TW202233772A - 塗料組成物及被覆物品 - Google Patents
塗料組成物及被覆物品 Download PDFInfo
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- TW202233772A TW202233772A TW110113158A TW110113158A TW202233772A TW 202233772 A TW202233772 A TW 202233772A TW 110113158 A TW110113158 A TW 110113158A TW 110113158 A TW110113158 A TW 110113158A TW 202233772 A TW202233772 A TW 202233772A
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- 239000008199 coating composition Substances 0.000 title claims abstract description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 41
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 31
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 17
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 239000003513 alkali Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 8
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- -1 chlorosilyl Chemical group 0.000 description 46
- 238000000576 coating method Methods 0.000 description 46
- 239000011248 coating agent Substances 0.000 description 41
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- 238000012360 testing method Methods 0.000 description 29
- 239000000203 mixture Substances 0.000 description 21
- 239000003973 paint Substances 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 13
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
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- 239000011701 zinc Substances 0.000 description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 238000011156 evaluation Methods 0.000 description 4
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
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- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SYMYWDHCQHTNJC-UHFFFAOYSA-J 3-oxobutanoate;zirconium(4+) Chemical compound [Zr+4].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O SYMYWDHCQHTNJC-UHFFFAOYSA-J 0.000 description 1
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- QGXMPHBQJFXJCI-UHFFFAOYSA-N 4-(dimethylamino)butyl prop-2-enoate Chemical group CN(C)CCCCOC(=O)C=C QGXMPHBQJFXJCI-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- VOAMNTKOJLSJCP-UHFFFAOYSA-N [Ca].[Zn].NC#N Chemical compound [Ca].[Zn].NC#N VOAMNTKOJLSJCP-UHFFFAOYSA-N 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- SIPHWXREAZVVNS-UHFFFAOYSA-N trichloro(cyclohexyl)silane Chemical compound Cl[Si](Cl)(Cl)C1CCCCC1 SIPHWXREAZVVNS-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-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
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- GHOGBIOKOYTCOD-UHFFFAOYSA-N tritert-butylalumane hydrate Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C.O GHOGBIOKOYTCOD-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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Abstract
Description
本發明有關塗料組成物及被覆物品,若進一步詳述,則有關包含有機樹脂及有機聚矽氧烷之塗料組成物及具有由該塗料組成物所成之硬化膜的被膜物品。
以有機聚矽氧烷系樹脂為主成分之塗料,由於塗膜硬度、耐藥品性、耐熱性、耐候性等優異,故在建築及土木工程結構物領域廣泛使用。
該有機聚矽氧烷系塗料雖具有上述優點,但相反地亦具有硬化速度慢,且所得塗膜之抗龜裂性差的缺點。
為了改善這些缺點,過去已知有使用混合有機聚矽氧烷、醇酸樹脂、聚酯樹脂、丙烯酸樹脂、環氧樹脂等之有機樹脂的組成物作為塗料的方法。作為此等組成物,提案有例如包含含矽烷基之乙烯系聚合物、含矽醇基之有機聚矽氧烷及含烷氧基之有機聚矽氧烷的塗料用組成物(專利文獻1)。
然而,該組成物雖改善了硬化性及耐龜裂性,但具有有機聚矽氧烷系樹脂塗膜的特徵之塗膜硬度、耐藥品性、耐熱性、耐候性等降低之問題。
此外,專利文獻2、3揭示使有機樹脂與有機矽烷或有機聚矽氧烷反應而進行複合化之方法,但該方法由於需要用以使樹脂複合化之合成設備,故就廣泛利用性方面存在問題。
因此,謀求為了引出有機聚矽氧烷與有機樹脂兩者的特性之簡便方法。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開平3-197548號公報
[專利文獻2] 日本特開平11-116683號公報
[專利文獻3] 日本特開平5-345877號公報
[用以解決發明之手段]
本發明係鑑於上述情況而完成者,目的係提供可簡便製造,可賦予具有優異抗龜裂性、塗膜硬度、耐藥品性、耐鹼性、耐熱性、耐候性之硬化被膜的包含有機樹脂與有機聚矽氧烷之塗料組成物。
[用以解決課題之手段]
本發明人等為了達成上述目的而重複進行積極研究,發現以特定比例混合含水解性矽烷基之丙烯酸樹脂與特定有機聚矽氧烷之塗料組成物,在常溫下可硬化,並且由該組成物所得之塗膜,滿足耐龜裂性等之上述特性,因而完成本發明。
亦即,本發明提供:
1. 一種塗料組成物,其包含:
(A)含水解性矽烷基之丙烯酸樹脂:100質量份,
(B)以下述平均單位式(I)表示之有機聚矽氧烷:5~50質量份,及
(C)硬化觸媒:0.1~50質量份
(式中,R
1分別獨立表示取代或非取代之碳原子數1~12之一價烴基,但R
1中至少1個係取代或非取代之碳原子數6~12之芳基,R
2表示氫原子或碳原子數1~6之烴基,a、b、c、d係滿足0≦a<1、0<b<1、0<c≦0.5、0≦d<1,且a+b+c+d=1之數,e係滿足0<e≦4之數)。
2. 如1之塗料組成物,其中前述式(I)中,R
1之全數中,取代或非取代之碳原子數6~12之芳基所佔之比例為40%以上。
3. 如1或2之塗料組成物,其中前述式(I)中,R
1分別獨立為碳原子數1~8之烷基、碳原子數2~8之烯基、碳原子數6~10之芳基或碳原子數7~10之芳烷基。
4. 如3之塗料組成物,其中前述式(I)中,R
1分別獨立為甲基或苯基。
5. 如1至4中任一項之塗料組成物,其中前述式(I)中,R
2之全數中,碳原子數1~6之烷基之比例為50%以上。
6. 如1至5中任一項之塗料組成物,其中前述式(I)中,b及c係滿足0.6≦b+c≦1之數。
7. 如1至6中任一項之塗料組成物,其中前述式(I)中,a為0。
8. 如1至7中任一項之塗料組成物,其中前述式(I)中,d為0。
9. 如1至8中任一項之塗料組成物,其中前述(B)有機聚矽氧烷之凝膠滲透層析法之聚苯乙烯換算之重量平均分子量(Mw)為1,000 ~10,000。
10. 如1至9中任一項之塗料組成物,其中前述(B)有機聚矽氧烷於25℃之動態黏度為50~200mm
2/s。
11. 如1至10中任一項之塗料組成物,其中前述(C)硬化觸媒包含有機錫化合物。
12. 一種硬化膜,其係由如1至10中任一項之塗料組成物形成。
13. 一種被覆物品,其具有基材、及於該基材之至少一面上直接或透過1層以上之其他層形成之如12之硬化膜。
[發明效果]
本發明之塗料組成物可僅藉混合含水解性矽烷基之丙烯酸樹脂與特定之有機矽氧烷而製造,且由於特定有機矽氧烷及/或其縮合物相對於上述丙烯酸樹脂以特定比例含有,故可賦予塗膜硬度、耐藥品性、耐鹼性、耐熱性、耐候性優異之硬化膜,因此適於製造各種被膜物品。
(1) (A)含水解性係矽烷基之丙烯酸樹脂
(A)成分的含水解性矽烷基之丙烯酸樹脂係於空氣中之濕氣及(C)硬化觸媒存在下水解縮合之成分。
本發明中,「水解性矽烷基」只要係藉由水解生成矽醇基,且該矽醇基經脫水縮合,形成矽氧烷鍵之基,具有直接鍵結於矽原子之一價水解性原子(藉由與水反應而生成矽醇基之原子)及直接鍵結於矽原子之一價水解性基(藉由與水反應而生成矽醇基之基)之兩者或一者的矽烷基則未特別限定。
作為上述水解性矽烷基之具體例,舉例為氯矽烷基、溴矽烷基等之鹵化矽烷基;甲氧基矽烷基、乙氧基矽烷基、丙氧基矽烷基、丁氧基矽烷基等之烷基矽烷基;及該等之任意組合。
作為含水解解性矽烷基之丙烯酸樹脂,舉例為例如包含源自含水解性矽烷基之聚合性不飽和化合物之單體單位與源自含(甲基)丙烯醯基化合物(但含水解性矽烷基之聚合不飽和化合物除外)之單體單位的聚合物。
本發明中,基於塗料組成物之貯存安定性及所形成之塗膜的硬化性及塗膜物性之觀點,以含水解性矽烷基之丙烯酸樹脂中的全部單體單位為基準,源自含水解性矽烷基之聚合性不飽和化合物的單體較佳為1~50質量%,更佳為2~30質量%,源自含(甲基)丙烯醯基之化合物的單體單位,較佳為50~99質量%,更佳為70~98質量%。
含水解性矽烷基之丙烯酸樹脂可藉由使含水解性矽烷基之聚合性不飽和化合物與含(甲基)丙烯醯基之化合物,以例如偶氮化合物、過氧化物等作為起始劑之習知自由基聚合方法等聚合而製造,且亦可使用市售品。
又,本說明書中,(甲基)丙烯醯基意指包含丙烯醯基及甲基丙烯醯基之兩者,(甲基)丙烯醯氧基係指包含丙烯醯氧基及甲基丙烯醯氧基之兩者,(甲基)丙烯酸係指包含丙烯酸及甲基丙烯酸之兩者。
又,作為含水解性矽烷基之聚合性不飽和化合物的單體單位亦可包含源自具有水解性矽烷基與(甲基)丙烯醯基之聚合性不飽和化合物,例如源自(甲基)丙烯醯氧基烷氧基矽烷之單體單位。
作為含水解性矽烷基之聚合性不飽和化合物的具體例,舉例為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二乙烯基二甲氧基矽烷、二乙烯基二乙氧基矽烷、乙烯基甲基二甲氧基矽烷、乙烯基甲基二乙氧基矽烷、乙烯基三(甲氧基乙氧基)矽烷等之乙烯基烷氧基矽烷;乙烯基三氯矽烷、二乙烯基二氯矽烷、乙烯基甲基二氯矽烷等之乙烯基氯矽烷;γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧基矽烷、β-(甲基)丙烯醯氧基乙基三甲氧基矽烷、β-(甲基)丙烯醯氧基乙基三乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、γ-(甲基)丙烯醯氧基丙基甲基二丙氧基矽烷、γ-(甲基)丙烯醯氧基丁基苯基二甲氧基矽烷、γ-(甲基)丙烯醯氧基丙基二乙基甲氧基矽烷等之(甲基)丙烯醯氧基烷氧基矽烷;及該等之任意組合等。
作為含(甲基)丙烯醯基之化合物具體例,舉例為(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯 (甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸十三烷酯等之含直鏈狀、分支狀或環狀烷基之(甲基)丙烯酸酯;N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸甲氧基丙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸乙氧基丙酯等之(甲基)丙烯酸烷氧基烷酯;聚乙二醇單甲氧基(甲基)丙烯酸酯等之聚烷二醇單烷氧基(甲基)丙烯酸酯等之含烷氧基之(甲基)丙烯酸酯;(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基環己基甲酯等之含環氧基之(甲基)丙烯酸酯;丙烯酸、甲基丙烯酸、(甲基)丙烯酸羥基烷酯與酸酐之半酯化物等之含羧基(甲基)丙烯酸酯;2-丙烯醯胺-2-甲基丙烷磺酸等之含磺酸基之(甲基)丙烯酸酯;(甲基)丙烯酸氫磷醯氧基乙酯、磷酸單-[(2-羥基乙基)(甲基)丙烯酸]酯等之含磷酸基之(甲基)丙烯酸酯;(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二乙胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯、(甲基)丙烯酸N-第三丁胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丁酯等之含胺基之(甲基)丙烯酸酯;氯化(甲基)丙烯醯氧基乙基三甲基銨、甲基丙烯酸二甲胺基乙基甲基氯化物等之含4級銨鹽基之(甲基)丙烯酸酯;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸2,3-二羥基丁酯、(甲基)丙烯酸4-羥基丁酯等之(甲基)丙烯酸羥基烷酯、對上述(甲基)丙烯酸羥基烷酯使ε-己內酯等之內酯開環聚合的化合物;聚乙二醇單(甲基)丙烯酸酯等之多元醇與丙烯酸或甲基丙烯酸的單酯化物等之含羥基之(甲基)丙烯酸酯等;(甲基)丙烯酸六氟異丙酯、(甲基)丙烯酸全氟辛基甲酯、(甲基)丙烯酸全氟辛基乙酯等之(甲基)丙烯酸氟烷酯;及該等之任意組合等。
含水解性矽烷基之丙烯酸樹脂之分子量並未特別的限制,基於硬化性、耐候性及塗裝性之觀點,凝膠滲透層析法之聚苯乙烯換算之重量平均分子量(Mw)較佳為1,000~100,000,更佳為2,000~80,000。
又,(A)成分可單獨使用1種,亦可組合2種以上使用。
R
1分別獨立表示取代或非取代之碳原子數1~12之一價烴基,但R
1中至少1個係取代或非取代之碳原子數6~12之芳基,R
2表示氫原子或碳原子數1~6之烴基,a、b、c、d係滿足0≦a<1、0<b<1、0<c≦0.5、0≦d<1,且a+b+c+d=1之數,e係滿足0<e≦4之數。
R
1之一價烴基可為直鏈、分支、環狀之任一者,舉例為例如碳原子數1~12,較佳為碳原子數1~8之烷基、碳原子數2~12,較佳碳原子數2~8之烯基、碳原子數6~12,較佳碳原子數6~10之芳基、碳原子數7~12,較佳碳原子數7~10之芳烷基等。
作為碳原子數1~12之烷基的具體例舉例為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、正己基、正庚基、正辛基等。
作為碳原子數2~12之烯基的具體例舉例為乙烯基、烯丙基等。
作為碳原子數6~12之芳基的具體例舉例為苯基、萘基等。
作為碳原子數7~12之芳烷基的具體例舉例為苄基、苯基乙基等。
且鍵結於該等一價烴基之碳原子的氫原子之一部分或全部可經氯、氟、溴等之鹵原子、或氰基等之其他取代基取代,作為該等之具體例舉例為氯甲基、溴乙基、三氟丙基、氯苯基、溴苯基等之鹵素取代烴基;氰基乙基等之氰基取代之烴基等。
該等中,作為R
1較佳為甲基、乙基、正丙基、異丙基、正丁基、異丁基、苯基、苄基、乙烯基,更佳為甲基、苯基。
又,上述R
1至少1個,較佳R
1總數中之40%以上為碳原子數6~12之芳基,較佳為可經鹵原子取代之碳數6~12之芳基。
另一方面,作為R
2之碳原子數1-6之烷基的具體例,舉例為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正己基等,該等中較佳為甲基、乙基。
又本發明中,R
2總數中,碳原子數1~6之烷基的比例較佳為50%以上。
a係滿足0≦a<1之數,但基於所得硬化物之龜裂抑制效果之觀點,較佳為0≦a≦0.3。
b係滿足0<b<1之數,但基於所得硬化物之耐擦傷性之觀點,較佳為0.2≦b≦1。
c係滿足0<c≦0.5之數,但基於組成物之硬化性及所得硬化物之硬度之觀點,較佳為0<c≦0.4。
d係滿足0≦d<1之數,但基於組成物之硬化性及所得硬化物之硬度之觀點,較佳為0≦d≦0.4。
e係滿足0<e≦4之數,但基於有效抑制縮合性官能基所致之縮合反應及所得硬化物之耐龜裂性、耐水性及耐候性之觀點,較佳為滿足0<e≦3之數。
又,a+b+c+d=1。
(B)成分可根據一般有機聚矽氧烷之製造方法製造,例如可藉由使具有水解性基之矽烷化合物水解縮合而獲得。
具有水解性基之矽烷化合物只要於矽原子上含有1~4個水解性基的氯或烷基,且具有滿足上述條件的有機取代基之矽烷化合物,則未特別限制。
作為其具體例,可舉例為四氯矽烷、四甲氧基矽烷、四乙氧基矽烷、四異丙氧基矽烷、四丁氧基矽烷、甲基三氯矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、甲基三異丙氧基矽烷、甲基三丁氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷、二甲基二異丙氧基矽烷、三甲基氯矽烷、三甲基甲氧基矽烷、三甲基乙氧基矽烷、三甲基異丙氧基矽烷、乙基三氯矽烷、乙基三甲氧基矽烷、乙基三乙氧基矽烷、丙基三氯矽烷、丙基三甲氧基矽烷、丙基三乙氧基矽烷、丁基三氯矽烷、丁基三甲氧基矽烷、丁基三乙氧基矽烷、己基三氯矽烷、己基三甲氧基矽烷、己基三乙氧基矽烷、苯基三氯矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、環己基三氯矽烷、環己基三甲氧基矽烷、環己基三乙氧基矽烷、丙基甲基二氯矽烷、丙基甲基二甲氧基矽烷、丙基甲基二乙氧基矽烷、己基甲基二氯矽烷、己基甲基二甲氧基矽烷、己基甲基二乙氧基矽烷、苯基甲基二氯矽烷、苯基甲基二甲氧基矽烷、苯基甲基二乙氧基矽烷、二苯基二氯矽烷、二苯基二甲氧基矽烷、二苯基二乙氧基矽烷、二甲基苯基氯矽烷、二甲基苯基甲氧基矽烷、二甲基苯基乙氧基矽烷及該等之部分水解物等,但基於操作性、副產物餾除容易性以及原料取得容易性,適宜為甲氧基矽烷、乙氧基矽烷。
又上述矽烷化合物可單獨使用1種,亦可組合2種以上使用。
實施水解時,可使用水解觸媒。作為水解觸媒可使用以往習知之觸媒,較佳其水溶液顯示pH1~7的酸性者,特佳為酸性的鹵化氫、磺酸、羧酸、酸性或弱酸性之無機鹽、離子交換樹脂等之固體酸等。
作為酸性觸媒之具體例舉例為氫氟酸、鹽酸、硝酸、硫酸、甲烷磺酸、對甲苯磺酸、甲酸、乙酸、馬來酸、苯甲酸、乳酸、磷酸、表面具有磺酸或羧酸基之陽離子交換樹脂等。
水解觸媒之使用量並未特別的限制,但若考慮反應快速進行且反應後之觸媒去除容易性,相對於水解性矽烷1莫耳,較佳為0.0002~0.5莫耳之範圍。
水解性矽烷與水解縮合反應所需的水量之比並未特別限制,但若考慮防止觸媒失活使反應充分進行,同時反應後的水去除容易性,相對於水解性矽烷1莫耳,較佳為水0.1~10莫耳之比例。
水解縮合時之反應溫度並未特別限制,但若考慮提高反應率並且防止水解性矽烷具有的有機官能基之分解,較佳為-10~150℃。
又,水解縮合時,亦可使用有機溶劑。可使用之有機溶劑的具體例舉例為甲醇、乙醇、丙醇、丙酮、甲基乙基酮、甲基異丁基酮、四氫呋喃、甲苯、二甲苯等。
又(B)成分較佳溶劑等除外之不揮發分為90質量%以上。揮發分多時,有成為使組成物硬化時之空隙發生所致之外觀惡化或機械性質降低的原因之虞。
(B)成分之分子量並未特別限制,但以凝膠滲透層析中的聚苯乙烯換算之重量平均分子量(Mw)較佳為1,000~ 10,000。
(B)成分之動黏度未特別限制,但較佳為50~200 mm
2/s。又,動黏度係依據JIS-Z-8803之利用Cannon-Fenske黏度計在25℃之測定值。
(B)成分之調配量,相對於上述(A)成分100質量份,為5~50質量份,較佳為10~40質量份。(B)成分之量若少於上述範圍,則所形成之塗膜的耐候性、耐熱性不足,另一方面若過多則耐溶劑性、耐鹼性等不足。
又,(B)成分之有機聚矽氧烷可為單一組成,亦可為組成不同的複數化合物之混合物。尤其,可藉由混合平均組成不同之複數化合物而較佳地製造。
(3)硬化觸媒(C)
作為(C)成分之硬化觸媒,只要為有機矽氧烷系塗料中一般使用者,則未特別限制,但較佳為有機金屬化合物,例如Ti、Al、Zr、Sn等之金屬烷氧化物化合物、金屬螯合化合物、金屬酯化合物等,較佳為含有機錫化合物者。
金屬烷氧化物化合物之具體例舉例為三甲氧化鋁、三乙氧化鋁、三正丙氧化鋁、三異丙氧化鋁、三正丁氧化鋁、三異丁氧化鋁、三-第二丁氧化鋁、三-第三丁氧化鋁等之烷氧化鋁;四甲基鈦酸鹽、四乙基鈦酸鹽、四正丙基鈦酸鹽、四異丙基鈦酸鹽、四正丁基鈦酸鹽、四異丁基鈦酸鹽、四-第三丁基鈦酸鹽、四正己基鈦酸鹽、四異辛基鈦酸鹽、四-正月桂基鈦酸鹽等之烷氧化鈦;四乙基鋯酸鹽、四正丙基鋯酸鹽、四異丙基鋯酸鹽、四-正丁基鋯酸鹽、四-第二丁基鋯酸鹽、四-第三丁基鋯酸鹽、四-正戊基鋯酸鹽、四-第三戊基鋯酸鹽、四-第三己基鋯酸鹽、四-正庚基鋯酸鹽、四-正辛基鋯酸鹽、四-正硬脂基鋯酸鹽等之烷氧化鋯;二丁基錫二丁氧化物等。
作為金屬螯合化合物之具體例,舉例為三(乙醯乙酸乙酯)鋁、三(乙醯乙酸正丙酯)鋁、三(乙醯乙酸異丙酯)鋁、三(乙醯乙酸正丁酯)鋁、異丙氧基雙(乙醯乙酸乙酯)鋁、三(乙醯丙酮酸酯)鋁、三(丙醯丙酮酸酯)鋁、二異丙氧基丙醯丙酮酸酯鋁、乙醯丙酮酸酯・雙(丙醯丙酮酸酯)鋁、單乙醯乙酸乙酯・雙(乙醯丙酮酸酯)鋁,乙醯丙酮酸酯鋁・二-第二丁酸酯、乙醯乙酸甲酯鋁・二-第二丁酸酯、二(乙醯乙酸甲酯)鋁・單-第三丁酸酯、二異丙氧基乙醯乙酸乙酯鋁、單乙醯丙酮酸酯・雙(乙醯乙酸乙酯)鋁等之鋁螯合化合物;二異丙氧基・雙(乙醯乙酸乙酯)鈦酸鹽、二異丙氧基・雙(乙醯丙酮酸酯)鈦酸鹽、二-正丁氧基・雙(乙醯乙酸酯)鈦酸鹽等之鈦螯合化合物;四(乙醯丙酮酸酯)鋯、四(乙醯乙酸正丙酯)鋯、四(乙醯乙酸乙酯)鋯等之鋯螯合化合物;二丁基錫二乙酸酯、二丁基錫二(2-乙基己酸酯)、二苄基錫二(2-乙基己酸酯)、二丁基錫二月桂酸酯、二丁基錫二異辛基丙二酸酯、二丁基錫二(乙醯乙酸酯)等之錫酯化合物等之錫螯合化合物,但使用錫螯合化合物時,就形成的塗膜的耐藥品性而言係較佳。
作為上述錫酯化合物,亦可使用市售品,舉例為例如NEOSTANN U-100、U-130、U-200、U-220H、U-303、U-700、U-810、U-820、U-830(以上為日東化成(股)製)、BT-120S(KANEKA(股)製)等。
(C)成分之調配量,只要足以使組成物硬化之量即可,但通常相對於(A)成分100質量份為0.1~50質量份,較佳為1~30質量份。
又,(C)成分之硬化觸媒可單獨使用,亦可組合2種以上使用。
(4)任意成分
本發明之塗料組成物於不阻礙本發明效果之範圍亦可包含任意添加劑。
作為添加劑之具體例,舉例為溶劑、非反應性矽氧油、反應性矽氧油、矽烷偶合劑等之密著賦予劑、非反應性高分子樹脂、填充劑、調平劑、流變調整劑、反應性稀釋劑、非反應性稀釋劑、界面活性劑、分散劑、消泡劑、脫水劑、抗老化劑、抗氧化劑、抗靜電劑、紅外吸收劑、紫外線吸收劑、光安定劑、螢光劑、染料、顏料、香水、研磨劑、防鏽劑、觸變賦予劑等。該些各可單獨使用1種,亦可組合2種以上使用。
作為顏料舉例為例如氧化鈦、紅色氧化鐵、花青系著色顏料、碳黑、氧化鋯粉末等之著色顏料;氧化矽、氧化鋇粉、沉降性硫酸鋇、碳酸鋇、碳酸鈣、石膏、黏土、白碳、矽藻土、滑石、碳酸鎂、氧化鋁白、光澤白、碳酸鈣(Tankaru)等之體質顏料;磷酸鋅、磷·矽酸鋅、磷酸鋁鋅、磷酸鈣鋅、磷酸鈣、焦磷酸鋁、焦磷酸鈣、三聚磷酸二氫鋁、偏磷酸鋁、偏磷酸鈣、氧化鋅、磷鉬酸鋅、磷鉬酸鋁、鋅、氧化鋅、鉬酸鋅、鉬酸鈣、硼酸鹽系、偏硼酸鋇、氰胺鋅鈣、矽酸鈣、偏矽酸鈣;於多孔質氧化矽粒子結合鈣、鋅、鈷、鉛、鍶、鋇等之陽離子之改質氧化矽、藉由離子交換結合陽離子而得之離子交換氧化矽、焦磷酸鋁、五氧化釩、釩酸鈣、偏釩酸銨等之釩系化合物等之防鏽顏料等,該等可單獨使用,亦可以組合2種以上使用。
本發明之塗料組成物包含顏料時,其含量基於形成之塗膜的耐候性之觀點,相對於(A)成分與(B)成分之合計固形分100質量份,以固形分質量計,較佳為5~100質量份,更佳為30~90質量份。
(5)製造方法
本發明之塗料組成物可藉由於常溫以任意順序混合上述(A)成分、(B)成分、(C)成分及任意成分並攪拌而獲得。
本發明之塗料組成物之黏度並未特別限制,但考慮使成形或塗佈作業性量好,抑制紋理等發生,則藉由旋轉黏度計測定之25℃下之黏度,較佳為100,000mPa・s以下,更佳為20,000mPa・s以下。黏度下限並未特別限制,較佳為10mPa・s以上。
(6)塗料組成物之硬化膜及被覆物品
將本發明之塗料組成物塗佈於被塗物,藉由使其硬化獲得硬化膜及被覆物品。
塗佈方法並未限制,可採用例如噴霧器塗佈、輥塗、刷塗、流塗等之已知方法。
本發明之塗料組成物在常溫可硬化,但為了促進硬化亦可根據需要進行加熱。
加熱溫度較佳為40~150℃,因此,形成的硬化塗膜可發揮優異的耐候性、耐熱性、耐鹼性。
作為被塗物舉例為玻璃或依期望經基底處理之金屬材料,例如鋼板、鍍鋅、不鏽鋼、鋁等,具有鹼性之基材舉例為例如水泥、砂漿、石板、石板瓦等,窯業系建材、塑膠等,以及在該等上形成舊塗膜者。
作為本發明之塗料組成物的用途並未特別限制,但舉例為橋樑、輸電塔、工廠、槽體等之鋼製構造物的重防腐蝕塗裝用途。
本發明之塗料組成物之長期耐候性優異,單獨以該組成物即可保護被塗物免受惡劣環境的影響,可賦予維持美觀之硬化膜,但根據必要亦可設置習知之底塗及/或中間塗層。
作為上述底塗塗料,可舉例為例如環氧樹脂塗料、改質環氧樹脂塗料、環氧樹脂系玻璃細片塗料、環氧樹脂被覆材料、超厚膜形環氧樹脂塗料、環氧樹脂富鋅塗料、無機富鋅塗料、氯化橡膠樹脂系塗料、鄰苯二甲酸樹脂系塗料、環氧酯樹脂塗料等,作為中間塗層塗料之例,可舉例為環氧樹脂系塗料、聚胺基甲酸酯系塗料、環氧樹脂MIO塗料、酚樹脂系MIO塗料、氯化橡膠樹脂系塗料、鄰苯二甲酸樹脂系塗料等。
[實施例]
以下舉例實施例及比較例更具體說明本發明,但本發明不限定於該等實施例。又,重量平均分子量係使用GPC(凝膠滲透層析儀,HLC-8220,TOSOH(股)製)以四氫呋喃(THF)作為展開溶劑而測定之值,不揮發分係利用於鋁盤上於105℃加熱乾燥3小時後之加熱殘量法之測定值,動黏度係使用Cannon-Fenske黏度計在25℃下測定之值。此外,自
1H-NMR及
29Si-NMR測定結果算出下述聚矽氧烷之平均單位式中各矽氧烷單位之構成比。
[1]塗料組成物之製造
[實施例1-1~1-4、比較例1-1~1-8]
以表1所示之組成比混合下述各成分,製造塗料組成物(i)~(xii)。
(A)成分
(A-1):含水解性矽烷基之丙烯酸樹脂(Zemlak YC-5920,KANEKA(股)製)
(A-2):含水解性矽烷基之丙烯酸樹脂(Zemlak YC-3623,KANEKA(股)製)
(B)成分
(B-1):結構單位比以(R
1SiO
3/2)
0.60(R
1 2SiO
2/2)
0.40(R
2O
1/2)
0.24表示,R
1為苯基(43%)、甲基(57%),R
2為甲基(73%)、氫原子(27%),重量平均分子量為1,800,不揮發分為96質量%,動黏度為100mm
2/s之有機聚矽氧烷
(B-2):結構單位比以(R
1SiO
3/2)
1.00(R
2O
1/2)
0.22表示,R
1為甲基,R
2為甲基(74%)、氫原子(26%),重量平均分子量為1,800,不揮發分為94質量%,動黏度為25mm
2/s之有機聚矽氧烷
(B-3):結構單位比以(SiO
4/2)
1.00(R
2O
1/2)
0.26表示,R
2為甲基(90%)、氫原子(10%),重量平均分子量為1,000,不揮發分87質量%,動黏度為5mm
2/s之有機聚矽氧烷
(B-4):結構單位比以(R
1SiO
3/2)
0.50(R
1 2SiO
2/2)
0.50(R
2O
1/2)
0.19表示,R
1為甲基,R
2為甲基(69%)、氫原子(31%),重量平均分子量為4,500,不揮發分為87質量%,動黏度為80mm
2/s之有機聚矽氧烷
(B-5):結構單位比以(R
1SiO
3/2)
0.40(R
1 2SiO
2/2)
0.60(R
2O
1/2)
0.19表示,R
1為苯基(38%)、甲基(62%),R
2為甲基(12%)、氫原子(88%),重量平均分子量為2,500,不揮發分為50質量%,動黏度為5 mm
2/s之有機聚矽氧烷
(C)成分
有機錫化合物系硬化觸媒(BT-120S,KANEKA(股)製)
[溶劑]
乙酸乙酯/乙酸丁酯=1/1(質量比)之混合物
[2]被覆物品之製造及評價
[實施例2-1~2-4、比較例2-1~2-8]
實施例1-1~1-4、比較例1-1~1-8所得之塗料組成物(i)~(xii)分別藉由流動塗佈器以乾燥塗膜厚成為30μm之方式塗佈於金屬基板上,以23℃、50%RH之條件下養生7天,獲得被膜。
針對所得被覆物品進行塗膜外觀、摩擦試驗、鉛筆硬度、耐鹼試驗、耐熱試驗、促進耐候性之評價。結果示於表2。
(1)塗膜外觀
以目視觀察,塗膜表面均一且不因凝集物而產生凹凸或龜裂者評價為○,塗膜表面不均一且龜裂,及因凝集物而產生凹凸或龜裂者評價為×。
(2)鉛筆硬度
依據JIS K5600-5-4以750g荷重下測定。
(3)摩擦試驗
將BEMCOT M-3II(旭化成(股)製,面積4cm
2)浸於丙酮中,以荷重500gf下對表面進行往復摩擦30次,以目視評價塗膜外觀。與摩擦試驗前的塗膜外觀相比,摩擦拭驗後未見到變化者評價為○,見到塗膜剝落或變白者評價為×。
(4)耐鹼試驗
耐鹼性試驗係依據JIS K5660-6-2,將試驗片於23℃條件下於氫氧化鈣飽和溶液中浸泡7天。浸泡後,以自來水輕輕清洗試驗片,乾燥2小時,藉由目視觀察塗膜之膨脹、裂開、剝落、光澤變化,藉以下三階段進行評價。
○:與現狀試驗片相比未見到大幅變化。
△:與現狀試驗片相比稍有脫光澤。
×:與現狀試驗片相比顯著有脫光澤、裂開、剝落。
(5)耐熱試驗
使用200℃乾燥器進行耐熱試驗。作為試驗條件,以200℃乾燥器進行24小時加熱後,在室溫下空氣冷卻2小時。試驗結束後,藉目視觀察塗膜之膨脹、裂開、剝落、光澤變化,藉以下三個階段進行評價。
○:與現狀試驗片相比未見到大幅變化。
△:與現狀試驗片相比稍有脫光澤。
×:與現狀試驗片相比顯著有脫光澤、裂開、剝落。
(6)促進耐候性
使用超促進耐候性試驗機(岩崎電氣(股)製EYE SUPER UV測試儀)進行促進耐候性測試。且,試驗片係使用聚酯塗裝鋼板(0.8×70×60mm)。作為試驗條件,將4小時照射(紫外線照射度90mW,黑板溫度63℃,70%RH)、4小時黑暗(黑板溫度63℃,70%RH)、4小時結露(黑板溫度30℃,90%RH)之12小時設為1個循環,試驗50個循環。試驗結束後,藉目視觀察塗膜之膨脹、裂開、剝落、光澤變化,藉以下三個階段進行評價。
○:與現狀試驗片相比未見到大幅變化。
△:與現狀試驗片相比稍有脫光澤。
×:與現狀試驗片相比顯著有脫光澤、裂開、剝落。
如表2所示,可知實施例2-1~2-4所得之塗膜之耐龜裂性、塗層硬度、耐藥品性、耐鹼性、耐熱性及耐候性優異。
另一方面,可知使用不含有機聚矽氧烷之組成物的比較例2-1、2-2之塗膜及使用(B)成分之調配量不足的組成物之比較例2-3之塗膜,耐鹼性、耐熱性、耐候性不足。且可知使用含有過量(B)成分的組成物之比較例2-4的塗膜,塗膜硬度、耐藥品性、耐鹼性差,使用包含本發明之(B)成分以外之有機聚矽氧烷的組成物之比較例2-5~2-8的塗膜,除了在摩擦試驗中見到剝落外,各種塗膜性能亦較差者。
Claims (13)
- 如請求項1之塗料組成物,其中前述式(I)中,R 1之全數中,取代或非取代之碳原子數6~12之芳基所佔之比例為40%以上。
- 如請求項1或2之塗料組成物,其中前述式(I)中,R 1分別獨立為碳原子數1~8之烷基、碳原子數2~8之烯基、碳原子數6~10之芳基或碳原子數7~10之芳烷基。
- 如請求項3之塗料組成物,其中前述式(I)中,R 1分別獨立為甲基或苯基。
- 如請求項1至4中任一項之塗料組成物,其中前述式(I)中,R 2之全數中,碳原子數1~6之烷基之比例為50%以上。
- 如請求項1至5中任一項之塗料組成物,其中前述式(I)中,b及c係滿足0.6≦b+c≦1之數。
- 如請求項1至6中任一項之塗料組成物,其中前述式(I)中,a為0。
- 如請求項1至7中任一項之塗料組成物,其中前述式(I)中,d為0。
- 如請求項1至8中任一項之塗料組成物,其中前述(B)有機聚矽氧烷之凝膠滲透層析法之聚苯乙烯換算之重量平均分子量(Mw)為1,000 ~10,000。
- 如請求項1至9中任一項之塗料組成物,其中前述(B)有機聚矽氧烷於25℃之動態黏度為50~200mm 2/s。
- 如請求項1至10中任一項之塗料組成物,其中前述(C)硬化觸媒包含有機錫化合物。
- 一種硬化膜,其係由如請求項1至10中任一項之塗料組成物形成。
- 一種被覆物品,其具有基材、及於該基材之至少一面上直接或透過1層以上之其他層形成之如請求項12之硬化膜。
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JP3120617B2 (ja) | 1992-02-13 | 2000-12-25 | ジェイエスアール株式会社 | コーティング用組成物 |
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