JP3733854B2 - INORGANIC FILM FORMING METHOD AND COATED ARTICLE - Google Patents
INORGANIC FILM FORMING METHOD AND COATED ARTICLE Download PDFInfo
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- JP3733854B2 JP3733854B2 JP2000327795A JP2000327795A JP3733854B2 JP 3733854 B2 JP3733854 B2 JP 3733854B2 JP 2000327795 A JP2000327795 A JP 2000327795A JP 2000327795 A JP2000327795 A JP 2000327795A JP 3733854 B2 JP3733854 B2 JP 3733854B2
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- inorganic
- coating
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- thermally
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- 238000000034 method Methods 0.000 title claims description 32
- 238000000576 coating method Methods 0.000 claims description 124
- 239000011248 coating agent Substances 0.000 claims description 123
- 239000000463 material Substances 0.000 claims description 73
- 239000004065 semiconductor Substances 0.000 claims description 52
- 230000003287 optical effect Effects 0.000 claims description 47
- 239000003973 paint Substances 0.000 claims description 45
- 229920002050 silicone resin Polymers 0.000 claims description 44
- -1 isostearoyl group Chemical group 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 18
- 150000001282 organosilanes Chemical class 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 5
- VELFFNYFZHVFNA-UHFFFAOYSA-N dioctyl phosphono phosphate Chemical group CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC VELFFNYFZHVFNA-UHFFFAOYSA-N 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002347 octyl 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])[H] 0.000 claims description 3
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical group CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 2
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical group CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000005641 methacryl group Chemical group 0.000 claims description 2
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 claims description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical group CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 239000000945 filler Substances 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 230000000694 effects Effects 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000008119 colloidal silica Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 238000005299 abrasion Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- LTOATULEBMBWSO-UHFFFAOYSA-N acetic acid;2-ethoxyethanol Chemical compound CC(O)=O.CCOCCO LTOATULEBMBWSO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-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
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical compound [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGHFDTDSFZTYBW-UHFFFAOYSA-N O-silylhydroxylamine Chemical class NO[SiH3] YGHFDTDSFZTYBW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FKHCXHCSCLRWFC-UHFFFAOYSA-N chloro(trimethyl)silane silane Chemical class [SiH4].C[Si](Cl)(C)C FKHCXHCSCLRWFC-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- SPBMDAHKYSRJFO-UHFFFAOYSA-N didodecyl hydrogen phosphite Chemical group CCCCCCCCCCCCOP(O)OCCCCCCCCCCCC SPBMDAHKYSRJFO-UHFFFAOYSA-N 0.000 description 1
- QHNXEVRKFKHMRL-UHFFFAOYSA-N dimethylazanium;acetate Chemical compound CNC.CC(O)=O QHNXEVRKFKHMRL-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- WNEDOMBPJDUQPS-BFIADXHOSA-L dioctyltin(2+);(z)-4-hydroxy-4-oxobut-2-enoate Chemical compound CCCCCCCC[Sn](OC(=O)\C=C/C(O)=O)(OC(=O)\C=C/C(O)=O)CCCCCCCC WNEDOMBPJDUQPS-BFIADXHOSA-L 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- UQMGAWUIVYDWBP-UHFFFAOYSA-N silyl acetate Chemical class CC(=O)O[SiH3] UQMGAWUIVYDWBP-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 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
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ハードコート性（表面硬度、耐磨耗性、耐擦傷性等）を保ちつつ光半導体の光触媒作用に由来する各種特性を十分に発揮する無機被膜を形成することのできる方法と、この方法により得られる塗装品に関する。
【０００２】
【従来の技術】
シリコーンレジンを主成分とする塗料を基材表面に塗布し、硬化することにより、防汚性等の性能を有する塗膜を形成する事が知られており、各種基材に適用されている。また、前記シリコーンレジンの構成成分として４官能のシリコーンレジンを用いた場合においては、上記防汚性等の性能に加えてハードコート性（表面硬度、耐磨耗性、耐擦傷性等）が向上することも知られている。さらには、シリコーンレジンを主成分とし、光半導体を含有する塗料を塗布、硬化して得られる塗膜においては、以下のような様々な効果が期待でき、各種基材に適用されている。
【０００３】
光半導体に励起波長（たとえば、４００ｎｍ）の光（紫外線）が当たると、有機物を酸化分解することができる活性酸素が発生するため、光半導体を含有する塗料を基材の表面にコーティングした材料には、その表面に付着したカーボン系汚れ成分（たとえば、自動車の排気ガス中に含まれるカーボン留分や、たばこのヤニ等）を分解する自己洗浄効果；アミン化合物、アルデヒド化合物に代表される悪臭成分を分解する消臭効果；大腸菌、黄色ブドウ球菌に代表される菌成分の発生を防ぐ抗菌効果；防かび効果等が期待される。また、光半導体を含有する塗料を基材の表面にコーティングした材料に紫外線が当たると、光半導体がその光触媒作用で、空気中の水分または該材料表面に付着した水分を水酸化ラジカル化し、この水酸化ラジカルが、水をはじく有機物等（該材料表面に付着したものと該材料表面中に含まれるもの）を分解除去することにより、該材料表面に対する水の接触角が低下して該材料表面が水に濡れ（馴染み）やすくなるという親水性（水濡れ性）向上効果もある。この親水性向上効果から、屋内の部材においては、ガラスや鏡が水滴で曇りにくい防曇効果が期待され、屋外部材においては、付着した汚れが雨水によって洗浄される防汚効果が期待される。また、光半導体を含有する塗料を基材表面にコーティングした材料には、光半導体の光触媒作用による帯電防止機能もあり、この機能によっても防汚効果が期待される。
【０００４】
【発明が解決しようとする課題】
ところが、上記の従来技術には、以下のような問題点があった。それは、シリコーンレジンの構成成分として４官能のシリコーンレジンを用い、かつ、光半導体が含有される場合、シリコーンレジンに対する光半導体の比率を増していくと、前記のような光半導体による効果がより期待できるが、その半面、ハードコート性が低減して、表面硬度、耐磨耗性や耐擦傷性等が低下する。逆に、シリコーンレジンに対する光半導体の比率を減じていくと、ハードコート性は向上あるいは維持されるが、その半面、光半導体による効果が低減する。
【０００５】
そこで、本発明の課題は、ハードコート性（表面硬度、耐磨耗性、耐擦傷性等）を保ちつつ光半導体の光触媒作用に由来する各種特性を十分に発揮する無機被膜を形成することのできる方法と、この方法により得られる塗装品とを提供することにある。
【０００６】
【課題を解決するための手段】
上記課題を解決するため、本発明者は種々検討を重ねた。その結果、４官能シリコーンレジンからなるシリコーンレジンおよび光半導体に加え、塗膜を硬化させようとする温度では熱分解せずに、それより高い温度で熱分解する熱分解性材料をさらに配合した無機塗料を用い、これを基材に塗装して塗膜を形成し、該塗膜を前記熱分解性材料が熱分解しない温度で硬化させた後、温度を前記熱分解性材料が熱分解する温度に上げて前記熱分解性材料を熱分解するようにすればよいことを実験で確認して、本発明を完成した。
【０００７】
すなわち、本発明に係る無機被膜形成方法は、一般式（１）：一般式ＳｉＸ4 （ここでＸは同一または異種の加水分解性基を示す）で表される４官能加水分解性オルガノシランの（部分）加水分解物を含む４官能シリコーンレジンからなるシリコーンレジンと光半導体とを含有する無機塗料を基材に塗装して塗膜を形成した後、該塗膜を硬化させることにより、前記基材の表面に無機被膜を形成する方法であって、前記無機塗料中に、その塗膜を硬化させようとする温度では熱分解せずに、それより高い温度で熱分解する熱分解性材料をも含有させるとともに、前記無機塗料の塗膜を、前記熱分解性材料が熱分解しない温度で硬化させた後、温度を前記熱分解性材料が熱分解する温度に上げて前記熱分解性材料を熱分解することを特徴とする。
【０００８】
なお、本明細書中、「（部分）加水分解」は「部分加水分解および／または加水分解」を意味する。
本発明に係る塗装品は、上記本発明の無機被膜形成方法により得られたものである。
【０００９】
【発明の実施の形態】
本発明で用いられる無機塗料の必須成分の一つであるシリコーンレジンは、４官能加水分解性オルガノシランの（部分）加水分解物を含む４官能シリコーンレジンからなり、バインダー樹脂および造膜成分として用いられるとともに、上記無機塗料から形成される無機被膜に表面親水性（水濡れ性）を付加することによって同膜に防曇性、雨水洗浄による防汚性等をもたらす成分である。また、上記無機被膜は、４官能シリコーンレジンの使用により、ハードコート性（表面硬度、耐磨耗性、耐擦傷性等）等にも優れたものとなる。
【００１０】
シリコーンレジンは、その形態を特に限定されず、たとえば、溶液状のものでも分散液状のもの等でも構わない。
４官能シリコーンレジンの原料として用いられる４官能加水分解性オルガノシランとしては、前記一般式（１）で表されるものが用いられる。
前記一般式（１）中、Ｘとしては、同一または異種の加水分解性基であれば特に限定はされないが、たとえば、アルコキシ基、アセトキシ基、オキシム基、エノキシ基、アミノ基、アミノキシ基、アミド基等が挙げられる。これらの中でも、入手の容易さおよびシリコーンレジンを調製しやすいことから、アルコキシ基が好ましい。また、アルコキシ基（ＯＲ基；Ｒはアルキル基）の中でも、Ｒが炭素数１〜８のアルキル基であるものが、入手の容易さ、シリコーンレジンの調製しやすさだけでなく、得られるシリコーンレジンを含む無機塗料を塗布し、硬化させる際に、縮合反応が起こりやすく、その結果、硬い無機被膜になりやすい等の点から特に好ましい。上記炭素数１〜８のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等が挙げられる。アルコキシ基中に含有されるアルキル基のうち、炭素数３以上のものについては、ｎ−プロピル基、ｎ−ブチル基等のように直鎖状のものであってもよいし、イソプロピル基、イソブチル基、ｔ−ブチル基等のように分岐を有するものであってもよい。
【００１１】
前記４官能加水分解性オルガノシランの具体例としては、特に限定はされないが、たとえば、４官能性の、アルコキシシラン類、アセトキシシラン類、オキシムシラン類、エノキシシラン類、アミノシラン類、アミノキシシラン類、アミドシラン類などが挙げられる。これらの中でも、入手の容易さおよびシリコーンレジンを調製しやすいことから、アルコキシシラン類が好ましい。また、このアルコキシシラン類の中でも、入手の容易さ、シリコーンレジンの調製しやすさだけでなく、得られるシリコーンレジンを含む無機塗料を塗布し、硬化させる際に、縮合反応が起こりやすく、その結果、硬い無機被膜になりやすい等の点から、アルコキシ基（ＯＲ基；Ｒはアルキル基）中のＲが上記炭素数１〜８のアルキル基であるアルコキシシラン類が特に好ましい。
【００１２】
４官能性アルコキシシラン類の具体例としては、特に限定はされないが、たとえば、テトラメトキシシラン、テトラエトキシシラン、テトラｎ−プロポキシシラン、テトライソプロポキシシラン、テトラ−ｔ−ブトキシシラン等のテトラアルコキシシランが挙げられる。これらの中でも、テトラメトキシシラン、テトラエトキシシランが好ましい。
さらに、一般にシランカップリング剤と呼ばれるオルガノシラン化合物もアルコキシシラン類に含まれる。
４官能加水分解性オルガノシランは、１種のみを用いてもよいし、２種以上を併用してもよい。
【００１３】
４官能シリコーンレジンは、たとえば、４官能加水分解性オルガノシランに硬化剤としての水および必要に応じて触媒等を必要量添加して、（部分）加水分解を行わせてプレポリマー化させることにより、調製することができる。
４官能加水分解性オルガノシランを（部分）加水分解する際に用いられる水の量は、特に限定はされないが、たとえば、４官能加水分解性オルガノシランの有する加水分解性基（Ｘ）に対する水（Ｈ2 Ｏ）のモル当量比（Ｈ2 Ｏ／Ｘ）で示せば、好ましくは０．３〜５、より好ましくは０．３５〜４、さらに好ましくは０．４〜３．５の範囲である。上記モル当量比が０．３未満であると、加水分解が十分進行せず、無機被膜が脆くなる恐れがあり、５を超えると、得られるシリコーンレジンが短時間でゲル化する傾向があるため、貯蔵安定性が低下する恐れがある。
【００１４】
４官能加水分解性オルガノシランを（部分）加水分解する際に必要に応じて用いられる触媒としては、特には限定はされないが、無機塗料の製造工程にかかる時間を短縮する点から、酸性触媒が好ましい。酸性触媒としては、特に限定はされないが、たとえば、酢酸、クロロ酢酸、クエン酸、安息香酸、ジメチルマロン酸、蟻酸、プロピオン酸、グルタール酸、グリコール酸、マレイン酸、マロン酸、トルエンスルホン酸、シュウ酸などの有機酸；塩酸、硝酸、ハロゲン化シラン等の無機酸；酸性コロイダルシリカ、酸化チタンゾル等の酸性ゾル状フィラー等が挙げられ、これらを１種または２種以上使用することができる。
【００１５】
４官能加水分解性オルガノシランの（部分）加水分解は、必要に応じ、加温（たとえば、４０〜１００℃に加熱）して行っても良い。
４官能加水分解性オルガノシランの（部分）加水分解は、必要に応じ、４官能加水分解性オルガノシランを適当な溶媒で希釈して行ってよい。そのような希釈溶媒（反応溶媒）としては、特に限定はされないが、たとえば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等の低級脂肪族アルコール類；エチレングリコール、エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテル等のエチレングリコール誘導体；ジエチレングリコール、ジエチレングリコールモノブチルエーテル等のジエチレングリコール誘導体；およびジアセトンアルコール等を挙げることができ、これらからなる群より選ばれた１種もしくは２種以上のものを使用することができる。これらの親水性有機溶媒と併用して、トルエン、キシレン、ヘキサン、ヘプタン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、メチルエチルケトオキシム等の１種もしくは２種以上も用いることができる。
【００１６】
本発明で用いられるシリコーンレジンの重量平均分子量（Ｍｗ）は、特に限定されるものではないが、ポリスチレン換算で５００〜１０００の範囲が好ましい。５００未満の場合はシリコーンレジンが不安定であったり、１０００より大きい場合は無機被膜が十分な硬度を保てない等の不都合がある。
本発明で用いられる無機塗料は、後で述べる光触媒効果による各種機能を得るとともに、形成される無機被膜の表面親水性を、光触媒効果でさらに高くしたり長期間維持させたりするために、必須成分としてさらに光半導体を含む。
光半導体としては、特に限定はされないが、たとえば、酸化チタン、酸化亜鉛、酸化錫、酸化鉄、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化ルテニウム、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化銅、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化マンガン、酸化コバルト、酸化ロジウム、酸化ニッケル、酸化レニウム等の金属酸化物の他、チタン酸ストロンチウム等が、塗膜の硬化（特に常温を含む低温での硬化）を促進する効果も得られる点で好ましい。これらの中でも、上記金属酸化物が、実用的に容易に利用可能な点で好ましく、金属酸化物の中でも特に酸化チタンが、その光触媒性能、硬化促進性能、安全性、入手の容易さおよびコストの面で好ましい。なお、酸化チタンを光半導体として用いる場合は、結晶型がアナタース型（アナターゼ型）であるものを用いる方が、光触媒性能および硬化促進性能が最も強く、しかも長期間発現するとともに、光触媒性能および硬化促進性能がより短時間で発現する点で好ましい。
【００１７】
光半導体は、１種のみ用いてもよいし、２種以上を組み合わせて用いてもよい。
なお、光半導体の原料となるものも、最終的に光半導体の性質を示す物であれば使用可能である。
光半導体に励起波長（たとえば、４００ｎｍ）の光（紫外線）が当たると活性酸素が発生することは公知である。活性酸素は有機物を酸化して分解することができるため、光半導体を含有する塗料を基材の表面にコーティングした材料には、その表面に付着したカーボン系汚れ成分（たとえば、自動車の排気ガス中に含まれるカーボン留分や、たばこのヤニ等）を分解する自己洗浄効果；アミン化合物、アルデヒド化合物に代表される悪臭成分を分解する消臭効果；大腸菌、黄色ブドウ球菌に代表される菌成分の発生を防ぐ抗菌効果；防かび効果等が期待される。また、光半導体を含有する塗料を基材の表面にコーティングした材料に紫外線が当たると、光半導体がその光触媒作用で、空気中の水分または該材料表面に付着した水分を水酸化ラジカル化し、この水酸化ラジカルが、水をはじく有機物等（該材料表面に付着したものと該材料表面中に含まれるもの）を分解除去することにより、該材料表面に対する水の接触角が低下して該材料表面が水に濡れ（馴染み）やすくなるという親水性（水濡れ性）向上効果もある。この親水性向上効果から、屋内の部材においては、ガラスや鏡が水滴で曇りにくい防曇効果が期待され、屋外部材においては、付着した汚れが雨水によって洗浄される防汚効果が期待される。
【００１８】
さらには、光半導体の光触媒作用による帯電防止機能もあり、この機能によっても防汚効果がさらに向上する。たとえば、光半導体を含む塗膜に紫外線を照射すると、この塗膜に含まれる光半導体の作用により塗膜の表面抵抗値が下がることで帯電防止効果が発現されて、塗膜表面がさらに汚れにくくなる。光半導体含有塗膜に紫外線が照射されたとき、どのようなメカニズムで塗膜の表面抵抗値が下がるのかはまだ明確には確認されていないが、紫外線照射により生成した電子とホ−ルが作用することで塗膜の表面抵抗値が下がるものと考えられる。
光半導体の表面に金属が担持されていると、光半導体の光触媒効果がより高くなる。そのメカニズムは、まだ明確には確認されていないが、光半導体の表面に金属が担持されることにより光半導体の電荷分離が促進されて、電荷分離により生成した電子とホ−ルの消失確立が小さくなることが関係していると考えられる。
【００１９】
光半導体の表面に担持してよい金属としては、たとえば、銀、銅、鉄、ニッケル、亜鉛、白金、金、パラジウム、カドミウム、コバルト、ロジウム、ルテニウム等が、光半導体の電荷分離をより促進させる点で好ましい。担持される金属は、１種のみでも２種以上でもよい。
金属の担持量は、特に限定はされないが、たとえば、光半導体に対し、０．１〜１０重量％であることが好ましく、０．２〜５重量％であることがより好ましい。担持量が０．１重量％未満だと、担持効果が充分に得られない傾向があり、１０重量％を超えて担持しても、効果はあまり増加せず、逆に変色や性能劣化等の問題が起きる傾向がある。
【００２０】
金属の担持方法としては、特に限定するわけではないが、浸積法、含浸法、光還元法等が挙げられる。
光半導体は、粘土架橋体の層間に挿入された形で用いても良い。光半導体が該粘土架橋体の層間で微粒子状に分散して光触媒性能が向上するからである。
本発明で用いられる無機塗料は、熱分解性材料をも必須成分として含む。この熱分解性材料としては、無機塗料の塗膜を硬化させようとする温度では熱分解せずに、それより高い温度で熱分解するものが用いられる。この熱分解性材料を無機塗料に含ませ、その塗膜を形成し、該塗膜を前記熱分解性材料が熱分解しない温度で硬化させた後、温度を前記熱分解性材料が熱分解する温度に上げて前記熱分解性材料を熱分解することにより、被膜表面の熱分解性材料が熱分解して、該被膜表面から光半導体が露出するか、あるいは、該被膜表面における光半導体の含有量が増加するため、光半導体の光触媒作用を効果的に引き出すことが可能となる。
【００２１】
このような熱分解性材料としては、特に限定はされないが、たとえば、有機金属化合物、シラン化合物等が挙げられる。
前記有機金属化合物としては、特に限定はされないが、たとえば、有機チタン化合物、有機アルミニウム化合物等が挙げられる。それらの具体例としては、特に限定はされないが、たとえば、以下に示す一般式（２）〜（４）、構造式（５）、一般式（６）〜（９）で表される有機チタン化合物および一般式（１０）で表される有機アルミニウム化合物等が挙げられる。
一般式（２）：Ti(O-C3H7)m (OC2H4N(C2H4OH)2)4-m （ｍは１〜３の整数）
一般式（３）：Ti(O-nC4H9) m (OC2H4N(C2H4OH)2)4-m（ｍは１〜３の整数）
一般式（４）：(C8H17O)m Ti(OCH2CH(C2H5)CH(OH)C3H7)4-m （ｍは１〜３の整数）
構造式（５）：Ti(C5H7O2)4
一般式（６）：Ti(OH)m (OCH(CH3)COOH)4-m （ｍは１〜３の整数）
一般式（７）：Ti(O-iC3H7)R1 m R2 3-m（ｍは１〜３の整数であり、Ｒ1 およびＲ2 はイソステアロイル基、オクタノイル基、メタクリル基、ドデシルベンゼンスルホニル基、ジオクチルホスフェート基、クミルフェニル基、ジオクチルパイロホスフェート基、ｎ−アミノエチル−アミノエチル基、アセチルアセトナト基または２−エチル−１，３−ヘキサンジオラト基を示す。）
一般式（８）：(R3)4Ti(R4)2（Ｒ3 はイソプロピル基、オクチル基または２，２−ジアリルオキシメチル−１−ブチル基を示し、Ｒ4 はジオクチルホスファイト基またはジドデシルホスファイト基を示す。）
一般式（９）：(R5)Ti(R6)2 （Ｒ5 はオキシアセテート基またはエチレン基を示し、Ｒ6 はジクミルフェニル基、ジオクチルパイロホスフェート基またはイソステアロイル基を示す。）
一般式（１０）：Al(R7) m (R8)3-m（ｍは０〜３の整数であり、Ｒ7 はアセチルアセトナート基を示し、Ｒ8 はエチルアセトナート基を示す。）
より具体的には、たとえば、上記一般式（７）においてＲ1 がイソステアロイル基でｍ＝３のイソプロピルトリイソステアロイルチタネートTi(O-iC3H7) （OCOC17H35)3 、上記一般式（１０）においてＲ7 がアセチルアセトナート基でｍ＝３のアセチルアセトアルミニウム（CH3COCHCOCH3)3Al等が挙げられる。
【００２２】
熱分解性材料として用いることのできる前記シラン化合物としては、特に限定はされないが、たとえば、一般式（１１）：Ｒ9 （ＣＨ3 ）m ＳｉＸ3-m （ここで、Ｒ9 はγーグリシドキシプロピル基またはγーメタクリロキシプロピル基を示し、Ｘは同一または異種の加水分解性基を示し、前記一般式（１）中のＸと同じであっても異なっていてもよく、ｍは０または１である）で表されるもの等が挙げられる。加水分解性基Ｘの具体例や好ましいものは、前記一般式（１）中のＸと同じである。このシラン化合物の具体例としては、特に限定はされないが、たとえば、γーグリシドキシプロピルトリメトキシシラン、γーグリシドキシプロピルメチルジメトキシシラン、γーメタクリロキシプロピルトリメトキシシラン、γーメタクリロキシプロピルメチルジメトキシシラン等が挙げられる。
【００２３】
熱分解性材料は、１種のみを用いてもよいし、２種以上を併用してもよい。
無機塗料中、熱分解性材料の含有量は、特に限定はされないが、無機塗料の全固形分に対して、好ましくは０．１〜２５重量％、より好ましくは１〜２０重量％、さらに好ましくは３〜１２重量％である。熱分解性材料の含有量が０．１重量％未満だと、その作用効果が発揮されにくくなる傾向があり、該含有量が２５重量％を超えると、被膜強度が低下する傾向がある。
本発明で用いられる無機塗料は、必要に応じ、該塗料の被膜の硬度をさらに高くする、表面平滑性と耐クラック性を改善する等の種々の目的で、フィラーをも含有していてもよい。
【００２４】
フィラーとしては、特に限定はされず、例えば、シリカ、アルミナ等の無機酸化物等の無機系フィラー；カーボンブラック等の有機系フィラー等、公知のものを使用できる。これらの中でも、無機系フィラー（特に無機酸化物）が、耐溶剤性・耐酸性等の化学的安定性、シリコーンレジン中への分散性、硬化被膜の耐摩耗性等の点から特に好ましい。フィラーは、１種のみ用いてもよいし、２種以上併用してもよい。
前記シリカとしては、特に限定はされず、公知のものを使用できる。無機塗料に導入する際のシリカの形態は、後述するように他のフィラーと同じく、特に限定はされず、たとえば、粉体の形でもゾル状の形（コロイダルシリカ）でもよい。上記コロイダルシリカとしては、特の限定はされないが、たとえば、水分散性あるいはアルコール等の非水系の有機溶媒分散性コロイダルが使用できる。一般に、このようなコロイダルシリカは、固形分としてのシリカを２０〜５０重量％含有しており、この値からシリカ配合量を決定できる。なお、水分散性コロイダルシリカを使用する場合には、同コロイダルシリカ中に固形分以外の成分として存在する水は、加水分解性オルガノシランの（部分）加水分解に使用できる（（部分）加水分解の際の水の使用量に加算される）とともに、無機塗料の硬化剤としても用いることができる。水分散性コロイダルシリカは、通常、水ガラスから作られるが、市販品として容易に入手することができる。また、有機溶媒分散性コロイダルシリカは、前記水分散性コロイダルシリカの水を有機溶媒と置換することで容易に調製することができる。このような有機溶媒分散性コロイダルシリカも水分散性コロイダルシリカと同様に市販品として容易に入手できる。有機溶媒分散性コロイダルシリカにおいて、コロイダルシリカが分散している有機溶媒の種類は、特に限定はされないが、たとえば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等の低級脂肪族アルコール類；エチレングリコール、エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテル等のエチレングリコール誘導体；ジエチレングリコール、ジエチレングリコールモノブチルエーテル等のジエチレングリコール誘導体；およびジアセトンアルコール等を挙げることができ、これらからなる群より選ばれた１種もしくは２種以上のものを使用することができる。これらの親水性有機溶媒と併用して、トルエン、キシレン、ヘキサン、ヘプタン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、メチルエチルケトオキシム等の１種もしくは２種以上も使用することができる。
【００２５】
なお、前述した光半導体にはフィラーとしての役目もあるので、以下では、この光半導体をフィラーの範疇に含めて説明する。
本発明で使用可能なフィラーは、粉末、微粒子粉末、溶液分散ゾル粒子等、無機塗料に分散可能なものであれば、いかなる形態のものでも構わないが、ゾル状、特にｐＨ７以下のゾル状であれば、硬化がより短時間で進み、使用する上で利便性に優れる。
フィラーを無機塗料中に分散させるための分散媒としては、フィラーを均一に分散させることのできるものであれば特に限定はされず、水系、非水系のいずれの溶媒も用いることができる。
【００２６】
フィラーの分散媒として使用可能な水系溶媒としては、特に限定はされないが、たとえば、水単独の他、親水性有機溶媒（たとえば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等の低級脂肪族アルコール類；エチレングリコール、エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテル等のエチレングリコール誘導体；ジエチレングリコール、ジエチレングリコールモノブチルエーテル等のジエチレングリコール誘導体；ジアセトンアルコール等）の少なくとも１種と水との混合溶媒を用いることができる。これらの水系溶媒の中でも、水−メタノール混合溶媒が、フィラーの分散安定性と、塗布後の分散媒の乾燥性の点で好ましい。
【００２７】
さらに、上記ゾル状フィラーとして水系のゾルを用い、これに、加水分解性オルガノシランの（部分）加水分解時に必要に応じて用いられる触媒の一例である酸性触媒の機能を兼ねさせることもできる。
フィラーの分散媒として使用可能な非水系溶媒としては、特に限定はされないが、たとえば、上記親水性有機溶媒と、トルエン、キシレン等の疎水性有機溶媒とからなる群の中から選ばれた少なくとも１種の有機溶媒を用いることができる。これらの非水系溶媒の中でも、メタノールが、フィラーの分散安定性と、塗布後の分散媒の乾燥性の点で好ましい。
【００２８】
フィラーは、特に限定されるわけではないが、上述した、有機溶媒、または、水と親水性有機溶媒との混合溶媒にフィラーが均一分散されてなるゾル状フィラーの形で、加水分解性オルガノシランの（部分）加水分解時に、その反応混合物に混合するか、あるいは、加水分解性オルガノシランの（部分）加水分解後に、生成したシリコーンレジンと混合することによって、無機塗料に導入することが、該無機塗料の造膜性、製造工程の簡素化の点で好ましい。しかし、これに限定されない。たとえば、粉体状のフィラーを分散機でシリコーンレジン中に直接分散させることで無機塗料に導入してもよい。
【００２９】
フィラーとしては、ガラス基材等に無機塗料を塗布した際の表面の平滑性および光沢性と、塗膜の透明性を確保するとともに、過酷な摩擦条件下に置かれても、充分な耐摩耗性を発揮し、塗膜表面の傷付きや、摩耗による塗膜表面からのフィラーの欠落が発生しにくい塗膜を得るために、平均一次粒子径が通常１０〜３０ｎｍのものが好ましい。フィラーの平均一次粒子径が１０ｎｍ未満だと、塗膜の強度や表面硬度を向上させる効果が弱く、塗膜の耐摩耗性が劣り、傷付きやすくなったり、摩耗によりフィラーが塗膜表面から欠落しやすくなったりする傾向がある。他方、３０ｎｍを超えると、基材表面の平滑性および光沢性が失われる、塗膜の完全な透明性が得られにくい（塗膜を透過する光の一部が拡散し、若干白濁する現象が起きる）等の傾向があり、表面の平滑性および光沢性や、安全上、防曇性が必要とされるガラス基材等には不向きである。
【００３０】
また、無機塗料中に分散した状態でのフィラーの平均分散粒子径は、好ましくは１０〜２００ｎｍ、より好ましくは１０〜１００ｎｍである。フィラーの平均分散粒子径が１０ｎｍ未満だと、塗膜の強度や表面硬度を向上させる効果が弱く、塗膜の耐摩耗性が劣り、傷付きやすくなったり、摩耗によりフィラーが塗膜表面から欠落しやすくなったりする傾向があり、２００ｎｍを超えると、基材表面の平滑性および光沢性が失われる、塗膜の完全な透明性が得られにくい（塗膜を透過する光の一部が拡散し、若干白濁する現象が起きる）等の傾向があり、表面の平滑性および光沢性や、安全上、防曇性が必要とされるガラス基材等には不向きである。
【００３１】
フィラーの配合量は、特に限定はされないが、たとえば、シリコーンレジンの縮合化合物換算量に対するフィラーの重量比率が、固形分基準で、０．１≦フィラー／シリコーンレジン≦４であることが好ましく、０．２≦フィラー／シリコーンレジン≦３であることがより好ましく、０．５≦フィラー／シリコーンレジン≦２であることがさらに好ましい。上記比率が０．１未満だと、フィラーの添加効果が充分に得られにくい傾向があり、また、４を超えると、クラックが発生しやすくなる等、塗膜性能が低下する傾向がある。
フィラーを無機塗料中に均一に分散させる方法としては、特に限定されるものではなく、たとえば、ホモジナイザー、ディスパー、ペイントシェーカー、ビーズミル等を用いた通常の各種分散方法を用いることができる。
【００３２】
塗布後の分散媒の乾燥温度も、熱分解性材料が熱分解しない温度であれば、特に限定はされず、分散媒の種類、所望される塗膜の表面硬度、耐摩耗性等に応じて適宜設定すればよい。
本発明で用いられる無機塗料は、１００℃を超える温度で加熱硬化させる場合は硬化触媒を含む必要はないが、シリコーンレジンの縮合反応を促進することによって塗布被膜の硬化を促進させたり常温でも硬化させたりする等の目的で必要に応じて、さらに硬化触媒を含むことができる。硬化触媒としては、特に限定はされないが、たとえば、アルキルチタン酸塩類；オクチル酸錫、ジブチル錫ジラウレート、ジオクチル錫ジマレエート等のカルボン酸金属塩類；ジブチルアミン−２−ヘキソエート、ジメチルアミンアセテート、エタノールアミンアセテート等のアミン塩類；酢酸テトラメチルアンモニウム等のカルボン酸第４級アンモニウム塩；テトラエチルペンタミン等のアミン類、Ｎ−β−アミノエチル−γ−アミノプロピルトリメトキシシラン、Ｎ−β−アミノエチル−γ−アミノプロピルメチルジメトキシシラン等のアミン系シランカップリング剤；ｐ−トルエンスルホン酸、フタル酸、塩酸等の酸類；アルミニウムアルコキシド、アルミニウムキレート等のアルミニウム化合物；酢酸リチウム、酢酸カリウム、蟻酸リチウム、蟻酸ナトリウム、リン酸カリウム、水酸化カリウム等のアルカリ金属塩；テトライソプロピルチタネート、テトラブチルチタネート、チタニウムテトラアセチルアセトネート等のチタニウム化合物；メチルトリクロロシラン、ジメチルジクロロシラン、トリメチルモノクロロシラン等のハロゲン化シラン類等が挙げられる。しかし、これらの他に、シリコーンレジンの縮合反応の促進に有効なものであれば特に制限はない。
【００３３】
本発明で用いられる無機塗料が硬化触媒をも含む場合、その量は、固形分基準で、シリコーンレジンの縮合化合物換算量に対し、好ましくは１０重量％以下、より好ましくは５％以下である。１０重量％を超えると、無機塗料の貯蔵安定性を損なう可能性がある。
本発明で用いられる無機塗料は、硬化触媒を用い、１００℃以下の低温に加熱するか常温放置することにより、シリコーンレジンの有する官能基同士（たとえば、Ｘ基とＸ基、Ｘ基とＯＨ基、または、ＯＨ基とＯＨ基等）が縮合反応して硬化被膜を形成する。したがって、このような無機塗料は、常温で硬化するときにも湿度の影響をほとんど受けない。また、１００℃を超える温度で加熱処理を行えば、硬化触媒を用いなくても縮合反応を促進して硬化被膜を形成することができる。
【００３４】
なお、レベリング剤、紫外線吸収剤、金属粉、ガラス粉、抗菌剤、酸化防止剤、色素、顔料、導電剤等の添加剤が、本発明の効果に悪影響を与えない範囲内で無機塗料に含まれていてもよい。
本発明で用いられる無機塗料は、取り扱いの容易さから必要に応じて各種有機溶媒で希釈して使用できるし、また、同有機溶媒で希釈したものであってもよい。有機溶媒の種類は、シリコーンレジンの各成分の有する有機基の種類、または、シリコーンレジンの各成分の分子量の大きさ等に応じて適宜選定することができる。このような有機溶媒としては、特に限定はされないが、たとえば、メタノール、エタノール、イソプロパノール、ｎ−ブタノール、イソブタノール等の低級脂肪族アルコール類；エチレングリコール、エチレングリコールモノブチルエーテル、酢酸エチレングリコールモノエチルエーテル等のエチレングリコール誘導体；ジエチレングリコール、ジエチレングリコールモノブチルエーテル等のジエチレングリコール誘導体；および、トルエン、キシレン、ヘキサン、ヘプタン、酢酸エチル、酢酸ブチル、メチルエチルケトン、メチルイソブチルケトン、メチルエチルケトオキシム、ジアセトンアルコール等を挙げることができ、これらからなる群より選ばれた１種もしくは２種以上を使用することができる。有機溶媒での希釈割合は特に制限はなく、必要に応じて希釈割合を適宜決定すれば良い。
【００３５】
本発明で用いられる無機塗料を製造する方法は、特に限定はされず、各成分を通常の方法および装置等を用いて混合すればよい。無機塗料に導入する際の各成分の形態についても、それ自身液状のものや、溶媒に溶解してなる溶液、分散媒中に分散してなる分散液等の液状、粉体等の固体状等を問わず、特に限定はされない。各成分を溶液または分散液の形で導入する場合、その溶媒または分散媒としては、たとえば、水、上述の有機溶媒、または、水と上述の有機溶媒との混合物を使用できる。また、各成分は、別個に添加してもよいし、あるいは、２成分以上を予め混合しておいてから残りの成分と混合したり、全成分を同時に混合したりしてもよく、その添加や混合の時期等についても特に限定はされない。
【００３６】
無機塗料を塗布する方法は、特に限定されるものではなく、たとえば、刷毛塗り、スプレーコート、浸漬（ディッピング、ディップコートとも言う）、ロールコート、フローコート（基材の被塗装部位の上部から塗料を流して塗装する流し塗り塗装法）、カーテンコート、ナイフコート、スピンコート、バーコート等の通常の各種塗布方法を選択することができる。
無機塗料の塗膜の硬化方法については、公知の方法を用いればよく、特に限定はされない。また、硬化の際の温度も、熱分解性材料が熱分解しない温度であれば、特に限定はされず、所望される硬化被膜性能や、フィラーや基材の耐熱性等に応じて常温〜加熱温度の広い範囲をとることができる。
【００３７】
塗膜の硬化後、熱分解性材料を熱分解させる際の加熱温度は、熱分解性材料が熱分解する最低温度以上の温度であればよく、使用する熱分解性材料の種類や、フィラーおよび基材の耐熱性等に応じて異なり、特に限定はされないが、たとえば、熱分解性材料が前記有機金属化合物および／またはシラン化合物の場合は２００〜３５０℃程度である。
本発明の方法により形成される無機被膜の厚みは、クラックや剥離等が発生しないためには、たとえば、０．０５〜２μｍ程度であればよいが、該無機被膜の各種機能をより効果的に発揮させたり常温での硬化時間をより短くしたりするとともに、該無機被膜が長期的に安定に密着、保持されるためには、０．１〜１μｍが好ましく、０．１〜０．５μｍがより好ましい。
【００３８】
無機塗料が塗布される基材（本発明の塗装品に用いられる基材でもある）としては、有機、無機を問わず、各種基材を用いることができ、特に限定はされないが、たとえば、ガラス、金属、プラスチック等が挙げられる。これらの基材は、塗装の際に塗膜を均一に形成できるようにするため、または、塗膜との密着性を向上させるために、前洗浄しておくと良い。その方法としては、特に限定はされないが、たとえば、アルカリ洗浄、ふっ化アンモニウム洗浄、プラズマ洗浄、ＵＶ洗浄等が挙げられる。
【００３９】
【実施例】
以下、実施例および比較例によって本発明を詳細に説明する。実施例および比較例中、特に断らない限り、「部」はすべて「重量部」を、「％」はすべて「重量％」を表す。また、分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）により、測定機種として東ソー（株）のＨＬＣ８０２０を用いて、標準ポリスチレンで検量線を作成し、その換算値として測定したものである。なお、本発明は、下記の実施例に限定されない。
＜実施例１＞
テトラエトキシシラン２０８部にメタノール３５６部を加え、さらに水１８部および０．０１Ｎの塩酸１８部を混合し、ディスパーを用いてよく混合した。得られた液を６０℃恒温槽中で２時間加熱して重量平均分子量を９５０に調製することにより、シリコーンレジンを得た。
【００４０】
次に、このシリコーンレジンに、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシラン（熱分解温度２８０℃）を、得ようとしている無機塗料の全固形分に対して１０％、光半導体として酸化チタン水ゾル（固形分２１％、平均一次粒子径２０ｎｍ）を光半導体／全シリコーンレジン（縮合化合物換算）の固形分基準で重量比が０．５となるように添加し、全固形分が５％になるようメタノールで希釈することにより、無機塗料を得た。
この無機塗料を１時間放置した後にスピンコータによりガラス基材に塗装して塗膜を形成し、この塗膜を２００℃で０．５時間硬化させた後、３００℃で０．５時間焼成して前記熱分解性材料を熱分解することにより、厚さ０．３μｍの無機被膜を有する塗装品を作製した。
【００４１】
＜実施例２＞
実施例１において、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシランの代わりにγーメタクリロキシプロピルトリメトキシシラン（熱分解温度３２０℃）を、得ようとしている無機塗料の全固形分に対して１０％添加して無機塗料を調製するとともに、塗膜の焼成温度を３４０℃に変更する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
＜実施例３＞
実施例１において、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシランの代わりにγ−グリシドキシプロピルメチルジメトキシシラン（熱分解温度２７０℃）を、得ようとしている無機塗料の全固形分に対して１０％添加する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
【００４２】
＜実施例４＞
実施例１において、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシランの代わりにアセチルアセトアルミニウム（ＣＨ3ＣＯＣＨＣＯＣＨ3）3Ａｌ（熱分解温度２００℃）を、得ようとしている無機塗料の全固形分に対して１０％添加して無機塗料を調製するとともに、塗膜の硬化温度を１５０℃に変更する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
＜実施例５＞
実施例１において、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシランの代わりにイソプロピルトリイソステアロイルチタネートＴｉ（Ｏ−ｉＣ3Ｈ7）（ＯＣＯＣ17Ｈ35）3（熱分解温度２５０℃）を、得ようとしている無機塗料の全固形分に対して５％添加する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
【００４３】
＜実施例６＞
実施例１において、フィラー成分としてシリカメタノールゾル（商品名：メタノールシリカゾル、日産化学工業製、粒径１０〜２０ｎｍ）をフィラー／全シリコーンレジン（縮合化合物換算）の固形分基準で重量比が１．５となるように添加する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
＜実施例７＞
実施例１において、熱分解性材料としてγ−グリシドキシプロピルトリメトキシシランの代わりにアセチルアセトアルミニウム（ＣＨ3ＣＯＣＨＣＯＣＨ3）3Ａｌ（熱分解温度２００℃）を、得ようとしている無機塗料の全固形分に対して２０％添加して無機塗料を調製するとともに、塗膜の硬化温度を１５０℃に変更する以外は実施例１と同様の操作を行って無機塗料を得た。次いで、この無機塗料を用い、実施例１と同様の方法で塗装品を作製した。
【００４４】
＜比較例１＞
実施例１において、熱分解性材料を全く添加せずに無機塗料を調製し、これをガラス基材に塗装する以外は実施例１と同様の方法で塗装品を作製した。
＜比較例２＞
実施例１において、塗膜の焼成温度を１５０℃（熱分解性材料が熱分解しない温度）に変更する以外は実施例１と同様の方法で塗装品を作製した。
＜比較例３＞
実施例４において、塗膜の焼成温度を１５０℃（熱分解性材料が熱分解しない温度）に変更する以外は実施例４と同様の方法で塗装品を作製した。
【００４５】
［塗膜性能の評価］
以上のようにして得られた塗装品の塗膜性能を以下の方法で評価した。
（光半導体による有機物の分解性）：
オレイン酸を一定量（０．２ｃｃ）塗膜面に滴下し、１時間放置後、オレイン酸を水拭きし、乾燥して試験片とした。これに紫外線（約１ｍＷ／ｃｍ2 ）を照射し、１２時間後の塗膜表面の水に対する接触角を測定し、光半導体による有機物の分解性を以下の基準で評価した。
◎：計測不能（≒０°）
○：５°以下
△：５°超〜１５°以下
×：１５°超
（耐摩耗性＝ハードコート性）：
トラバース式摩耗試験機を用い、キャンバス布を塗装品の塗装面に接触させ、１０００回往復摺動（荷重１００ｇ／ｃｍ2 、ストローク１００ｍｍ）させることにより、摩耗試験を行った。そして、摩耗試験後、塗膜表面の傷の発生度合いを光学顕微鏡で観察した。その判定基準は以下の通りである。
【００４６】
○：傷無し。
△：傷が１ｃｍ2 当たり数本発生。
×：傷が多数発生。剥離あり。
評価結果を表１に示す。
【００４７】
【表１】
表１にみるように、実施例１〜７はいずれも、比較例１〜３に比べ、光半導体による有機物の分解性が良好であった。これに対し、熱分解性材料を全く添加しなかった比較例１は、熱分解性材料を添加した実施例１〜７と比べて、光半導体による有機物の分解性が低かった。また、実施例１〜７と比べて焼成温度が低い比較例２、３は、光半導体による有機物の分解性と、耐摩耗性が悪かった。
【００４９】
【発明の効果】
本発明は、ハードコート性（表面硬度、耐磨耗性、耐擦傷性等）を保ちつつ光半導体の光触媒作用に由来する各種特性を十分に発揮する無機被膜を形成することのできる方法と、この方法により得られる塗装品とを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a method capable of forming an inorganic coating that sufficiently exhibits various properties derived from the photocatalytic action of an optical semiconductor while maintaining hard coat properties (surface hardness, abrasion resistance, scratch resistance, etc.) The present invention relates to a coated product obtained by this method.
[0002]
[Prior art]
It is known to form a coating film having performance such as antifouling property by applying a coating containing silicone resin as a main component to the surface of the substrate and curing it, and it is applied to various substrates. In addition, when a tetrafunctional silicone resin is used as a component of the silicone resin, hard coat properties (surface hardness, abrasion resistance, scratch resistance, etc.) are improved in addition to the antifouling performance and the like. It is also known to do. Furthermore, coating films obtained by applying and curing a coating containing a silicone resin as a main component and containing an optical semiconductor can be expected to have the following various effects and are applied to various substrates.
[0003]
When light (ultraviolet light) having an excitation wavelength (for example, 400 nm) hits an optical semiconductor, active oxygen capable of oxidatively decomposing organic matter is generated. Therefore, the surface of the base material is coated with a coating containing the optical semiconductor. Is a self-cleaning effect that decomposes carbon-based soil components adhering to the surface (for example, carbon fractions contained in automobile exhaust gas and cigarette dust); malodorous components typified by amine compounds and aldehyde compounds Deodorizing effect that degrades; antibacterial effect that prevents the generation of bacterial components typified by Escherichia coli and Staphylococcus aureus; In addition, when UV light hits a material coated with a coating containing a photo semiconductor on the surface of the base material, the photo semiconductor acts as a hydroxyl radical on the moisture in the air or on the surface of the material by photocatalysis. Hydroxyl radicals decompose and remove organic substances (such as those attached to the material surface and those contained in the material surface) that repel water, thereby reducing the contact angle of water with the material surface and reducing the surface of the material. There is also an effect of improving hydrophilicity (water wettability), which makes it easy to get wet with water (familiarity). From this hydrophilicity-improving effect, the indoor member is expected to have an anti-fogging effect in which glass and mirrors are not easily fogged by water droplets, and the outdoor member is expected to have an anti-fouling effect in which attached dirt is washed away by rainwater. In addition, the material obtained by coating the base material surface with a coating containing an optical semiconductor also has an antistatic function due to the photocatalytic action of the optical semiconductor, and this function is also expected to have an antifouling effect.
[0004]
[Problems to be solved by the invention]
However, the above prior art has the following problems. That is, when a tetrafunctional silicone resin is used as a constituent component of a silicone resin and an optical semiconductor is contained, if the ratio of the optical semiconductor to the silicone resin is increased, the effect of the optical semiconductor as described above is expected more. However, on the other hand, hard coat properties are reduced, and surface hardness, abrasion resistance, scratch resistance, and the like are reduced. Conversely, when the ratio of the optical semiconductor to the silicone resin is decreased, the hard coat property is improved or maintained, but on the other hand, the effect of the optical semiconductor is reduced.
[0005]
Therefore, an object of the present invention is to form an inorganic coating that sufficiently exhibits various characteristics derived from the photocatalytic action of an optical semiconductor while maintaining hard coat properties (surface hardness, abrasion resistance, scratch resistance, etc.). It is in providing the method which can be performed, and the coated article obtained by this method.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the present inventor has made various studies. As a result, in addition to the silicone resin consisting of a tetrafunctional silicone resin and an optical semiconductor, an inorganic material further blended with a thermally decomposable material that does not thermally decompose at a temperature at which the coating film is to be cured but thermally decomposes at a higher temperature. A paint is applied to a base material to form a coating film. After the coating film is cured at a temperature at which the thermally decomposable material is not thermally decomposed, the temperature is a temperature at which the thermally decomposable material is thermally decomposed. It was confirmed by experiments that the pyrolyzable material should be pyrolyzed and the present invention was completed.
[0007]
That is, the inorganic film forming method according to the present invention has the general formula (1): general formula SiX.Four(Wherein X represents the same or different hydrolyzable groups) containing a tetrafunctional silicone resin containing a (partial) hydrolyzate of a tetrafunctional hydrolyzable organosilane and an optical semiconductor A method of forming an inorganic coating on the surface of the substrate by coating the substrate with an inorganic coating to form a coating and then curing the coating, wherein the coating is applied to the inorganic coating. In addition to containing a thermally decomposable material that does not thermally decompose at a higher temperature than the temperature at which the film is to be cured, the thermally decomposable material does not thermally decompose the inorganic coating film. After curing at a temperature, the temperature is raised to a temperature at which the thermally decomposable material is thermally decomposed to thermally decompose the thermally decomposable material.
[0008]
In the present specification, “(partial) hydrolysis” means “partial hydrolysis and / or hydrolysis”.
The coated article according to the present invention is obtained by the inorganic film forming method of the present invention.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The silicone resin, which is one of the essential components of the inorganic coating used in the present invention, comprises a tetrafunctional silicone resin containing a (partial) hydrolyzate of a tetrafunctional hydrolyzable organosilane, and is used as a binder resin and a film-forming component. In addition, by adding surface hydrophilicity (water wettability) to the inorganic coating formed from the above-mentioned inorganic paint, it is a component that provides the film with antifogging properties, antifouling properties by washing with rainwater, and the like. In addition, the inorganic coating is excellent in hard coat properties (surface hardness, abrasion resistance, scratch resistance, etc.) and the like by using a tetrafunctional silicone resin.
[0010]
The form of the silicone resin is not particularly limited, and may be, for example, a solution or a dispersion.
As the tetrafunctional hydrolyzable organosilane used as a raw material for the tetrafunctional silicone resin, those represented by the general formula (1) are used.
In the general formula (1), X is not particularly limited as long as it is the same or different hydrolyzable group. For example, alkoxy group, acetoxy group, oxime group, enoxy group, amino group, aminoxy group, amide Groups and the like. Among these, an alkoxy group is preferable because it is easily available and a silicone resin can be easily prepared. Among alkoxy groups (OR group; R is an alkyl group), those in which R is an alkyl group having 1 to 8 carbon atoms are not only easy to obtain and easy to prepare silicone resins, but also obtained silicone When an inorganic coating containing resin is applied and cured, a condensation reaction is likely to occur, and as a result, a hard inorganic coating is likely to be formed. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Among the alkyl groups contained in the alkoxy group, those having 3 or more carbon atoms may be linear such as n-propyl group, n-butyl group, isopropyl group, isobutyl group, etc. It may have a branch such as a group or a t-butyl group.
[0011]
Specific examples of the tetrafunctional hydrolyzable organosilane are not particularly limited. For example, tetrafunctional alkoxysilanes, acetoxysilanes, oximesilanes, enoxysilanes, aminosilanes, aminoxysilanes, Amidosilanes etc. are mentioned. Among these, alkoxysilanes are preferable because they are easily available and a silicone resin can be easily prepared. Also, among these alkoxysilanes, not only the availability and ease of preparation of silicone resins, but also condensation reactions are likely to occur when applying and curing an inorganic coating containing the resulting silicone resin. Alkoxysilanes in which R in the alkoxy group (OR group; R is an alkyl group) is the above alkyl group having 1 to 8 carbon atoms are particularly preferable from the viewpoint of easily forming a hard inorganic film.
[0012]
Specific examples of the tetrafunctional alkoxysilanes are not particularly limited. For example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, and tetra-t-butoxysilane are available. Is mentioned. Among these, tetramethoxysilane and tetraethoxysilane are preferable.
Furthermore, organosilane compounds generally called silane coupling agents are also included in the alkoxysilanes.
Only one type of tetrafunctional hydrolyzable organosilane may be used, or two or more types may be used in combination.
[0013]
The tetrafunctional silicone resin can be prepolymerized by, for example, adding a necessary amount of water as a curing agent and a catalyst or the like as necessary to a tetrafunctional hydrolyzable organosilane, and performing (partial) hydrolysis. Can be prepared.
The amount of water used when (partially) hydrolyzing the tetrafunctional hydrolyzable organosilane is not particularly limited. For example, water relative to the hydrolyzable group (X) of the tetrafunctional hydrolyzable organosilane ( H2O) molar equivalent ratio (H2O / X) is preferably in the range of 0.3 to 5, more preferably 0.35 to 4, and still more preferably 0.4 to 3.5. If the molar equivalent ratio is less than 0.3, hydrolysis does not proceed sufficiently and the inorganic coating film may become brittle. If it exceeds 5, the resulting silicone resin tends to gel in a short time. , Storage stability may be reduced.
[0014]
The catalyst used as necessary when (partially) hydrolyzing the tetrafunctional hydrolyzable organosilane is not particularly limited, but from the viewpoint of shortening the time required for the production process of the inorganic coating, an acidic catalyst is used. preferable. The acidic catalyst is not particularly limited. For example, acetic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionic acid, glutaric acid, glycolic acid, maleic acid, malonic acid, toluenesulfonic acid, Examples include organic acids such as acids; inorganic acids such as hydrochloric acid, nitric acid, and halogenated silane; acidic sol-like fillers such as acidic colloidal silica and titanium oxide sol, and one or more of these can be used.
[0015]
The (partial) hydrolysis of the tetrafunctional hydrolyzable organosilane may be performed by heating (for example, heating to 40 to 100 ° C.) as necessary.
(Partial) hydrolysis of the tetrafunctional hydrolyzable organosilane may be carried out by diluting the tetrafunctional hydrolyzable organosilane with an appropriate solvent, if necessary. Such a diluting solvent (reaction solvent) is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol; ethylene glycol, ethylene glycol monobutyl ether, ethylene acetate Examples include ethylene glycol derivatives such as glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One or more selected from the group consisting of these are used. be able to. In combination with these hydrophilic organic solvents, one or more of toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used.
[0016]
Although the weight average molecular weight (Mw) of the silicone resin used by this invention is not specifically limited, The range of 500-1000 is preferable in polystyrene conversion. If it is less than 500, the silicone resin is unstable, and if it is more than 1000, the inorganic coating cannot maintain sufficient hardness.
The inorganic paint used in the present invention is an essential component for obtaining various functions due to the photocatalytic effect described later, and for further increasing the surface hydrophilicity of the formed inorganic film by the photocatalytic effect or maintaining it for a long period of time. In addition, an optical semiconductor is included.
The optical semiconductor is not particularly limited. For example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, oxide In addition to metal oxides such as copper, vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, cobalt oxide, rhodium oxide, nickel oxide, rhenium oxide, strontium titanate, etc. are used to cure the coating (especially at low temperatures including normal temperature). This is preferable in that the effect of accelerating the curing of (a) is also obtained. Among these, the metal oxide is preferable in terms of practical and easy use, and titanium oxide is particularly preferable among the metal oxides because of its photocatalytic performance, curing acceleration performance, safety, availability, and cost. In terms of surface. When titanium oxide is used as an optical semiconductor, the one with a crystal type of anatase type (anatase type) has the strongest photocatalytic performance and curing acceleration performance, and it develops for a long period of time. This is preferable in that the acceleration performance is manifested in a shorter time.
[0017]
Only one type of optical semiconductor may be used, or two or more types may be used in combination.
In addition, what becomes the raw material of an optical semiconductor can be used if it finally shows the property of an optical semiconductor.
It is known that active oxygen is generated when light (ultraviolet light) having an excitation wavelength (for example, 400 nm) hits an optical semiconductor. Since active oxygen can be decomposed by oxidizing organic substances, the surface of a base material coated with a coating containing an optical semiconductor contains carbon-based soil components (for example, in automobile exhaust gas). Of self-cleaning that decomposes carbon fractions and cigarette crabs contained in foods; deodorizing effects that decompose malodorous components typified by amine compounds and aldehyde compounds; fungal components typified by Escherichia coli and Staphylococcus aureus Antibacterial effect to prevent occurrence; antifungal effect is expected. In addition, when UV light hits a material coated with a coating containing a photo semiconductor on the surface of the base material, the photo semiconductor acts as a hydroxyl radical on the moisture in the air or on the surface of the material by photocatalysis. Hydroxyl radicals decompose and remove organic substances (such as those attached to the material surface and those contained in the material surface) that repel water, thereby reducing the contact angle of water with the material surface and reducing the surface of the material. There is also an effect of improving hydrophilicity (water wettability), which makes it easy to get wet with water (familiarity). From this hydrophilicity-improving effect, the indoor member is expected to have an anti-fogging effect in which glass and mirrors are not easily fogged by water droplets, and the outdoor member is expected to have an anti-fouling effect in which attached dirt is washed away by rainwater.
[0018]
Furthermore, there is an antistatic function by the photocatalytic action of the optical semiconductor, and this function further improves the antifouling effect. For example, when ultraviolet light is applied to a coating film containing a photosemiconductor, the surface resistance value of the coating film decreases due to the action of the photosemiconductor contained in the coating film, so that an antistatic effect is exhibited and the coating film surface is further less likely to become dirty. Become. Although the mechanism by which the surface resistance value of the coating film decreases when UV light is applied to the photo-semiconductor-containing coating film has not yet been clearly confirmed, the action of electrons and holes generated by UV irradiation is effective. By doing so, it is considered that the surface resistance value of the coating film decreases.
When a metal is supported on the surface of the optical semiconductor, the photocatalytic effect of the optical semiconductor is further increased. Although the mechanism has not been clearly confirmed yet, the metal is supported on the surface of the optical semiconductor to promote the charge separation of the optical semiconductor, and the disappearance of electrons and holes generated by the charge separation is established. It seems to be related to becoming smaller.
[0019]
Examples of the metal that may be supported on the surface of the optical semiconductor include silver, copper, iron, nickel, zinc, platinum, gold, palladium, cadmium, cobalt, rhodium, and ruthenium, which further promote charge separation of the optical semiconductor. This is preferable. Only one type or two or more types of metals may be supported.
Although the amount of metal supported is not particularly limited, for example, it is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight with respect to the optical semiconductor. If the loading amount is less than 0.1% by weight, the loading effect tends not to be obtained sufficiently. Even if the loading amount exceeds 10% by weight, the effect does not increase so much. Problems tend to occur.
[0020]
The method for supporting the metal is not particularly limited, and examples thereof include an immersion method, an impregnation method, and a photoreduction method.
You may use an optical semiconductor in the form inserted between the layers of a clay crosslinked body. This is because the photo-semiconductor is dispersed in the form of fine particles between the clay cross-linked bodies to improve the photocatalytic performance.
The inorganic paint used in the present invention contains a thermally decomposable material as an essential component. As the thermally decomposable material, a material that does not thermally decompose at a temperature at which the coating film of the inorganic coating is to be cured but thermally decomposes at a higher temperature is used. The thermally decomposable material is included in an inorganic paint, a coating film is formed, the coating film is cured at a temperature at which the thermally decomposable material is not thermally decomposed, and then the temperature is thermally decomposed by the thermally decomposable material. By thermally decomposing the thermally decomposable material by raising the temperature, the thermally decomposable material on the coating surface is thermally decomposed to expose the optical semiconductor from the coating surface, or the optical semiconductor is contained on the coating surface. Since the amount increases, the photocatalytic action of the optical semiconductor can be effectively extracted.
[0021]
Such a thermally decomposable material is not particularly limited, and examples thereof include organometallic compounds and silane compounds.
Although it does not specifically limit as said organometallic compound, For example, an organic titanium compound, an organoaluminum compound, etc. are mentioned. Specific examples thereof are not particularly limited. For example, organic titanium compounds represented by the following general formulas (2) to (4), structural formula (5), and general formulas (6) to (9) And organoaluminum compounds represented by the general formula (10).
General formula (2): Ti (O-CThreeH7)m(OC2HFourN (C2HFourOH)2)4-m (M is an integer from 1 to 3)
General formula (3): Ti (O-nCFourH9)m(OC2HFourN (C2HFourOH)2)4-m(M is an integer from 1 to 3)
General formula (4) :( C8H17O)mTi (OCH2CH (C2HFive) CH (OH) CThreeH7)4-m(M is an integer from 1 to 3)
Structural formula (5): Ti (CFiveH7O2)Four
General formula (6): Ti (OH)m(OCH (CHThreeCOOH)4-m(M is an integer from 1 to 3)
General formula (7): Ti (O-iCThreeH7) R1 mR2 3-m(M is an integer of 1 to 3, R1And R2Is an isostearoyl group, octanoyl group, methacryl group, dodecylbenzenesulfonyl group, dioctyl phosphate group, cumylphenyl group, dioctyl pyrophosphate group, n-aminoethyl-aminoethyl group, acetylacetonato group or 2-ethyl-1,3- A hexanediolato group is shown. )
General formula (8) :( RThree)FourTi (RFour)2(RThreeRepresents isopropyl group, octyl group or 2,2-diallyloxymethyl-1-butyl group;FourRepresents a dioctyl phosphite group or a didodecyl phosphite group. )
General formula (9) :( RFive) Ti (R6)2(RFiveRepresents an oxyacetate group or an ethylene group, R6Represents a dicumylphenyl group, a dioctylpyrophosphate group or an isostearoyl group. )
Formula (10): Al (R7)m (R8)3-m(M is an integer from 0 to 3, R7Represents an acetylacetonate group, R8Represents an ethylacetonate group. )
More specifically, for example, in the general formula (7), R1Is an isostearoyl group and m = 3 isopropyl triisostearoyl titanate Ti (O-iCThreeH7) (OCOC17H35)ThreeIn the general formula (10), R7Is an acetylacetonate group and m = 3 acetylacetoaluminum (CHThreeCOCHCOCHThree)ThreeAl etc. are mentioned.
[0022]
Although it does not specifically limit as said silane compound which can be used as a thermally decomposable material, For example, General formula (11): R9(CHThree)mSiX3-m(Where R9Represents γ-glycidoxypropyl group or γ-methacryloxypropyl group, X represents the same or different hydrolyzable group, and may be the same as or different from X in the general formula (1). Often, m is 0 or 1). Specific examples and preferred examples of the hydrolyzable group X are the same as those in the general formula (1). Specific examples of the silane compound are not particularly limited. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Examples include propylmethyldimethoxysilane.
[0023]
Only 1 type may be used for a thermally decomposable material and it may use 2 or more types together.
The content of the thermally decomposable material in the inorganic coating is not particularly limited, but is preferably 0.1 to 25% by weight, more preferably 1 to 20% by weight, and still more preferably based on the total solid content of the inorganic coating. Is 3 to 12% by weight. When the content of the thermally decomposable material is less than 0.1% by weight, the effect tends to be hardly exhibited, and when the content exceeds 25% by weight, the coating strength tends to be lowered.
The inorganic coating used in the present invention may also contain a filler for various purposes such as further increasing the hardness of the coating film of the coating or improving the surface smoothness and crack resistance, if necessary. .
[0024]
The filler is not particularly limited, and known fillers such as inorganic fillers such as inorganic oxides such as silica and alumina; and organic fillers such as carbon black can be used. Among these, inorganic fillers (particularly inorganic oxides) are particularly preferable from the viewpoints of chemical stability such as solvent resistance and acid resistance, dispersibility in silicone resin, and abrasion resistance of the cured coating. Only 1 type of filler may be used and it may use 2 or more types together.
The silica is not particularly limited, and a known silica can be used. The form of silica when introduced into the inorganic coating is not particularly limited, as will be described later, as in other fillers. For example, it may be in the form of a powder or a sol form (colloidal silica). Although it does not specifically limit as said colloidal silica, For example, non-aqueous organic-solvent dispersoid colloids, such as water dispersibility or alcohol, can be used. Generally, such colloidal silica contains 20 to 50% by weight of silica as a solid content, and the amount of silica can be determined from this value. When water-dispersible colloidal silica is used, water present as a component other than solid content in the colloidal silica can be used for (partial) hydrolysis of hydrolyzable organosilane ((partial) hydrolysis. In addition, it can be used as a curing agent for inorganic paints. Water-dispersible colloidal silica is usually made from water glass, but can be easily obtained as a commercial product. The organic solvent-dispersible colloidal silica can be easily prepared by replacing the water of the water-dispersible colloidal silica with an organic solvent. Such an organic solvent-dispersible colloidal silica can be easily obtained as a commercial product, similarly to the water-dispersible colloidal silica. In the organic solvent-dispersible colloidal silica, the type of the organic solvent in which the colloidal silica is dispersed is not particularly limited. For example, lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene And ethylene glycol derivatives such as glycol, ethylene glycol monobutyl ether, and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and diacetone alcohol. One kind selected from the group consisting of these Alternatively, two or more types can be used. In combination with these hydrophilic organic solvents, one or more of toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime and the like can be used.
[0025]
In addition, since the optical semiconductor described above also has a role as a filler, the optical semiconductor will be described below including the category of filler.
The filler that can be used in the present invention may be in any form as long as it is dispersible in an inorganic paint, such as powder, fine particle powder, and solution-dispersed sol particles. If so, the curing proceeds in a shorter time, and the convenience in use is excellent.
The dispersion medium for dispersing the filler in the inorganic paint is not particularly limited as long as the filler can be uniformly dispersed, and any aqueous or non-aqueous solvent can be used.
[0026]
The aqueous solvent that can be used as the filler dispersion medium is not particularly limited. For example, in addition to water alone, a hydrophilic organic solvent (for example, lower aliphatic such as methanol, ethanol, isopropanol, n-butanol, and isobutanol). Alcohols; ethylene glycol derivatives such as ethylene glycol, ethylene glycol monobutyl ether, and acetic acid ethylene glycol monoethyl ether; diethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; diacetone alcohol, etc.) and a mixed solvent of water and water be able to. Among these aqueous solvents, a water-methanol mixed solvent is preferable in view of dispersion stability of the filler and drying property of the dispersion medium after coating.
[0027]
Furthermore, an aqueous sol can be used as the sol-like filler, and this can also serve as an acidic catalyst which is an example of a catalyst used as needed during (partial) hydrolysis of the hydrolyzable organosilane.
The non-aqueous solvent that can be used as the filler dispersion medium is not particularly limited. For example, at least one selected from the group consisting of the above hydrophilic organic solvents and hydrophobic organic solvents such as toluene and xylene. Various organic solvents can be used. Among these non-aqueous solvents, methanol is preferable in terms of the dispersion stability of the filler and the drying property of the dispersion medium after coating.
[0028]
The filler is not particularly limited, but is a hydrolyzable organosilane in the form of a sol-like filler in which the filler is uniformly dispersed in the above-described organic solvent or a mixed solvent of water and a hydrophilic organic solvent. Mixing into the reaction mixture at the (partial) hydrolysis of, or introducing into the inorganic coating by mixing with the silicone resin produced after (partial) hydrolysis of the hydrolyzable organosilane, It is preferable in terms of the film forming property of the inorganic coating and the simplification of the manufacturing process. However, it is not limited to this. For example, the powdery filler may be introduced into the inorganic paint by directly dispersing it in the silicone resin with a disperser.
[0029]
As a filler, it ensures smoothness and glossiness of the surface when an inorganic paint is applied to a glass substrate, etc., and transparency of the coating film, and also provides sufficient wear resistance even under severe friction conditions. In order to obtain a coating film that exhibits good properties and is less susceptible to scratches on the coating film surface and lack of filler loss from the coating film surface due to wear, those having an average primary particle size of usually 10 to 30 nm are preferred. If the average primary particle diameter of the filler is less than 10 nm, the effect of improving the strength and surface hardness of the coating film is weak, the wear resistance of the coating film is inferior, scratches easily, and the filler is missing from the coating film surface due to wear. It tends to be easy to do. On the other hand, if it exceeds 30 nm, the smoothness and glossiness of the substrate surface are lost, and complete transparency of the coating film is difficult to obtain (a part of the light transmitted through the coating film diffuses and becomes slightly cloudy) It is not suitable for glass substrates and the like that require smoothness and glossiness of the surface and anti-fogging properties for safety.
[0030]
Moreover, the average dispersed particle diameter of the filler in a state dispersed in the inorganic paint is preferably 10 to 200 nm, more preferably 10 to 100 nm. When the average dispersed particle size of the filler is less than 10 nm, the effect of improving the strength and surface hardness of the coating film is weak, the abrasion resistance of the coating film is inferior, scratches easily, and the filler is missing from the coating film surface due to wear. When the thickness exceeds 200 nm, the smoothness and glossiness of the substrate surface are lost, and it is difficult to obtain complete transparency of the coating film (a part of the light transmitted through the coating film is diffused). However, it is not suitable for glass substrates and the like that require smoothness and glossiness of the surface, and anti-fogging properties for safety.
[0031]
The blending amount of the filler is not particularly limited. For example, it is preferable that the weight ratio of the filler to the equivalent amount of the silicone resin condensation compound is 0.1 ≦ filler / silicone resin ≦ 4 based on the solid content. More preferably, 2 ≦ filler / silicone resin ≦ 3, and more preferably 0.5 ≦ filler / silicone resin ≦ 2. When the ratio is less than 0.1, the effect of adding the filler tends to be difficult to obtain, and when it exceeds 4, the coating film performance tends to decrease, such as cracking is likely to occur.
The method for uniformly dispersing the filler in the inorganic paint is not particularly limited, and for example, various usual dispersion methods using a homogenizer, a disper, a paint shaker, a bead mill, and the like can be used.
[0032]
The drying temperature of the dispersion medium after coating is not particularly limited as long as the thermally decomposable material is not thermally decomposed, depending on the type of the dispersion medium, the desired surface hardness of the coating film, wear resistance, and the like. What is necessary is just to set suitably.
The inorganic paint used in the present invention does not need to contain a curing catalyst when it is cured by heating at a temperature exceeding 100 ° C., but it accelerates the curing of the coating film by accelerating the condensation reaction of the silicone resin or cures at room temperature. A curing catalyst may be further included as necessary for the purpose of allowing the catalyst to be used. Although it does not specifically limit as a curing catalyst, For example, alkyl titanates; Carboxylic acid metal salts, such as tin octylate, dibutyltin dilaurate, dioctyltin dimaleate; Dibutylamine-2-hexoate, dimethylamine acetate, ethanolamine acetate Quaternary ammonium salts of carboxylic acids such as tetramethylammonium acetate; amines such as tetraethylpentamine, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ -Amine-based silane coupling agents such as aminopropylmethyldimethoxysilane; acids such as p-toluenesulfonic acid, phthalic acid and hydrochloric acid; aluminum compounds such as aluminum alkoxide and aluminum chelate; lithium acetate, potassium acetate and lithium formate Alkali metal salts such as sodium, sodium formate, potassium phosphate, potassium hydroxide; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium tetraacetylacetonate; halogens such as methyltrichlorosilane, dimethyldichlorosilane, trimethylmonochlorosilane Silanes and the like. However, other than these, there is no particular limitation as long as it is effective for promoting the condensation reaction of the silicone resin.
[0033]
When the inorganic paint used in the present invention also contains a curing catalyst, the amount thereof is preferably 10% by weight or less, more preferably 5% or less, based on the solid content, with respect to the amount of silicone resin condensed compound. If it exceeds 10% by weight, the storage stability of the inorganic paint may be impaired.
The inorganic coating used in the present invention uses a curing catalyst and is heated to a low temperature of 100 ° C. or lower or left at room temperature, so that the functional groups of the silicone resin (for example, X group and X group, X group and OH group) Or an OH group and an OH group) undergo a condensation reaction to form a cured film. Therefore, such an inorganic coating is hardly affected by humidity even when cured at room temperature. Moreover, if heat processing are performed at the temperature exceeding 100 degreeC, even if it does not use a curing catalyst, a condensation reaction can be accelerated | stimulated and a cured film can be formed.
[0034]
Additives such as leveling agents, ultraviolet absorbers, metal powders, glass powders, antibacterial agents, antioxidants, dyes, pigments, and conductive agents are included in inorganic paints within the range that does not adversely affect the effects of the present invention. It may be.
The inorganic paint used in the present invention can be used after being diluted with various organic solvents as required for ease of handling, or may be diluted with the same organic solvent. The type of the organic solvent can be appropriately selected according to the type of organic group of each component of the silicone resin, the size of the molecular weight of each component of the silicone resin, or the like. Such an organic solvent is not particularly limited, but examples thereof include lower aliphatic alcohols such as methanol, ethanol, isopropanol, n-butanol, and isobutanol; ethylene glycol, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate. And ethylene glycol derivatives such as diethylene glycol and diethylene glycol monobutyl ether; and toluene, xylene, hexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc. , One or more selected from the group consisting of these can be used. The dilution ratio in the organic solvent is not particularly limited, and the dilution ratio may be appropriately determined as necessary.
[0035]
The method for producing the inorganic paint used in the present invention is not particularly limited, and each component may be mixed using a normal method and apparatus. As for the form of each component when introduced into the inorganic coating material, it is a liquid itself, a solution dissolved in a solvent, a liquid such as a dispersion dispersed in a dispersion medium, a solid such as a powder, etc. There is no particular limitation. When introducing each component in the form of a solution or a dispersion, for example, water, the above-mentioned organic solvent, or a mixture of water and the above-mentioned organic solvent can be used as the solvent or dispersion medium. Each component may be added separately, or two or more components may be mixed in advance and then mixed with the remaining components, or all components may be mixed simultaneously. There is no particular limitation on the mixing time and the like.
[0036]
The method of applying the inorganic coating is not particularly limited. For example, brush coating, spray coating, dipping (also called dipping or dip coating), roll coating, flow coating (coating from the upper part of the substrate to be coated) Can be selected from ordinary coating methods such as curtain coating, knife coating, spin coating, and bar coating.
About the hardening method of the coating film of an inorganic coating material, a well-known method should just be used and it does not specifically limit. Also, the temperature at the time of curing is not particularly limited as long as the thermally decomposable material is not thermally decomposed, and it is room temperature to heated depending on the desired cured film performance, the heat resistance of the filler and the substrate, and the like. A wide range of temperatures can be taken.
[0037]
After the coating is cured, the heating temperature for thermally decomposing the thermally decomposable material may be any temperature that is equal to or higher than the minimum temperature at which the thermally decomposable material is thermally decomposed. The temperature varies depending on the heat resistance of the substrate and is not particularly limited. For example, when the thermally decomposable material is the organometallic compound and / or the silane compound, the temperature is about 200 to 350 ° C.
The thickness of the inorganic coating formed by the method of the present invention may be, for example, about 0.05 to 2 μm in order to prevent cracks, peeling, etc., but various functions of the inorganic coating can be more effectively performed. 0.1-1 μm is preferable and 0.1-0.5 μm is preferable so that the inorganic coating can be stably adhered and held for a long period of time while being allowed to exert or shorten the curing time at room temperature. More preferred.
[0038]
As the base material to which the inorganic paint is applied (which is also the base material used in the coated product of the present invention), various kinds of base materials can be used regardless of whether they are organic or inorganic. , Metal, plastic and the like. These base materials are preferably pre-cleaned so that a coating film can be formed uniformly during coating, or in order to improve adhesion to the coating film. The method is not particularly limited, and examples thereof include alkali cleaning, ammonium fluoride cleaning, plasma cleaning, and UV cleaning.
[0039]
【Example】
Hereinafter, the present invention will be described in detail by examples and comparative examples. In Examples and Comparative Examples, unless otherwise specified, “parts” all represent “parts by weight” and “%” all represent “% by weight”. Further, the molecular weight is measured by GPC (gel permeation chromatography), using a standard polystyrene with a calibration curve using HLC8020 manufactured by Tosoh Corporation as a measurement model, and measuring the converted value. The present invention is not limited to the following examples.
<Example 1>
356 parts of methanol was added to 208 parts of tetraethoxysilane, 18 parts of water and 18 parts of 0.01N hydrochloric acid were mixed, and mixed well using a disper. The obtained liquid was heated in a constant temperature bath at 60 ° C. for 2 hours to adjust the weight average molecular weight to 950, thereby obtaining a silicone resin.
[0040]
Next, to this silicone resin, γ-glycidoxypropyltrimethoxysilane (thermal decomposition temperature 280 ° C.) as a thermally decomposable material is 10% with respect to the total solid content of the inorganic paint to be obtained, as an optical semiconductor. Titanium oxide water sol (solid content 21%, average primary particle diameter 20 nm) was added so that the weight ratio was 0.5 based on the solid content of the optical semiconductor / total silicone resin (condensed compound equivalent). An inorganic paint was obtained by diluting with methanol to 5%.
The inorganic paint is left for 1 hour, and then coated on a glass substrate by a spin coater to form a coating film. The coating film is cured at 200 ° C. for 0.5 hour and then baked at 300 ° C. for 0.5 hour. By thermally decomposing the thermally decomposable material, a coated product having an inorganic coating having a thickness of 0.3 μm was produced.
[0041]
<Example 2>
In Example 1, instead of γ-glycidoxypropyltrimethoxysilane as a thermally decomposable material, γ-methacryloxypropyltrimethoxysilane (thermal decomposition temperature: 320 ° C.) was added to the total solid content of the inorganic paint to be obtained. In addition, 10% was added to prepare an inorganic paint, and an inorganic paint was obtained by performing the same operation as in Example 1 except that the firing temperature of the coating film was changed to 340 ° C. Next, a coated product was produced in the same manner as in Example 1 using this inorganic paint.
<Example 3>
In Example 1, γ-glycidoxypropylmethyldimethoxysilane (pyrolysis temperature of 270 ° C.) was used instead of γ-glycidoxypropyltrimethoxysilane as the thermally decomposable material, and the total solid content of the inorganic paint to be obtained The same operation as in Example 1 was carried out except that 10% was added to obtain an inorganic paint. Next, a coated product was produced in the same manner as in Example 1 using this inorganic paint.
[0042]
<Example 4>
In Example 1, acetylacetoaluminum (CH) was used instead of γ-glycidoxypropyltrimethoxysilane as the thermally decomposable material.ThreeCOCHCOCHThree)ThreeExcept for preparing an inorganic paint by adding 10% of Al (thermal decomposition temperature 200 ° C.) to the total solid content of the inorganic paint to be obtained, and changing the curing temperature of the coating film to 150 ° C. The same operation as 1 was performed to obtain an inorganic paint. Next, a coated product was produced in the same manner as in Example 1 using this inorganic paint.
<Example 5>
In Example 1, isopropyl triisostearoyl titanate Ti (O-iC) was used instead of γ-glycidoxypropyltrimethoxysilane as the thermally decomposable material.ThreeH7) (OCOC17H35)ThreeAn inorganic paint was obtained in the same manner as in Example 1, except that 5% of the thermal decomposition temperature (250 ° C.) was added to the total solid content of the inorganic paint to be obtained. Next, a coated product was produced in the same manner as in Example 1 using this inorganic paint.
[0043]
<Example 6>
In Example 1, silica methanol sol (trade name: methanol silica sol, manufactured by Nissan Chemical Industries, particle size 10 to 20 nm) was used as the filler component in a weight ratio of 1. based on the solid content of filler / total silicone resin (condensed compound equivalent). An inorganic paint was obtained by performing the same operation as in Example 1 except that the amount was 5 so as to be 5. Next, a coated product was produced in the same manner as in Example 1 using this inorganic paint.
<Example 7>
In Example 1, acetylacetoaluminum (CH) was used instead of γ-glycidoxypropyltrimethoxysilane as the pyrolyzable material.ThreeCOCHCOCHThree)ThreeExample (Except for changing the curing temperature of the coating film to 150 ° C.) while adding 20% of Al (thermal decomposition temperature 200 ° C.) to the total solid content of the inorganic coating material to be obtained to prepare the inorganic coating material. The same operation as 1 was performed to obtain an inorganic paint. Next, using this inorganic paint, a coated product was produced in the same manner as in Example 1.
[0044]
<Comparative Example 1>
In Example 1, a coated product was produced in the same manner as in Example 1 except that an inorganic paint was prepared without adding any thermally decomposable material and this was applied to a glass substrate.
<Comparative example 2>
In Example 1, a coated product was produced in the same manner as in Example 1 except that the firing temperature of the coating film was changed to 150 ° C. (the temperature at which the thermally decomposable material was not thermally decomposed).
<Comparative Example 3>
In Example 4, a coated product was produced in the same manner as in Example 4 except that the firing temperature of the coating film was changed to 150 ° C. (the temperature at which the thermally decomposable material was not thermally decomposed).
[0045]
[Evaluation of coating film performance]
The coating film performance of the coated product obtained as described above was evaluated by the following method.
(Decomposability of organic substances by optical semiconductors):
A certain amount (0.2 cc) of oleic acid was dropped onto the coating surface and left for 1 hour, after which oleic acid was wiped with water and dried to obtain a test piece. Ultraviolet rays (about 1mW / cm2), And the contact angle of water on the surface of the coating film 12 hours later was measured, and the decomposability of the organic matter by the optical semiconductor was evaluated according to the following criteria.
: Measurement impossible (≒ 0 °)
○: 5 ° or less
Δ: Over 5 ° to 15 ° or less
×: Over 15 °
(Abrasion resistance = hard coat property):
Using a traverse type wear tester, the canvas cloth was brought into contact with the painted surface of the coated product, and reciprocated 1000 times (load 100 g / cm)2, The stroke was 100 mm). Then, after the abrasion test, the degree of scratches on the coating film surface was observed with an optical microscope. The judgment criteria are as follows.
[0046]
○: No scratch.
Δ: Scratch is 1 cm2Several per hit.
X: Many scratches occurred. There is peeling.
The evaluation results are shown in Table 1.
[0047]
[Table 1]
As can be seen from Table 1, in Examples 1 to 7, the organic matter was easily decomposed by the optical semiconductor as compared with Comparative Examples 1 to 3. On the other hand, Comparative Example 1 in which no thermally decomposable material was added had a lower organic matter decomposability by the optical semiconductor than Examples 1 to 7 in which the thermally decomposable material was added. Moreover, the comparative examples 2 and 3 whose baking temperature is low compared with Examples 1-7 were bad in the decomposability | degradability of the organic substance by an optical semiconductor, and abrasion resistance.
[0049]
【The invention's effect】
The present invention is a method capable of forming an inorganic coating that sufficiently exhibits various properties derived from the photocatalytic action of an optical semiconductor while maintaining hard coat properties (surface hardness, abrasion resistance, scratch resistance, etc.) A coated product obtained by this method can be provided.
Claims (8)
一般式（２）：Ti(O-C3H7)m (OC2H4N(C2H4OH)2)4-m （ｍは１〜３の整数）
一般式（３）：Ti(O-nC4H9) m (OC2H4N(C2H4OH)2)4-m（ｍは１〜３の整数）
一般式（４）：(C8H17O)m Ti(OCH2CH(C2H5)CH(OH)C3H7)4-m （ｍは１〜３の整数）
構造式（５）：Ti(C5H7O2)4
一般式（６）：Ti(OH)m (OCH(CH3)COOH)4-m （ｍは１〜３の整数）
一般式（７）：Ti(O-iC3H7)R1 m R2 3-m（ｍは１〜３の整数であり、Ｒ1 およびＲ2 はイソステアロイル基、オクタノイル基、メタクリル基、ドデシルベンゼンスルホニル基、ジオクチルホスフェート基、クミルフェニル基、ジオクチルパイロホスフェート基、ｎ−アミノエチル−アミノエチル基、アセチルアセトナト基または２−エチル−１，３−ヘキサンジオラト基を示す。）
一般式（８）：(R3)4Ti(R4)2（Ｒ3 はイソプロピル基、オクチル基または２，２−ジアリルオキシメチル−１−ブチル基を示し、Ｒ4 はジオクチルホスファイト基またはジドデシルホスファイト基を示す。）
一般式（９）：(R5)Ti(R6)2 （Ｒ5 はオキシアセテート基またはエチレン基を示し、Ｒ6 はジクミルフェニル基、ジオクチルパイロホスフェート基またはイソステアロイル基を示す。）
一般式（１０）：Al(R7) m (R8)3-m（ｍは０〜３の整数であり、Ｒ7 はアセチルアセトナート基を示し、Ｒ8 はエチルアセトナート基を示す。）The organometallic compound is represented by the following general formulas (2) to (4), structural formula (5), organic titanium compounds represented by general formulas (6) to (9), and general formula (10). The inorganic film forming method according to claim 3, which is at least one selected from the group consisting of organoaluminum compounds.
General formula (2): Ti (OC 3 H 7 ) m (OC 2 H 4 N (C 2 H 4 OH) 2 ) 4-m (m is an integer of 1 to 3)
Formula (3): Ti (O—nC 4 H 9 ) m (OC 2 H 4 N (C 2 H 4 OH) 2 ) 4-m (m is an integer of 1 to 3)
Formula (4) :( C 8 H 17 O) m Ti (OCH 2 CH (C 2 H 5) CH (OH) C 3 H 7) 4-m (m is an integer of 1 to 3)
Structural formula (5): Ti (C 5 H 7 O 2 ) 4
General formula (6): Ti (OH) m (OCH (CH 3 ) COOH) 4-m (m is an integer of 1 to 3)
General formula (7): Ti (O—iC 3 H 7 ) R 1 m R 2 3-m (m is an integer of 1 to 3, R 1 and R 2 are isostearoyl group, octanoyl group, methacryl group, A dodecylbenzenesulfonyl group, a dioctyl phosphate group, a cumylphenyl group, a dioctyl pyrophosphate group, an n-aminoethyl-aminoethyl group, an acetylacetonato group or a 2-ethyl-1,3-hexanediolato group.
Formula (8): (R 3 ) 4 Ti (R 4 ) 2 (R 3 represents an isopropyl group, an octyl group or a 2,2-diallyloxymethyl-1-butyl group, and R 4 represents a dioctyl phosphite group or Indicates a dododecyl phosphite group.)
General formula (9): (R 5 ) Ti (R 6 ) 2 (R 5 represents an oxyacetate group or ethylene group, and R 6 represents a dicumylphenyl group, a dioctylpyrophosphate group or an isostearoyl group.)
Formula (10): Al (R 7 ) m (R 8) 3-m (m is an integer of 0 to 3, R 7 represents an acetyl acetonate group, R 8 represents an ethyl acetonate group. )
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