more specifically from 1 to about 8 carbon atoms, thiocarbamate, dithiocarbamate, ether, thioether, disulfide, trisulfide, tetrasulfide, pentasulfide, hexasulfide, polysulfide, xanthate, trithiocarbonate, dithiocarbonate or isocyanurato group, or another -Si(OR 3 ) group wherein R 3 is as hereinafter defined;
- each R 1 is a linear, branched or cyclic divalent organic group of from 1 to about 12 carbon atoms, more specifically from 1 to about 10 carbon atoms, and most specifically from 1 to about 8 carbon atoms, e.g., a divalent hydrocarbon group such as the non-limiting examples of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, cyclohexylene, arylene, aralkylene or alkarylene group, and optionally containing one or more heteroatoms such as the non-limiting examples of O, S and NR 4 in which R 4 is hydrogen or an alkyl group of from 1 to 4 carbon atoms;
- each R 2 independently is alkyl, aryl, alkaryl or aralkyl group of from 1 to about 16 carbon atoms, more specifically from 1 to about 12 carbon atoms, and still more specifically from 1 to 4 carbon atoms, and optionally containing one or more halogen atoms, more specifically a fluorine atom;
- each R 3 independently is an alkyl group of from 1 to about 12 carbon atoms, more specifically from 1 to about 8 carbon atoms and still more specifically from 1 to 4 carbon atoms;
- subscript a is 0 or 1
- subscript b is 0, 1 or 2 and a+b is 0, 1 or 2;
- the amount of alkoxysilane of Formula A when subscript a is 0 or 1, subscript b is 0, 1 or 2 and a+b is 2 is from 0 to about 8 weight percent of the coating forming composition, the amount of alkoxysilane of Formula A when a + b is 0 is from 0 to about 15 weight percent of the coating forming composition,
- alkoxysilane of Formula A in which subscript a is 0 or 1, subscript b is 0 or 1 and a+b is 1 and of alkoxysilane of Formula B is from about 8 to about 40 weight percent, and
- the total amount of alkoxysilane of Formulas A and B does not exceed about 50, preferably about 45, more preferably about 40 weight percent of the coating forming
- the coating forming composition having a viscosity at 25°C within the range of from about 3.0 to about 7.0 cStks, more specifically from about 4.0 to about 5.5 cStks and still more specifically from about 4.5 to about 5.0 cStks.
- the viscosity is measured at 25°C in accordance with the DIN 53015 standard, "Viscometry - Measurement of Viscosity by Means of the Rolling Ball
- Viscometer by Hoeppler employing a Hoeppler Falling Ball Viscometer Model 356-001 equipped with a Haake DC 10 temperature control unit and ball set 800-0182, in particular, ball no. 2 having a diameter of 15.598 mm, a weight of 4.4282 g and a density of 2.229 g/cm 3 .
- the at least one alkoxysilane (i) selected from the group consisting of Formulas A and B can be also hydrolyzed and condensed products thereof.
- the resulting hydrolysed and condensed products or oligomers can be for example linear or cyclic polysiloxanes comprising from 2 to 30 siloxy units, preferably from 2 to 10 siloxy units, and remaining alkoxy groups.
- the provisos concerning the amounts of the alkoxysilanes (i), that is, the amount of alkoxysilane of Formula A when subscript a is 0 or 1, subscript b is 0, 1 or 2 and a+b is 2 is from 0 to about 25 weight percent of the coating forming composition
- the amount of alkoxysilane of Formula A when a+b is 0 is from 0 to about 15 weight percent of the coating forming composition
- alkoxysilane of Formula A in which subscript a is 0 or 1, subscript b is 0 or 1 and a+b is 1 and of alkoxysilane of Formula B is from about 8 to about 40 weight percent of the coating forming composition, and
- the total amount of alkoxysilane of Formulas A and B does not exceed about 50, preferably about 45, more preferably about 40 weight percent of the coating forming
- oligomers include in particular oligomeric glycidoxypropyl- trimethoxysilane.
- step (a) adding metal oxide (ii) and water (v) to the chilled mixture of step (a);
- step (b) adding water-miscible organic solvent (iii) and the remainder of acid hydrolysis catalyst (iv) to the mixture resulting from step (b);
- step (c) aging the mixture resulting from step (c) under conditions of elevated temperature and for a period of time effective to provide a curable coating forming composition having a viscosity at 25°C within the range of from about 3.0 to about 7.0 cStks, more specifically from about 4.0 to about 5.5 cStks and still more specifically from about 4.5 to about 5.0 cStks; and, e) optionally, adding condensation catalyst (vi) at, during or following any of the preceding steps.
- the metal oxide (ii) is a colloidal suspension of at least one metal oxide selected from the group consisting of silica, alumina, titania, ceria, tin oxide, zirconia, antimony oxide, indium oxide, iron oxide, titania doped with iron oxide and/or zirconia and rare earth oxide, or when the metal oxide (ii) is selected from a mixture of alumina and silica.
- step (b) adding the alkoxysilane (i) (or a mixture thereof) to the chilled mixture of step (b);
- step c) allowing the mixture obtained in step c) to warm to room temperature (approximately 25°C) (either preferably by letting it reach room temperature for example overnight or less preferred by supplying heat),
- the metal oxide (ii) is selected from silica modified with alumina.
- silica modified with alumina particles such as Levasil ® 100S/45 (now: Levasil CS45-58P) (AkzoNobel) and Levasil ® 200S/30 (now: Levasil CS30-516P) (AkzoNobel) and acetic acid (iv) is stirred in a flask.
- the mixture is cooled to 0 - 10°C while the alkoxysilanes (i) are dropwise added within 20 - 50 min.
- the mixture is stirred while the solution is allowed to come to room temperature.
- the solvents (iii) such as alcohols, the catalyst (vi) and the flow additive (vii) are added.
- the whole mixture is stirred for at least 15 min to obtain a coating forming composition.
- a metal possessing a surface- protective coating i.e., a coating which imparts corrosion resistance and/or abrasion resistance to a surface of a non-coated or pre-coated metal, is obtained by the coating process which further comprises:
- Curable coating forming compositions of the invention possess excellent storage stability and cured surface-protective coatings obtained therefrom tend to exhibit one or more functionally advantageous properties such as high levels of corrosion and abrasion resistance, adherence to metal surfaces, flexibility (resistance to cracking or crazing caused by flexing of the metal) and acid and/or alkali resistance.
- the generally outstanding optical clarity of the cured coatings herein allows the aesthetically attractive quality of the underlying substrate surface to be shown to good effect.
- composition percentages are given in weight percent unless otherwise indicated. [0013] It will be understood that any numerical range recited herein includes all sub-ranges within that range and any combination of the various endpoints of such ranges or sub-ranges.
- coating forming composition shall be understood to mean a composition, while not itself a practical or useful coating composition, following processing as described herein in detail forms a high quality and effective thermally curable surface-protective coating for application to a metal surface.
- metal as used herein shall be understood herein to apply to metals per se, metal alloys, metalized parts and metal or metalized parts possessing one or more non-metallic protective layers.
- hydrolytically condensed is meant that one or more silanes in the coating composition-forming mixture are first hydrolyzed followed by the condensation reaction of hydrolyzed product with itself or with other hydrolyzed and/or unhydrolyzed components of the mixture.
- Alkoxysilane (i) present in the coating forming composition can be one or more dialkoxysilane, trialkoxysilane and/or tetraalkoxysilane of Formula A and/or one or more trialkoxysilane of Formula B as described above provided at least one such trialkoxysilane is included therein.
- dialkoxysilanes of Formula A include dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, 3-cyanopropylphenyldimethoxysilane, diphenyldimethoxysilane, Diphenyldiethoxysilane, di(p-tolyl)dimethoxysilane,
- alkoxy silanes including the dialkoxysilanes, also include hydrolysed and condensed products thereof (oligomers).
- examples of trialkoxysilanes of Formula A include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, n- propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n- propyltributoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n- pentyltrimethoxysilane, n-hexyltrimethoxysilane, isoocyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxy
- glycidoxypropyltrimethoxysilane are especially advantageous.
- alkoxysilanes including the trialkoxysilanes, also include hydrolysed and condensed products thereof (oligomers).
- tetraalkoxysilanes i.e., tetraalkyl orthosilicates
- examples of tetraalkoxysilanes (i.e., tetraalkyl orthosilicates) of Formula A include tetramethoxysilane, dimethoxydiethoxysilane, tetraethoxysilane, methoxytriethoxysilane, tetrapropoxy silane, and the like, and their mixtures.
- trialkoxysilanes of Formula B include l,2-bis(trimethoxysilyl)ethane, l,2-bis(triethoxysilyl)ethane, bis(trimethoxysilylpropyl)disulfide,
- bis(triethoxysilylpropyl)tetrasulfide bis(3-triethoxysilylpropyl)amine, bis(3- trimethoxysilylpropyl)amine, and the like, and their mixtures.
- Metal oxide component (ii) is generally provided in the form of particles, e.g., approximately spherical or equiaxial particles, ranging in average particle size from about 5 nm to about 500 nm, more specifically from about 10 to about 200 nm and still more specifically from about 10 to about 60 nm.
- the average particle sizes are determined in particular by Low Angle Laser Light Scattering (LALLS) using the full Mie theory, in particular, using Mastersizer 2000 or 3000, Malvern Instruments).
- LALLS Low Angle Laser Light Scattering
- Metal oxide (ii) is advantageously provided as an aqueous colloidal dispersion thereof, for example, an aqueous colloidal dispersion of a metal oxide such as silica, alumina, titania, ceria, tin oxide, zirconia, antimony oxide, indium oxide, iron oxide, titania doped with iron oxide and/or zirconia, rare earth oxide, as well as mixtures and complex oxides thereof.
- metal oxides (ii) in powder form may be dispersed within the coating composition.
- a preferred metal oxide (ii) is aqueous colloidal silica.
- Aqueous dispersions of colloidal silica which may advantageously be utilized in the present invention include those having an average particle size ranging from about 20 to about 150 nm and preferably from about 5 to about 30 nm. Such dispersions are known in the art, commercially available ones of which include, for example, Ludox ® (Sigma Aldrich), Snowtex ® (Nissan Chemical), and
- Bindzil ® (AkzoNobel) and Nalco ® Colloidal Silica (Nalco Chemical Company), Levasil ® (AkzoNobel).
- Such dispersions are available in the form of acidic and basic hydrosols.
- Both acidic and basic colloidal silica can be incorporated in the coating forming composition of the present invention.
- Colloidal silicas having a low alkali content may provide a more stable coating composition and may therefore be preferred.
- Particularly preferred colloidal silicas include Nalco ® 1034A (Nalco Chemical Company) and Snowtex ® O40, Snowtex ST-033 and Snowtex ® OL-40 (Nissan Chemical), Ludox ® AS40 and Ludox ® HS 40 (Sigma- Aldrich), Levasil 200/30 and Levasil ® 200 S/30 (now Levasil CS30-516P) (AkzoNobel) and Cab-O- Sperse ® A205 (Cabot Corporation).
- the total amount of alkoxysilane of Formulas A and B preferably does not exceed about 40 weight percent of the coating forming composition.
- the metal oxide (ii) is selected from a mixture of alumina and silica.
- the weight ratio of alumina to silica is from about 1:99 to about 99: 1, preferably from about 5:95 to about 90: 10, more preferably about 5:95 to about 75:25.
- Such mixtures are preferably prepared by admixing aqueous colloidal dispersions of alumina and silica. Using a mixture of alumina and silica provides for good adhesion to aluminum surface, very high abrasion resistance, good corrosion protection, heat resistance, and acid and alkali resistance.
- the metal oxide (ii) is selected from silica modified with alumina.
- silica modified with alumina may be silica the surface of which has been modified with alumina.
- silica modified with alumina is sometimes referred to as AI2O3-S1O2 - core- shell particles.
- the metal oxide (ii) may be advantageously provided as an aqueous colloidal dispersion.
- the use of such silica modified with alumina or AI2O3-S1O2 - core- shell particles is particularly helpful to protect anodized aluminum components on the exterior of automobiles, e.g. roof rails and trim parts and provides high corrosion resistance caused by high or low pH liquids, high scratch resistance and high heat resistance.
- the use of such silica modified with alumina in the coating forming composition according to the invention provides for high scratch resistance under long-term highly acidic environment conditions.
- silica modified with alumina examples include for example Levasil-types such as Levasil ® lOOS/45 (now: Levasil CS45-58P) dispersion (45% in water) containing silica particles surface modified with AI2O3 having an average particle size of about 30 nm, and Levasil ® 200S/30 (now: Levasil CS30-516P) dispersion (30% in water) containing silica particles surface modified with AI2O3 having an average particle size of about 17 nm, and a surface area of about 85 m 2 /g (in Levasil ® 100S/45) and about 160 m 2 /g (Levasil ® 200S/30).
- Levasil-types such as Levasil ® lOOS/45 (now: Levasil CS45-58P) dispersion (45% in water) containing silica particles surface modified with AI2O3 having an average particle size of about 30 nm
- a mixture comprising at least two silicas modified with alumina having different average particle sizes may be used.
- a mixture of two silicas modified with alumina having different average particle sizes may be used wherein the weight ratio of the silica modified with alumina having the smaller particle size (e.g. 10 to 25 nm) is higher than the amount of the silica modified with alumina having the bigger particle size (e.g. 26 to 40 nm), preferably the ratio small/big is about 10: 1 to about 1:2, preferably about 10: 1 to about 2: 1. This measure provides for particularly high scratch resistances.
- the amount of metal oxide(s) (ii) incorporated in the coating forming composition herein may in general vary from about 5 to about 50, more specifically from about 10 to about 40 and still more specifically from about 10 to about 30, weight percent based on the weight of the composition.
- water-miscible solvent(s) (iii) that may be incorporated in the coating forming composition of the invention are alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethyleneglycol butyl ether, and combinations thereof.
- alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, methoxypropanol, ethylene glycol, diethyleneglycol butyl ether, and combinations thereof.
- Other water-miscible organic solvents such as acetone, methyl ethyl ketone, ethylene glycol monopropyl ether and 2-butoxy ethanol can also be utilized.
- these solvents are used in combination with water, the latter together with any water associated with metal oxide (ii) and/or other component(s) of the coating composition providing part or all of water (v) thereof.
- the total amount of water-miscible solvent(s) (iii) present in the coating forming composition can vary widely, e.g., from about 10 to about 80, more specifically from about 10 to about 65, more specifically from about 10 to about 60 and still more specifically from about 10 to about 50, weight percent based on the total weight thereof.
- the coating forming composition comprises as the metal oxide (ii) silica modified with alumina
- the total amount of water-miscible solvent(s) (iii) present in the coating forming composition can vary widely, e.g., from about 40 to about 70, more specifically from about 50 to about 65 weight percent based on the total weight thereof.
- any of the acidic hydrolysis catalysts heretofore employed for the hydrolysis of alkoxysilanes can be incorporated in the coating forming composition herein.
- Illustrative acid hydrolysis catalysts (iv) include sulfuric acid, hydrochloric acid, acetic acid, propanoic acid, 2- methyl propanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid (enanthic acid), hexanoic acid, octanoic acid (caprylic acid), oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzeneacetic acid, propanedioic acid (malonic acid), butanedioic acid
- Acid hydrolysis catalyst (iv) will be present in the coating forming composition of the invention in at least a catalytically effective amount which in most cases can range from about 0.1 to about 5, more specifically from about 0.5 to about 4.5, and more specifically from about 2 to about 4, weight percent based on the total weight of coating forming composition. In certain embodiments, e.g., when the coating forming composition comprises as the metal oxide (ii) silica modified with alumina, the amount of the acid hydrolysis catalyst (iv) can also range from about 0.1 to about 2 weight percent based on the total weight of coating forming composition. [0038] Water (v)
- the water component of the coating forming composition herein is advantageously deionized (DI) water.
- DI deionized
- Some or even all of the total water present in the coating composition- forming mixture may be added as part of one or more other components of the mixture, e.g., aqueous colloidal dispersion of metal oxide (ii), water-miscible solvent (iii), acid hydrolysis catalyst (iv) optional condensation catalyst (vi) and/or other optional components (vii) such as those hereinafter described.
- the total amount of water (v) can range within widely varying limits, e.g., from about 5 to about 40, more specifically from about 5 to about 30 and still more specifically from about 5 to about 15, weight percent based on the total weight of coating forming composition.
- Optional condensation catalyst (vi) catalyzes the condensation of partially or completely hydrolyzed silane components (a) and (b) of the coating forming composition herein and thus functions as a cure catalyst.
- the coating forming composition can be cured in the absence of optional condensation catalyst (vi)
- efficient curing may require more intensive conditions, e.g., the application of elevated temperature (thermal curing) and/or extended cure times, both of which may be undesirable from a cost and/or productivity standpoint.
- optional condensation catalyst (vi) generally results in improved shelf life of the coating forming composition.
- condensation catalysts (vi) that may optionally be present in the coating forming composition herein are tetrabutylammonium carboxylates of the formula
- R 5 is selected from the group consisting of hydrogen, alkyl groups containing from 1 to about 8 carbon atoms, and aromatic groups containing about 6 to about 20 carbon atoms.
- R 5 is a group containing about 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
- condensation catalysts e.g., mineral acids and alkali metal hydroxides
- the foregoing tetrabutylammonium carboxylates being somewhat milder in their catalytic action tend to optimize the shelf life of the coating forming compositions containing them.
- Exemplary tetrabutylammonium carboxylate condensation catalysts of the foregoing formula are tetra-n- butylammonium acetate (TBAA), tetrabutylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate and tetra-n-butylammonium propionate.
- TBAA tetra-n- butylammonium acetate
- tetrabutylammonium formate tetra-n-butylammonium benzoate
- tetra-n-butylammonium-2-ethylhexanoate tetra-n-butylammonium-p-ethylbenzoate
- the preferred condensation catalysts are tetrabutylammonium carboxylate, tetra-n- butylammonium acetate (TBAA), tetra-n-butylammonium formate, tetra-n-butylammonium benzoate, tetra-n-butylammonium-2-ethylhexanoate, tetra-n-butylammonium-p-ethylbenzoate, and tetra-n-butylammonium propionate, tetramethylammonium acetate, tetramethylammonium benzoate, tetrahexylammonium acetate, dimethylanilium formate, dimethylammonium acetate, tetramethylammonium carboxylate, tetramethylammonium-2-ethylhexanoate,
- benzyltrimethylammonium acetate tetraethylammonium acetate, tetraisopropylammonium acetate, triethanol-methylammonium acetate, diethanoldimethylammonium acetate,
- TBD monoethanoltrimethylammonium acetate, ethyltriphenylphosphonium acetate, TBD acetate (l,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD)), as well as combinations of two or more thereof.
- tetra-n- butylammonium acetate and tetra-n-butylammonium formate are generally preferred with tetra- n-butylammonium acetate being more preferred.
- condensation catalyst (vi) can be present in the coating forming composition herein in at least a catalytically effective amount, e.g., from about 0.0001 to about 1 weight percent based on the total weight thereof.
- One or more other optional components (vii) are suitable for inclusion in the coating forming composition herein.
- the coating forming composition can also include one or more surfactants functioning as leveling agents or flow additives.
- suitable surfactants include fluorinated surfactants such as Fluorad ® (3M), silicone polyethers such as Silwet ® and CoatOSil ® (Momentive Performance Materials, Inc.) and silicone surface additives such as polyether-modified silicones, such as BYK-302 (BYK Chemie USA).
- the coating composition herein composition can also include a UV absorber such as benzotriazole, benzophenones, dibenzylresorcinol.
- Preferred UV absorbers are those capable of co-condensing with silanes, specific examples of which include 4-[gamma-(trimethoxysilyl) propoxyl]-2-hydroxy benzophenone, 4-[gamma-(triethoxysilyl) propoxyl]-2-hydroxy benzophenone and 4,6- dibenzoyl-2-(3-triethoxysilylpropyl) resorcinol.
- silanes specific examples of which include 4-[gamma-(trimethoxysilyl) propoxyl]-2-hydroxy benzophenone, 4-[gamma-(triethoxysilyl) propoxyl]-2-hydroxy benzophenone and 4,6- dibenzoyl-2-(3-triethoxysilylpropyl) resorcinol.
- the coating forming composition herein can also include one or more antioxidants such as a hindered phenol (e.g. Irganox ® 1010 (Ciba Specialty Chemicals), dyes such as methylene green, methylene blue, and the like), fillers such as Titanium dioxide, zinc phosphate, barytes, aluminium flakes, etc. and plasticizer such as dibutylpthalate.
- a hindered phenol e.g. Irganox ® 1010 (Ciba Specialty Chemicals)
- dyes such as methylene green, methylene blue, and the like
- fillers such as Titanium dioxide, zinc phosphate, barytes, aluminium flakes, etc.
- plasticizer such as dibutylpthalate.
- thermally curable coating composition of the invention chilling a mixture of alkoxysilane(s) (i) and a portion of the acid hydrolysis catalyst (iv), subsequent addition of the remaining portion of acid hydrolysis catalyst (iv) and aging of the resulting mixture under predetermined conditions of elevated temperature and time leads to a thermally curable composition having a range of viscosity of from about 3.0 to about 7.0 cStks, in another embodiment more specifically from about 4.0 to about 5.5 cStks and still in another embodiment more specifically from about 4.5 to about 5.0 cStks.
- Chilling can be done for example by using an ice bath, ice/NaCl mixture or dry ice/isopropanol mixture. More specifically the alkoxysilanes (i) and the acid hydrolysis catalyst (iv) are placed in a glass bottle and then placed in an ice bath to chill the mixture while monitoring temperature through an external thermometer. Chilling the mixture of the alkoxysilanes (i) and the acid hydrolysis catalyst (iv) is preferably done to a temperature of about -20°C to about 15°C, preferably of about -10 °C to about 10°C, more preferably of about 0 to about 10 °C.
- a mixture of trialkoxysilane of Formulas A and/or B, optional dialkoxysilane and/or tetraalkoxysilane of Formula A and from about 10 to about 40 percent of the total amount of acid hydrolysis catalyst (iv) is chilled to within a range of temperature of from about -20°C to about 15°C, and preferably from about -10 °C to about 10°C. While in the chilled condition, metal oxide (ii), e.g., aqueous colloidal silica, is slowly added to the mixture.
- the chilled mixture is allowed to rise in temperature to or about ambient, e.g., from about 20°C to about 30°C.
- the alkoxysilane component(s) (i) of the mixture undergo an initial level of hydrolysis followed by condensation of the resulting hydrolyzates.
- metal oxide (ii) is selected from silica modified with alumina it is preferred to chill these formulations for some hours/overnight, e.g. for about 2 to about 10 hours.
- composition herein water-miscible solvent(s) (iii) and the remaining acid hydrolysis catalyst (iv) are added to the now ambient temperature reaction medium and under continuous stirring over a period of, e.g., from about 5 to about 24, and more specifically from about 8 to about 15, hours during which further hydrolysis of silanes and/or partial hydrolyzates and condensation of the thus-formed hydrolyzates thereof takes place.
- the metal oxide (ii) is selected from silica modified with alumina it is preferred to add the whole amount of the acid hydrolysis catalyst (iv) directly in the beginning, so there is no addition of the acid hydrolysis catalyst (iv) at this point.
- the initial portion of acid hydrolysis catalyst (iv) is added in such a way, e.g., dropwise, as to prevent agglomeration and precipitation of metal oxide particulate (ii) thereby allowing the alkoxysilane component(s) (i) to undergo hydrolysis and functionalize metal oxide particles (ii). With the silanization of metal oxide particulates (ii), the pH of the mixture will reach almost neutral.
- metal oxide (ii) is selected from silica modified with alumina usually pH ranges of about 3 to about 4 such as about 3.5 to about 3.8 are achieved with no additional pH adjustment.
- Acid hydrolysis catalyst (iv) may be added at the second stage to maintain the final pH of the mixture so that the condensation of silanol is controlled and gel formation is inhibited thereby providing relatively long shelf life, e.g., a coating forming composition containing less than about 5, preferably less than about 2 and more preferably less than about 1, weight percent gel of the total weight thereof after storage under ambient temperature of not less than about 15 days, more specifically not less than about 20 days and still more specifically not less than about 30 days. In certain embodiments storage at temperatures in the range of about 0 to about 15 °C preferably at about 5 to about 10°C might be appropriate,
- optional condensation catalyst (vi) may be added in at least a catalytically effective amount at, during or following any of steps (a) - (d) of preparing the curable coating composition.
- the amounts of optional condensation catalyst (v) can vary widely, e.g., from about 0.01 to about 0.5, and more specifically from about 0.05 to about 0.2, weight percent based on the total weight of coating forming composition.
- the optimum amount of residual silanol is obtained by accelerating the condensation reaction during aging as more fully described below. Once the desired viscosity level is obtained, the curable coating composition can be applied to a desired substrate to produce a uniform, transparent and hard coating thereon (steel wool abrasion resistance test with 1 kg load as described in Table 5 below.
- reaction mixture is now ready for aging.
- Aging of the foregoing coating composition-forming mixture is carried out at elevated temperature over a period of time which has been experimentally determined to result in a viscosity within the aforestated range of from about 3.0 to about 7.0 cStks.
- metal oxide (ii) is selected from silica modified with alumina aging is normally not required.
- Achieving such viscosity results in a curable coating composition with good-to- excellent cured coating properties.
- a lower viscosity may lead to reduced hardness of the coating film and to post curing that may occur on continued exposure of the coating.
- a higher viscosity may lead to cracking of the coating film during curing and subsequent exposure conditions.
- a viscosity within the range of from about 3.0 to about 7.0 cStks can be achieved by heating the coating-forming mixture in an air oven, e.g., to a temperature of from about 25 to about 100 °C for from about 30 min. to about 1 day, more specifically at a temperature of from about 25 to about 75 °C for from about 30 min. to about 5 days and still more specifically at a temperature from about 25 to about 50 °C for from about 3 to about 10 days.
- the hydroxyl-containing hydrolyzable silane is partially hydrolyzed when less than an equivalent amount of water reacts with the hydrolyzable silyl group.
- the silane is considered partially hydrolyzed when the percent hydrolysis is in the range of about 1 to about 94 percent.
- the hydroxyl-containing hydrolyzable silane is considered substantially fully hydrolyzed when the percent hydrolysis is in the range of from about 95 to about 100 percent.
- the partially hydrolyzed hydroxyl-containing hydrolyzable silane has better stability in an aqueous solution because the R ⁇ O-Si group terminates the polymerization reaction of the silanol condensation and maintains a lower average molecular weight oligomeric composition that is derived from the hydroxyl-containing hydrolyzable silane.
- the lower average molecular weight oligomeric composition adsorbs more uniformly onto the metal substrate resulting in better adhesion.
- the coating forming composition of the invention will typically have a solids content of from about 10 to about 50, more specifically from about 15 to about 40 and still more specifically from about 20 to about 30, weight percent.
- the pH of the coating composition will often come within the range of from about 3 to about 7, and more specifically from about 4 to about 6.
- the pH of the coating composition will often come within the range of from about 3 to about 4 such as about 3.5 to about 3.8.
- the curable coating composition can be coated onto a metal substrate with or without the use of a primer and preferably without a primer.
- Suitable metals include steel, stainless steel, aluminum, anodized aluminum, magnesium, copper, bronze, alloys of each of these metals, and the like, with anodized aluminum being a particularly desirable substrate due to its inherent corrosion resistance property and strength to weight ratio.
- the coating forming composition can be applied to a metal surface or other substrate employing any conventional or otherwise known technique such as spraying, brushing and flow coating. Also dip-coating is possible.
- Wet, i.e., freshly applied, coating thicknesses can be made to vary over a fairly broad range, e.g., from about 10 to about 150, more specifically from about 20 to about 100, and still more specifically from about 40 to about 80, microns.
- As-applied coatings of such thicknesses upon drying will generally provide cured coatings having thicknesses ranging respectively from about 3 to 30, more specifically from about 5 to about 20 and still more specifically, from about 10 to about 15, microns.
- metal oxide (ii) is selected from silica modified with alumina typically dry coating thicknesses (DFT) of about 2 to about 10 microns, preferably about 3 to about 7 microns are adjusted.
- DFT dry coating thicknesses
- thermally accelerated curing may be carried out within a temperature regime of from about 80 to about 200 °C over a period of from about 30 to about 90 minutes to provide a cured, optically clear, hard protective coating on the substrate metal.
- the cured coating obtained from the coating forming composition of the invention may be in direct contact with the metal surface, may serve as the sole coating therein, may be superimposed upon one or more other coatings and/or may itself possess one or more other coatings superimposed thereon.
- the cured coating composition in addition to imparting corrosion and/or abrasion resistance properties to its metal substrate may also function as an aesthetic coating in which case it will constitute the sole or outermost coating on the metal substrate.
- the advantages of the coating forming composition of the invention over known alkoxy silane -based coating forming compositions lie not only in the exceptional storage stability of the former, attributable it is believed to the particular combination of starting components and their amounts and to the unique process by which the coating forming composition is obtained, in particular, its separate cooling, split-addition of hydrolysis catalyst and aging steps, but to the ease of its application to any of a variety of metal and metalized surfaces and the dependably uniform properties of the cured coating.
- the cured coating composition of the invention exhibits outstanding properties including a high level of adhesion to its metal substrate, corrosion resistance, flexibility (resistance to cracking and crazing), abrasion/wear resistance and optical clarity, the latter being a particularly sought-after property where the cured coating composition is to additionally function as a decorative coating.
- Comparative Example 1 illustrates a curable coating forming composition prepared in accordance with Burger et al. U.S. Patent No. 6,695,904 and applied to an anodized aluminum panel of 15 cm length, 4 cm width and 4 mm thickness.
- a mixture of methyltrimethoxysilane, 62.0g, tetraethoxysilane, 18.1g, and aqueous colloidal silica, 23.13 g (40 wt% suspension) was prepared to which was added dropwise at -5°C 1.3 gm of 37 weight percent sulfuric acid as acid hydrolysis catalyst.
- the mixture was continuously stirred at 20°C for one hour to provide a coating composition.
- the reaction mixture had gelled.
- Examples 1-15 illustrate the preparation of coating forming compositions of the invention and their performance as cured coatings on anodized aluminum panels of 15cm length, 4cm width and 4mm thickness and on stainless steel panels of 15cm length, 10cm width and lmm thickness.
- a coating layer having an approximate thickness of 10 microns may be carried out by any suitable means, e.g., by dip, flow or spray coating. Dip coating was used for applying an approximately 10 micron thick layer of coating forming composition to the anodized aluminium panels while flow coating was used for applying a coating of this thickness to the stainless steel panels.
- the coating formulations were prepared by either of the following procedure:
- a glass bottle was charged with acetic acid and trialkoxy silane. After cooling down the reaction mixture in an ice bath to 0 °C, mixture of silica nanoparticles and water were drop wise added to the chilled mixture of silanes and acetic acid while maintaining temperature below 10 °C. The mixture was then allowed to stir for approx. 1-2 hours. Alumina nano-particle dispersion was then added to the mixture, and allowed to stir for another approx. 12-14 hours while the solution temperature slowly increased to room temperature. Then, alcohols and remaining acetic acid were added and stirred for approximately 12 hours following which TBAA catalyst and flow additive were added. After this, the formulations were aged approx. for 5 days at 50 °C in hot air oven prior to coating on metal surface.
- the coating solutions can be prepared by reacting alkoxy silane with different nanoparticles separately.
- This method may be a better choice over one-pot procedure for the compositions where there is a tendency of nanoparticles to settle down in the formulation.
- this method can in general be used for coating compositions having any ratios of two different nanoparticles.
- a glass bottle was charged with acetic acid and trialkoxy silane. After cooling down the reaction mixture in an ice bath to 0 °C, mixture of silica nanoparticles and water were drop wise added to the chilled mixture of silanes and acetic acid while maintaining temperature below 10 °C. The mixture was then allowed to stir for approx. 16 hours while the solution temperature slowly rose to room temperature.
- a portion of alkoxy silane preferably 1 : 1 weight percentage of silane and nanoparticle
- nanoparticle alumina
- the coating composition is a thermal cure single layer optically clear protective coating which was directly applied on anodized aluminium surfaces.
- Application of thin layer coating of approximate thickness around 10 microns was achieved by dip/flow/spray coating. After coating on aluminium substrates, volatiles evaporate at ambient condition (approx. 20-25 °C, 40+10 %RH) and a tack free coating layer is formed within 25-30 minutes. After solvent flush off the coated panels were baked in hot air oven between 130-200°C for 30-60 minutes to obtain completely cured, clear hard coat on metal surface.
- Coating appearance This test is done by visual inspection. To pass, the coating shall be smooth, glossy, optically clear, and free from any coating defects.
- Hydrochloric (HC1) acid solution for 10 minutes. After exposure, panels are taken out from solution, washed with DI water and dried in ambient condition. To pass, there should not be softening of the coating film, adhesion loss, delamination, cracking or corrosion.
- Alkaline resistance test The coated panels are dipped into a pH 13.5 sodium hydroxide buffer solution for 10 minutes.
- the buffer solution is prepared by mixing appropriate weight of sodium hydroxide, sodium phosphate dodecahydrate, sodium chloride and Deionized water. After exposure, panels are taken out from solution, washed with DI water and dried in ambient condition. To pass, there should not be softening of the coating film, adhesion loss, delamination, cracking or corrosion.
- Sulfuric acid resistance test The coated panels are dipped into a pH 2.1 H2SO4 solution for 5 days. After exposure, panels are taken out from solution, washed with DI water and dried in ambient condition. To pass, there should not be softening of the coating film, adhesion loss, delamination, cracking or corrosion.
- Corrosion resistance test-Kesternich test (Acid rain simulation): This test is done as per DIN 50017 up to 3 cycle. To pass this test, coating shall not exhibit any softening, delamination, loss of adhesion, changes in visual appearance or any other coating defects.
- examples 16-25 comprising silica and alumina particles, all provide good coating properties such as adhesion, abrasion and pH resistance tests (HCl and NaOH buffer solution). In particular the examples also provide very good results regarding scratch resistance, pH resistance test including sulfuric acid resistance and in the Kesternich tests.
- Examples 26 to 30 (AhCb-SiC - core-shell particles as the metal oxide (ii)) Table 13: Starting Materials
- the clear coating compositions were directly applied onto anodized aluminum with a layer thickness of 2 ⁇ to 8 ⁇ .
- Application of the coating compositions was achieved by dip/flow or spray coating. After coating anodized aluminum substrates, solvent flush off takes 2 - 20 min. to obtain a tack free coating layer. Coated substrates are then cured in a hot air oven at 130°C to 200°C for 30 min. to 2 hours to obtain complete curing.
- S0 2 lab test transferred from DIN50018 - 2,0S: 0.67 wt.% S0 2 solution in a 5L bottle that is placed into a water bath at 40°C.
- the coated samples are placed with the bottom part into this solution, whereas the upper part experiences the S0 2 atmosphere.
- the coating should not change optically after five days.
- Alkaline resistance according to TL182 No change in appearance after the following test series on the same component in a temperature range of 23 °C to 35°C:
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US15/664,023 US20190031918A1 (en) | 2017-07-31 | 2017-07-31 | Curable surface-protective coating composition, processes for its preparation and application to a metallic substrate and resulting coated metallic substrate |
EP18165148 | 2018-03-29 | ||
PCT/US2018/044559 WO2019027991A1 (en) | 2017-07-31 | 2018-07-31 | CURABLE SURFACE PROTECTIVE COATING COMPOSITION, METHODS FOR PREPARATION AND APPLICATION TO METALLIC SUBSTRATE, AND COATED METALLIC SUBSTRATE OBTAINED THEREBY |
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JP (1) | JP7324186B2 (de) |
KR (1) | KR20200079479A (de) |
CN (1) | CN111065694A (de) |
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US11370937B2 (en) | 2019-03-04 | 2022-06-28 | Momentive Performance Materials Inc. | Protective coating composition and coated metallic substrate comprising same |
US20200283908A1 (en) | 2019-03-04 | 2020-09-10 | Momentive Performance Materials Inc. | Protective coating composition and coated metallic substrate comprising same |
CN110183665B (zh) * | 2019-05-28 | 2022-01-14 | 安庆北化大科技园有限公司 | 一种含巯基mtq树脂的制备方法及其应用 |
CN112266690A (zh) * | 2020-11-04 | 2021-01-26 | 芜湖天航重工股份有限公司 | 风电塔筒表层耐磨防腐涂料及其制备方法 |
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JPS53111336A (en) * | 1977-03-11 | 1978-09-28 | Toray Ind Inc | Coating composition |
ZA795994B (en) * | 1978-11-30 | 1981-05-27 | Gen Electric | Silicone resin coating composition |
US4476281A (en) * | 1978-11-30 | 1984-10-09 | General Electric Company | Silicone resin coating composition |
US4309319A (en) * | 1978-11-30 | 1982-01-05 | General Electric Company | Silicone resin coating composition |
US4311738A (en) * | 1980-05-27 | 1982-01-19 | Dow Corning Corporation | Method for rendering non-ferrous metals corrosion resistant |
JPS6232157A (ja) * | 1985-08-02 | 1987-02-12 | Yoshio Ichikawa | コ−テイング用組成物 |
US4990376A (en) * | 1988-04-25 | 1991-02-05 | General Electric Company | Flexible silicone coatings for plastic substrates and methods for making thermoformable, abrasion-resistant thermoplastic articles |
US4863520A (en) * | 1988-07-05 | 1989-09-05 | General Electric Company | Method for curing silicone coatings on plastic substrates, and curable compositions related thereto |
JPH0649412A (ja) * | 1992-07-28 | 1994-02-22 | Matsushita Electric Works Ltd | コーティング組成物 |
US6348269B1 (en) * | 1998-10-23 | 2002-02-19 | Sdc Coatings, Inc. | Composition for providing an abrasion resistant coating on a substrate having improved adhesion and improved resistance to crack formation |
JP2000144051A (ja) * | 1998-11-18 | 2000-05-26 | Teijin Chem Ltd | コーティング用組成物 |
JP2001192615A (ja) * | 1999-11-01 | 2001-07-17 | Jsr Corp | コーティング組成物 |
DE10141687A1 (de) | 2001-08-25 | 2003-03-06 | Degussa | Siliciumverbindungen enthaltendes Mittel zur Beschichtung von Oberflächen |
JP3995447B2 (ja) * | 2001-11-05 | 2007-10-24 | 株式会社ニデック | ハードコート組成物 |
DE10320779A1 (de) * | 2003-05-09 | 2004-11-18 | Degussa Ag | Korrosionsschutz auf Metallen |
WO2005100020A2 (en) * | 2004-04-09 | 2005-10-27 | Vision-Ease Lens | Primer-less abrasion coating for organic glass articles |
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DE102009017822A1 (de) * | 2009-04-20 | 2010-10-21 | Evonik Degussa Gmbh | Wässrige Silansysteme basierend auf Tris(alkoxysilylalkyl)aminen und deren Verwendung |
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JP5665046B2 (ja) | 2010-10-27 | 2015-02-04 | コクヨ株式会社 | 椅子 |
DE102011084183A1 (de) * | 2011-03-25 | 2012-09-27 | Evonik Degussa Gmbh | Wässrige Korrosionsschutzformulierung auf Silanebasis |
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KR102220245B1 (ko) * | 2012-12-25 | 2021-02-25 | 아크조노벨코팅스인터내셔널비.브이. | 코팅 조성물, 이의 제조 방법 및 이의 용도 |
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