JP2000190415A - Organic-inorganic multilayered material and its production - Google Patents
Organic-inorganic multilayered material and its productionInfo
- Publication number
- JP2000190415A JP2000190415A JP10372732A JP37273298A JP2000190415A JP 2000190415 A JP2000190415 A JP 2000190415A JP 10372732 A JP10372732 A JP 10372732A JP 37273298 A JP37273298 A JP 37273298A JP 2000190415 A JP2000190415 A JP 2000190415A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- metal alkoxide
- photocatalytic
- intermediate layer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 89
- 230000001699 photocatalysis Effects 0.000 claims abstract description 88
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 229920000620 organic polymer Polymers 0.000 claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 30
- 150000004703 alkoxides Chemical group 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 15
- -1 alkoxide compound Chemical class 0.000 claims description 56
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000004417 polycarbonate Substances 0.000 claims description 40
- 229920000515 polycarbonate Polymers 0.000 claims description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- 239000011240 wet gel Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011368 organic material Substances 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 230000001747 exhibiting effect Effects 0.000 claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims description 9
- 239000011147 inorganic material Substances 0.000 claims description 9
- 238000007146 photocatalysis Methods 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 230000001877 deodorizing effect Effects 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229920001230 polyarylate Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 230000003373 anti-fouling effect Effects 0.000 claims description 2
- 230000000249 desinfective effect Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 98
- 239000002344 surface layer Substances 0.000 abstract description 10
- 230000002542 deteriorative effect Effects 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 35
- 239000000243 solution Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 26
- 239000000377 silicon dioxide Substances 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 125000005370 alkoxysilyl group Chemical group 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 235000019645 odor Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 241000208125 Nicotiana Species 0.000 description 4
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LZHBMLBPOPGWAN-UHFFFAOYSA-N 2-[diethoxy(ethyl)silyl]acetic acid Chemical compound CCO[Si](CC)(CC(O)=O)OCC LZHBMLBPOPGWAN-UHFFFAOYSA-N 0.000 description 1
- SGFSMOHWPOFZQW-UHFFFAOYSA-N 2-chloroethyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCl SGFSMOHWPOFZQW-UHFFFAOYSA-N 0.000 description 1
- RVAVNACMMZDOCR-UHFFFAOYSA-N 2-isocyanatoethyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)CCN=C=O RVAVNACMMZDOCR-UHFFFAOYSA-N 0.000 description 1
- OSOGUZMKNNPEDS-UHFFFAOYSA-N 2-triethoxysilylacetic acid Chemical compound CCO[Si](CC(O)=O)(OCC)OCC OSOGUZMKNNPEDS-UHFFFAOYSA-N 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- SFDCAZKBEYDAOX-UHFFFAOYSA-N 3-(2-methyl-3-triethoxysilylpropyl)oxolane-2,5-dione Chemical compound CCO[Si](OCC)(OCC)CC(C)CC1CC(=O)OC1=O SFDCAZKBEYDAOX-UHFFFAOYSA-N 0.000 description 1
- UHHLNBWADPJPGB-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propanoic acid Chemical compound CO[Si](C)(C)CCC(O)=O UHHLNBWADPJPGB-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 1
- RGSFIOGHTAVOKZ-UHFFFAOYSA-N 3-isocyanatopropyl-dimethyl-propan-2-yloxysilane Chemical compound CC(C)O[Si](C)(C)CCCN=C=O RGSFIOGHTAVOKZ-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AUJPCGCOZGYPNY-UHFFFAOYSA-N 4-(2-triethoxysilylethyl)benzenesulfonyl chloride Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=C(S(Cl)(=O)=O)C=C1 AUJPCGCOZGYPNY-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QOZVPNFFOMWHRW-UHFFFAOYSA-N CCO[SiH3].N=C=O.N=C=O.N=C=O Chemical compound CCO[SiH3].N=C=O.N=C=O.N=C=O QOZVPNFFOMWHRW-UHFFFAOYSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004954 Polyphthalamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- DWSOOSUUDHCQIU-UHFFFAOYSA-N [SiH4].SCCC[Si](OC)(OC)C Chemical compound [SiH4].SCCC[Si](OC)(OC)C DWSOOSUUDHCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- AQWQNOHMVQOYGN-UHFFFAOYSA-N butoxy-diethyl-(2-isocyanatoethyl)silane Chemical compound CCCCO[Si](CC)(CC)CCN=C=O AQWQNOHMVQOYGN-UHFFFAOYSA-N 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- UUDQUXWIZNNGNO-UHFFFAOYSA-N copper;ethanol Chemical compound [Cu].CCO.CCO UUDQUXWIZNNGNO-UHFFFAOYSA-N 0.000 description 1
- QFYBRRIPNPVECS-UHFFFAOYSA-N copper;methanol Chemical compound [Cu].OC.OC QFYBRRIPNPVECS-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XVCNAZQXIVBYAD-UHFFFAOYSA-N di(propan-2-yl)-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C(C)C)(C(C)C)OC(C)C XVCNAZQXIVBYAD-UHFFFAOYSA-N 0.000 description 1
- AEAHGYRFZRBAPR-UHFFFAOYSA-N di(propan-2-yl)-propan-2-yloxysilane Chemical compound CC(C)O[SiH](C(C)C)C(C)C AEAHGYRFZRBAPR-UHFFFAOYSA-N 0.000 description 1
- YEMJITXWLIHJHJ-UHFFFAOYSA-N di(propan-2-yloxy)silane Chemical compound CC(C)O[SiH2]OC(C)C YEMJITXWLIHJHJ-UHFFFAOYSA-N 0.000 description 1
- FPVYGENKGLKEPF-UHFFFAOYSA-N dibutoxy-ethyl-(2-isocyanatoethyl)silane Chemical compound CCCCO[Si](CC)(CCN=C=O)OCCCC FPVYGENKGLKEPF-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- ZWTJVXCCMKLQKS-UHFFFAOYSA-N diethoxy(ethyl)silicon Chemical compound CCO[Si](CC)OCC ZWTJVXCCMKLQKS-UHFFFAOYSA-N 0.000 description 1
- APUUFJCSYXHJEI-UHFFFAOYSA-N diethoxy-bis(3-isocyanatopropyl)silane Chemical compound O=C=NCCC[Si](OCC)(CCCN=C=O)OCC APUUFJCSYXHJEI-UHFFFAOYSA-N 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FIYYPCHPELXPMO-UHFFFAOYSA-N ethanol tungsten Chemical compound [W].CCO.CCO.CCO.CCO.CCO.CCO FIYYPCHPELXPMO-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- JWUYLPBBRZEABA-UHFFFAOYSA-N ethoxy-bis(3-isocyanatopropyl)-methylsilane Chemical compound O=C=NCCC[Si](C)(OCC)CCCN=C=O JWUYLPBBRZEABA-UHFFFAOYSA-N 0.000 description 1
- HHBOIIOOTUCYQD-UHFFFAOYSA-N ethoxy-dimethyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(C)CCCOCC1CO1 HHBOIIOOTUCYQD-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- BOIMYFSVSNOKFY-UHFFFAOYSA-N ethyl-dimethoxy-(7-oxabicyclo[4.1.0]heptan-6-ylmethoxy)silane Chemical compound C1CCCC2OC21CO[Si](OC)(OC)CC BOIMYFSVSNOKFY-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920006375 polyphtalamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LJTHRDIGXSIYMM-UHFFFAOYSA-N propan-1-olate tantalum(5+) Chemical compound [Ta+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] LJTHRDIGXSIYMM-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- IEKMLKYASCBALX-UHFFFAOYSA-N propoxy(tripropyl)silane Chemical compound CCCO[Si](CCC)(CCC)CCC IEKMLKYASCBALX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 235000019615 sensations Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- DEKZKCDJQLBBRA-UHFFFAOYSA-N tributoxy(butyl)silane Chemical compound CCCCO[Si](CCCC)(OCCCC)OCCCC DEKZKCDJQLBBRA-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- USLHPQORLCHMOC-UHFFFAOYSA-N triethoxygallane Chemical compound CCO[Ga](OCC)OCC USLHPQORLCHMOC-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は表面層として光触媒
作用を示す材料を備える有機−無機多層材料及びその製
造方法に関する。かかる有機−無機多層材料は、様々な
臭いや汚れの除去や除菌等が要求される用途に有用な機
能性材料である。The present invention relates to an organic-inorganic multilayer material having a photocatalytic material as a surface layer and a method for producing the same. Such an organic-inorganic multilayer material is a functional material useful for applications requiring removal of various odors and stains, sterilization, and the like.
【０００２】[0002]
【従来の技術】最近、光触媒作用を示す材料である酸化
チタンが消臭、防汚や抗菌、除菌材として使用されてき
ている。これは、酸化チタンに光が当たるとその表面に
ＯＨラジカル等の活性酸素種が生成し、それらによって
表面に付着したほとんどの有機物が、最終的には二酸化
炭素と水にまで分解されることを利用している。このよ
うな酸化チタンの光触媒作用は非常に強いため、酸化チ
タンはこれまではタイル等のセラミックスのような無機
材料表面に担持させることが多かった。2. Description of the Related Art Recently, titanium oxide, which is a photocatalytic material, has been used as a deodorant, antifouling, antibacterial, and disinfecting material. This means that when light is applied to titanium oxide, active oxygen species such as OH radicals are generated on the surface, and most organic substances attached to the surface are eventually decomposed into carbon dioxide and water. We are using. Since the photocatalytic action of titanium oxide is very strong, titanium oxide has often been supported on the surface of inorganic materials such as ceramics such as tiles.
【０００３】しかし今後は他の材料、例えば成形性等に
優れるプラスチックや繊維等の有機材料に担持させる必
要が多くなると考えられる。ところが酸化チタンは、上
記したように非常に強い光触媒作用を示すため様々な不
都合が生じる。すなわち、酸化チタンに接している基材
部分が、その強い酸化作用のために著しい劣化を受け
る。無機材料と違って、有機材料の場合にはこの劣化は
耐用寿命の短縮につながる。[0003] However, it is thought that it will be necessary in the future to support it on other materials, for example, organic materials such as plastics and fibers which are excellent in moldability and the like. However, various inconveniences occur because titanium oxide exhibits a very strong photocatalytic action as described above. That is, the base portion in contact with the titanium oxide undergoes significant deterioration due to its strong oxidizing action. Unlike inorganic materials, in the case of organic materials this degradation leads to a shortened useful life.
【０００４】これを防ぐために、酸化チタンを基材に担
持するときにはこれまで、接着剤としてフッ素系樹脂や
シリコン系樹脂等の難分解性樹脂を使用する方法（特開
平７−１７１４０８、特開平７−２６５７１４）や酸化
チタン微粒子を多孔質体に担持させる方法（特開平３−
１５７１２５、特開平７−２１３９１３）が提案され
た。しかし、これらの方法を採っても酸化チタンと接着
剤となる樹脂や基材とが接触することより、これらの材
料の劣化を充分に防止できない。In order to prevent this, when titanium oxide is supported on a substrate, a method using a hardly decomposable resin such as a fluorine resin or a silicon resin as an adhesive (Japanese Patent Laid-Open No. 7-171408, Japanese Patent Laid-Open No. -265714) and a method of supporting titanium oxide fine particles on a porous body (Japanese Patent Laid-Open No.
157125, and JP-A-7-2113913) have been proposed. However, even if these methods are employed, the deterioration of these materials cannot be sufficiently prevented due to the contact between the titanium oxide and the resin or base material serving as the adhesive.
【０００５】また、酸化チタン粒子を部分的にアルキル
シリケートでコーティングする方法（特開平１０−３３
９８８）も提案されているが、アルキルシリケートの添
加量が少ないと酸化チタンと基材との接触面積が大きく
なり、やはり基材の劣化を防止できない。逆にアルキル
シリケートの添加量を多くすると材料中の酸化チタンの
相対量が減少することによって、光触媒作用が充分に発
揮されない。Further, a method of partially coating titanium oxide particles with an alkyl silicate (JP-A-10-33)
988) has also been proposed, but if the amount of the added alkyl silicate is small, the contact area between the titanium oxide and the base material increases, and the deterioration of the base material cannot be prevented. Conversely, if the addition amount of the alkyl silicate is increased, the relative amount of titanium oxide in the material is reduced, so that the photocatalysis is not sufficiently exhibited.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、上記
従来の方法の問題を解決し、表面層として光触媒作用を
示す材料を備えながら、それを担持する基材が劣化しな
い有機−無機多層材料、及びその製造方法を提供するこ
とである。SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned problems of the conventional method, and to provide an organic-inorganic multilayer in which a material having a photocatalytic action is provided as a surface layer and a substrate supporting the same is not deteriorated. It is to provide a material and a method of manufacturing the same.
【０００７】[0007]
【課題を解決するための手段】本発明は、基材と基材の
表面上に順次形成された中間層と光触媒作用層とを有す
る有機−無機多層材料において、該中間層が、官能基と
して金属アルコキシド基を有する有機重合体、又は金属
アルコキシド化合物と反応可能な官能基を有する有機重
合体と金属アルコキシド化合物との混合物を、加水分解
及び重縮合することにより架橋して得られる有機−無機
ハイブリッド材料で成り、該光触媒作用層が、光触媒作
用を示す金属酸化物を含む材料で成る、有機−無機多層
材料を提供するものであり、そのことにより上記目的が
達成される。SUMMARY OF THE INVENTION The present invention provides an organic-inorganic multilayer material having a substrate, an intermediate layer and a photocatalytic layer formed sequentially on the surface of the substrate, wherein the intermediate layer has a functional group An organic-inorganic hybrid obtained by crosslinking an organic polymer having a metal alkoxide group or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound by hydrolysis and polycondensation. The present invention provides an organic-inorganic multilayer material, wherein the photocatalytic layer is made of a material, and the photocatalytic layer is made of a material containing a metal oxide exhibiting a photocatalytic action.
【０００８】[0008]
【発明の実施の形態】基材 基材としては、従来と同様、タイル等のセラミックスの
ような無機材料を用いることもできるが、有機材料を用
いることもできる。例えば、熱可塑性樹脂や熱硬化性樹
脂などの汎用プラスチックス材料及びエンジニアリング
プラスチックス材料等の高分子材料を用いることができ
る。基材の形状としては、板状の他、糸、フィルム、球
状、ブロック等の各種形状の成形体であるものも含まれ
る。BEST MODE FOR CARRYING OUT THE INVENTION Substrate As a substrate, an inorganic material such as ceramics such as tiles can be used as in the prior art, but an organic material can also be used. For example, polymer materials such as general-purpose plastics materials such as thermoplastic resins and thermosetting resins and engineering plastics materials can be used. Examples of the shape of the base material include not only a plate shape but also a molded product having various shapes such as a thread, a film, a sphere, and a block.
【０００９】金属アルコキシド化合物と反応可能な官能
基を有する有機重合体 金属アルコキシド化合物と反応可能な官能基を有する有
機重合体（Ａ）とは、主骨格として有機鎖部分を有し、
官能基として金属アルコキシド化合物と反応可能な官能
基を有する化合物をいう。この有機重合体（Ａ）はいか
なる方法で合成されたものであってもよい。 Functionality capable of reacting with a metal alkoxide compound
The organic polymer (A) having a functional group capable of reacting with the organic polymer metal alkoxide compound having a group has an organic chain portion as a main skeleton,
A compound having a functional group capable of reacting with a metal alkoxide compound as a functional group. This organic polymer (A) may be synthesized by any method.
【００１０】有機重合体（Ａ）は主骨格として有機鎖部
分を有する。かかる主骨格の例としては、ポリエチレ
ン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、
ポリメタクリル酸メチル；ポリアミド、ポリアセター
ル、ポリカーボネート、ポリエステル、ポリフェニレン
エーテル；ポリメチルペンテン、ポリサルホン、ポリエ
ーテルサルホン、ポリフタルアミド；ポリフェニレンサ
ルファイド、ポリアリーレート、ポリイミド、ポリエー
テルイミド；ポリエーテルケトン等の熱可塑性樹脂や熱
可塑性エラストマーの骨格；フェノール樹脂、エポキシ
樹脂、アクリル樹脂、メラミン樹脂、アルキッド樹脂、
尿素樹脂、シリコーン樹脂等の熱硬化性樹脂の骨格等が
挙げられる。The organic polymer (A) has an organic chain portion as a main skeleton. Examples of such a main skeleton include polyethylene, polypropylene, polyvinyl chloride, polystyrene,
Polymethyl methacrylate; polyamide, polyacetal, polycarbonate, polyester, polyphenylene ether; polymethylpentene, polysulfone, polyethersulfone, polyphthalamide; polyphenylene sulfide, polyarylate, polyimide, polyetherimide; heat of polyetherketone, etc. Skeleton of plastic resin or thermoplastic elastomer; phenol resin, epoxy resin, acrylic resin, melamine resin, alkyd resin,
Examples include a skeleton of a thermosetting resin such as a urea resin and a silicone resin.
【００１１】有機重合体（Ａ）は上述したような重合体
や前駆体の１成分を主骨格としたものでも良く、これら
多成分の共重合体骨格でも良い。また、複数種を混合し
たものでも良く、分岐状、線状いずれの形状でも良い。
更にハロゲン化炭化水素系、エーテル系、アルコール
系、非プロトン性極性溶媒のような溶剤に溶解するかま
たは膨潤することが望ましく、数平均分子量は５００〜
５００００、好ましくは１０００〜１５０００である。The organic polymer (A) may have a main skeleton of one of the above-mentioned polymers and precursors, or may have a multi-component copolymer skeleton. Further, a mixture of a plurality of types may be used, and any of a branched shape and a linear shape may be used.
Further, it is preferable that the compound is dissolved or swells in a solvent such as a halogenated hydrocarbon, ether, alcohol, or aprotic polar solvent, and has a number average molecular weight of 500 to 500.
50,000, preferably 1,000 to 15,000.
【００１２】この中でも熱可塑性樹脂が有機重合体
（Ａ）として好ましく、高性能という点ではポリアミ
ド、ポリアセタール、ポリカーボネート、ポリサルホ
ン、ポリアリーレート等のエンジニアリングプラスチッ
クがより好ましい。Of these, thermoplastic resins are preferred as the organic polymer (A), and engineering plastics such as polyamide, polyacetal, polycarbonate, polysulfone, and polyarylate are more preferred in terms of high performance.
【００１３】有機重合体（Ａ）が有する官能基は金属ア
ルコキシド化合物（Ｂ）と反応可能なものであれば良
く、特に限定されないが、具体的には金属アルコキシド
基、水酸基、アミノ基、カルボキシル基等が挙げられ
る。特に金属アルコキシド基が好ましい。有機重合体
（Ａ）の官能基当量は１〜１００、好ましくは１〜５
０、更に好ましくは２〜１０である。有機重合体（Ａ）
の官能基当量が１を下回ると材料の性能が低下する可能
性があり、１００を上回ると材料がもろくなる可能性が
ある。１分子の有機重合体（Ａ）が有する官能基は全て
同一でも良く、複数種であっても良い。The functional group contained in the organic polymer (A) is not particularly limited as long as it can react with the metal alkoxide compound (B), and specific examples thereof include a metal alkoxide group, a hydroxyl group, an amino group and a carboxyl group. And the like. Particularly, a metal alkoxide group is preferable. The functional equivalent of the organic polymer (A) is 1 to 100, preferably 1 to 5
0, more preferably 2 to 10. Organic polymer (A)
If the functional group equivalent of is less than 1, the performance of the material may decrease, and if it exceeds 100, the material may become brittle. The functional groups of one molecule of the organic polymer (A) may be all the same, or may be a plurality of types.
【００１４】金属アルコキシド化合物（Ｂ）としては、
金属酸化物とされた場合に光触媒作用を示さず、有機材
料でなる基材と接したとしても接した部分が劣化されな
いものであれば、あらゆるタイプの化合物を用いること
ができる。その中でも好ましいものは、式（１） ＡpＭ 式（１） ［式中、Ａは炭素数１〜８、好ましくは１〜４のアルコ
キシ基であり、ＭはＳｉ、Ｚｒ、Ｆｅ、Ｓｎ、Ｂ、Ａ
ｌ、Ｇｅ、Ｃｅ、Ｔａ、Ｂａ、Ｇａ、Ｐｂ及びＷ等から
なる群、好ましくはＳｉ及びＺｒからなる群から選択さ
れる金属元素であり、ｐは２〜６の整数である。］で表
される化合物である。As the metal alkoxide compound (B),
Any type of compound can be used as long as it does not exhibit a photocatalytic action when formed into a metal oxide and does not deteriorate the portion in contact with a substrate made of an organic material. Among them, preferred are the formula (1) Ap M Formula (1) wherein A is an alkoxy group having 1 to 8, preferably 1 to 4 carbon atoms, and M is Si, Zr, Fe, Sn, B, A
1, a metal element selected from the group consisting of Ge, Ce, Ta, Ba, Ga, Pb, W and the like, preferably the group consisting of Si and Zr, and p is an integer of 2-6. ] It is a compound represented by these.
【００１５】具体的には、テトラメトキシシラン、テト
ラエトキシシラン、テトライソプロポキシシラン、テト
ラブトキシシラン等のテトラアルコキシシラン類、テト
ラｎ−プロポキシジルコニウム、テトライソプロポキシ
ジルコニウム、テトラブトキシジルコニウム等のテトラ
アルコキシジルコニウム類、及びジエトキシバリウム、
トリメトキシホウ素、トリエトキシガリウム、トリブト
キシアルミニウム、テトラエトキシゲルマニウム、テト
ラブトキシ鉛、ペンタｎ−プロポキシタンタル、ヘキサ
エトキシタングステン等の金属アルコキシド類が挙げら
れる。Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and tetrabutoxysilane, and tetraalkoxyzirconium such as tetra-n-propoxyzirconium, tetraisopropoxyzirconium and tetrabutoxyzirconium And diethoxybarium,
Metal alkoxides such as trimethoxyboron, triethoxygallium, tributoxyaluminum, tetraethoxygermanium, tetrabutoxylead, pentan-propoxytantalum, and hexaethoxytungsten are exemplified.
【００１６】金属アルコキシド化合物（Ｂ）の他の例
は、式（２） ＲkＡlＭ（Ｒ’mＸ）n 式（２） ［式中、Ｒは水素、炭素数１〜１２、好ましくは１〜５
のアルキル基またはフェニル基であり、Ａは炭素数１〜
８、好ましくは１〜４のアルコキシ基であり、ＭはＳ
ｉ、Ｚｒ、Ｆｅ、Ｓｎ、Ｂ、Ａｌ、Ｇｅ、Ｃｅ、Ｔａ及
びＷ等からなる群、好ましくはＳｉ及びＺｒからなる群
から選択される金属元素であり、Ｒ’は炭素数１〜４、
好ましくは２〜４のアルキレン基またはアルキリデン基
であり、Ｘはイソシアネート基、エポキシ基、カルボキ
シル基、酸ハロゲン化物基、酸無水物基、アミノ基、チ
オール基、ビニル基、メタクリル基、ハロゲン基等の一
般的な官能基であり、ｋは０〜５の整数であり、ｌは１
〜５の整数であり、ｍは０または１の整数であり、ｎは
０〜５の整数である。］で表される化合物である。Another example of the metal alkoxide compound (B) is represented by the following formula (2): R k Al M (R ′ mx ) n formula (2) wherein R is hydrogen, having 1 to 12 carbon atoms, preferably Is 1-5
Is an alkyl group or a phenyl group, and A has 1 to 1 carbon atoms.
8, preferably 1-4 alkoxy groups, wherein M is S
i, Zr, Fe, Sn, B, Al, Ge, Ce, Ta, W and the like, preferably a metal element selected from the group consisting of Si and Zr, wherein R ′ has 1 to 4 carbon atoms;
X is preferably an alkylene group or an alkylidene group of 2 to 4, and X is an isocyanate group, an epoxy group, a carboxyl group, an acid halide group, an acid anhydride group, an amino group, a thiol group, a vinyl group, a methacryl group, a halogen group, or the like. Wherein k is an integer from 0 to 5 and l is 1
M is an integer of 0 or 1, and n is an integer of 0 to 5. ] It is a compound represented by these.
【００１７】Ｓｉを例に取り、具体的に例示すれば、ト
リメトキシシラン、トリエトキシシラン、トリｎ−プロ
ポキシシラン、ジメトキシシラン、ジエトキシシラン、
ジイソプロポキシシラン、モノメトキシシラン、モノエ
トキシシラン、モノブトキシシラン、メチルジメトキシ
シラン、エチルジエトキシシラン、ジメチルメトキシシ
ラン、ジイソプロピルイソプロポキシシラン、メチルト
リメトキシシラン、エチルトリエトキシシラン、ｎ−プ
ロピルトリｎ−プロポキシシラン、ブチルトリブトキシ
シラン、ジメチルジメトキシシラン、ジエチルジエトキ
シシラン、ジイソプロピルジイソプロポキシシラン、ジ
ブチルジブトキシシラン、トリメチルメトキシシラン、
トリエチルエトキシラン、トリｎ−プロピルｎ−プロポ
キシシラン、トリブチルブトキシシラン、フェニルトリ
メトキシラン、ジフェニルジエトキシシラン、トリフェ
ニルメトキシシラン等の（アルキル）アルコキシシラ
ン；３−イソシアネートプロピルトリエトキシシラン、
２−イソシアネートエチルトリｎ−プロポキシシラン、
３−イソシアネートプロピルメチルジメトキシシラン、
２−イソシアネートエチルエチルジブトキシシラン、３
−イソシアネートプロピルジメチルイソプロポキシシラ
ン、２−イソシアネートエチルジエチルブトキシシラ
ン、ジ（３−イソシアネートプロピル）ジエトキシシラ
ン、ジ（３−イソシアネートプロピル）メチルエトキシ
シラン、エトキシシラントリイソシアネート等のイソシ
アネート基を有する（アルキル）アルコキシシラン；３
−グリシドキシプロピルトリエトキシシラン、３−グリ
シドキシプロピルメチルジメトキシシラン、３−グリシ
ドキシプロピルジメチルエトキシシラン、２−（３，４
−エポキシシクロヘキシル）エチルトリメトキシシラ
ン、３，４−エポキシブチルトリメトキシシラン等のエ
ポキシ基を有する（アルキル）アルコキシシラン；カル
ボキシメチルトリエトキシシラン、カルボキシメチルエ
チルジエトキシシラン、カルボキシエチルジメチルメト
キシシラン等のカルボキシル基を有する（アルキル）ア
ルコキシシラン；３−（トリエトキシシリル）−２−メ
チルプロピルコハク酸無水物等の酸無水物基を有するア
ルコキシシラン；２−（４−クロロスルフォニルフェニ
ル）エチルトリエトキシシラン等の酸ハロゲン化物基を
有するアルコキシシラン；３−アミノプロピルトリメト
キシシラン、３−アミノプロピルトリエトキシシラン、
Ｎ−２−（アミノエチル）−３−アミノプロピルトリエ
トキシシラン、Ｎ−２−（アミノエチル）−３−アミノ
プロピルメチルジメトキシシラン、Ｎ−フェニル−３−
アミノプロピルトリメトキシシラン等のアミノ基を有す
る（アルキル）アルコキシシラン；３−メルカプトプロ
ピルトリメトキシシラン、２−メルカプトエチルトリエ
トキシシラン、３−メルカプトプロピルメチルジメトキ
シシラン等のチオール基を有する（アルキル）アルコキ
シシラン；ビニルトリメトキシシラン、ビニルトリエト
キシシラン、ビニルメチルジエトキシシラン等のビニル
基を有する（アルキル）アルコキシシラン；３−メタク
リロキシプロピルトリメトキシシラン、３−メタクリロ
キシプロピルトリエトキシシラン、３−メタクリロキシ
ピロピルメチルジメチルシラン等のメタクリル基を有す
る（アルキル）アルコキシシラン；トリエトキシフルオ
ロシラン、３−クロロプロピルトリメトキシシラン、３
−ブロモプロピルトリエトキシシラン、２−クロロエチ
ルメチルジメトキシシラン等のハロゲン基を有する（ア
ルキル）アルコキシシラン；を挙げることができる。Taking Si as an example, specific examples include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, dimethoxysilane, diethoxysilane,
Diisopropoxysilane, monomethoxysilane, monoethoxysilane, monobutoxysilane, methyldimethoxysilane, ethyldiethoxysilane, dimethylmethoxysilane, diisopropylisopropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n-propyltrin -Propoxysilane, butyltributoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldiisopropoxysilane, dibutyldibutoxysilane, trimethylmethoxysilane,
(Alkyl) alkoxysilanes such as triethylethoxysilane, tri-n-propyln-propoxysilane, tributylbutoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane; 3-isocyanatopropyltriethoxysilane;
2-isocyanatoethyltri-n-propoxysilane,
3-isocyanatopropylmethyldimethoxysilane,
2-isocyanatoethylethyldibutoxysilane, 3
-Isocyanate groups having an isocyanate group such as isocyanatopropyldimethylisopropoxysilane, 2-isocyanatoethyldiethylbutoxysilane, di (3-isocyanatopropyl) diethoxysilane, di (3-isocyanatopropyl) methylethoxysilane, ethoxysilanetriisocyanate, etc. ) Alkoxysilane; 3
-Glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4
(Epoxycyclohexyl) ethyltrimethoxysilane, (alkyl) alkoxysilane having an epoxy group such as 3,4-epoxybutyltrimethoxysilane; carboxymethyltriethoxysilane, carboxymethylethyldiethoxysilane, carboxyethyldimethylmethoxysilane and the like (Alkyl) alkoxysilane having a carboxyl group; alkoxysilane having an acid anhydride group such as 3- (triethoxysilyl) -2-methylpropylsuccinic anhydride; 2- (4-chlorosulfonylphenyl) ethyltriethoxysilane Alkoxysilane having an acid halide group such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-
(Alkyl) alkoxysilanes having an amino group such as aminopropyltrimethoxysilane; (alkyl) alkoxysilanes having a thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane and 3-mercaptopropylmethyldimethoxysilane Silane; (alkyl) alkoxysilane having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryl (Alkyl) alkoxysilanes having a methacryl group such as loxypropylpyrmethyldimethylsilane; triethoxyfluorosilane, 3-chloropropyltrimethoxysilane,
(Alkyl) alkoxysilanes having a halogen group, such as -bromopropyltriethoxysilane and 2-chloroethylmethyldimethoxysilane.
【００１８】もちろんＳｉだけではなく、Ｚｒ、Ｆｅ、
Ｓｎ、Ｂ、Ａｌ、Ｇｅ、Ｃｅ、ＴａやＷ等の金属におい
ても、金属酸化物とされた場合に光触媒作用を示さない
同様の化合物を例示することができる。Of course, not only Si but also Zr, Fe,
In the case of metals such as Sn, B, Al, Ge, Ce, Ta, and W, similar compounds that do not exhibit a photocatalytic action when formed into a metal oxide can be exemplified.
【００１９】これらの金属アルコキシド化合物（Ｂ）は
１種類だけでも良く、２種以上を併用しても良い。ま
た、Ｍｇ［Ａｌ（iso-ＯＣ3Ｈ7）4］2、Ｂａ［Ｚｒ
2（ＯＣ2Ｈ5）9］2、（Ｃ3Ｈ7Ｏ）2Ｚｒ［Ａｌ（ＯＣ3
Ｈ7）4］2等の１分子内に２種以上の金属元素が含まれ
ているような金属アルコキシド化合物やテトラメトキシ
シランオリゴマーやテトラエトキシシランオリゴマー等
の１分子内に２個以上の繰り返し単位を有するオリゴマ
ータイプの金属アルコキシド化合物を用いても良い。ま
た、アルコキシ基がアセトキシ基やアセチルアセトキシ
基であっても良い。These metal alkoxide compounds (B) may be used alone or in combination of two or more. Further, Mg [Al (iso-OC 3 H 7 ) 4 ] 2 , Ba [Zr
2 (OC 2 H 5 ) 9 ] 2 , (C 3 H 7 O) 2 Zr [Al (OC 3
H 7) 4] 2 or more repeating units per molecule, such as a metal alkoxide compound and tetramethoxysilane oligomer and tetraethoxysilane oligomer appears to contain two or more metal elements in one molecule of 2, etc. An oligomer-type metal alkoxide compound having the following formula: Further, the alkoxy group may be an acetoxy group or an acetylacetoxy group.
【００２０】有機重合体（Ａ）の中で官能基として水酸
基、アミノ基、カルボキシル基等を有するものは常法に
より金属アルコキシド（Ｂ）と反応させることができ
る。その結果、官能基としてより反応性が高い金属アル
コキシド基を有する有機重合体が得られる。有機重合体
（Ａ）と金属アルコキシド（Ｂ）との反応方法は、例え
ば、特願平９−３２７８４２号の明細書第００３９段落
〜第００５４段落に詳細に記載されている。The organic polymer (A) having a hydroxyl group, amino group, carboxyl group or the like as a functional group can be reacted with the metal alkoxide (B) by a conventional method. As a result, an organic polymer having a highly reactive metal alkoxide group as a functional group is obtained. The reaction method between the organic polymer (A) and the metal alkoxide (B) is described in detail, for example, in Japanese Patent Application No. 9-327842, paragraphs 0039 to 0054 of the specification.
【００２１】中間層 中間層とは基材と光触媒作用層との中間に位置すること
により光触媒作用層が基材に接触するのを防止する層を
いう。中間層は光触媒作用を示さず、有機材料でなる基
材と接したとしても基材の接した部分が劣化されず、ま
た、基材及び光触媒作用層との接着性が良好な材料で形
成することが好ましい。 Intermediate layer The intermediate layer is a layer located between the substrate and the photocatalytic layer to prevent the photocatalytic layer from contacting the substrate. The intermediate layer does not exhibit photocatalysis, and even if it comes into contact with a substrate made of an organic material, the part in contact with the substrate is not deteriorated, and is formed of a material having good adhesion to the substrate and the photocatalytic layer. Is preferred.
【００２２】中間層として好ましい材料は、官能基とし
て金属アルコキシド基を有する有機重合体、又は金属ア
ルコキシド化合物と反応可能な官能基を有する有機重合
体と金属アルコキシド化合物との混合物を、加水分解及
び重縮合することにより架橋して得られる有機−無機ハ
イブリッド材料である。Preferred materials for the intermediate layer are an organic polymer having a metal alkoxide group as a functional group, or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound, by hydrolysis and polymerization. An organic-inorganic hybrid material obtained by crosslinking by condensation.
【００２３】有機−無機ハイブリッド材料中の有機重合
体成分の含有率は特に制限はないが、塗膜として有機材
料の基材にコーティングする場合には、基材との密着性
をより高めるために基材との接触面部分では５０重量％
以上であることが好ましい。また、基材の劣化を防ぐた
めに、光触媒作用を示す材料との界面部分では有機重合
体成分の含有率は０％に近いほど望ましく、言い換えれ
ば金属酸化物成分の含有率が１００％に近いほど良い。
光触媒作用を示す材料の含有率は、特性をより発現させ
るために最も高い領域では５０重量％以上であることが
望ましい。The content of the organic polymer component in the organic-inorganic hybrid material is not particularly limited. However, when a coating is applied to a substrate of an organic material as a coating film, it is necessary to further improve the adhesion to the substrate. 50% by weight at the contact surface with the substrate
It is preferable that it is above. Further, in order to prevent the deterioration of the base material, the content of the organic polymer component is desirably closer to 0% at the interface with the photocatalytic material, in other words, the content of the metal oxide component is closer to 100%. good.
The content of the photocatalytic material is desirably 50% by weight or more in the highest region in order to further develop the characteristics.
【００２４】中間層を基材の表面上に順次形成された第
１中間層と第２中間層とからなる２重構造とし、第１中
間層は、官能基として金属アルコキシド基を有する有機
重合体、又は金属アルコキシド化合物と反応可能な官能
基を有する有機重合体と金属アルコキシド化合物との混
合物を、加水分解及び重縮合することにより架橋して得
られる有機−無機ハイブリッド材料で構成し、第２中間
層は金属アルコキシド化合物を加水分解及び重縮合する
ことにより架橋して得られる無機材料で構成してもよ
い。The intermediate layer has a double structure consisting of a first intermediate layer and a second intermediate layer sequentially formed on the surface of the substrate, and the first intermediate layer is an organic polymer having a metal alkoxide group as a functional group. Or an organic-inorganic hybrid material obtained by crosslinking a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound by hydrolysis and polycondensation; The layer may be composed of an inorganic material obtained by crosslinking the metal alkoxide compound by hydrolysis and polycondensation.
【００２５】この場合は、光触媒作用層は金属酸化物で
成る第２中間層と接触し、有機−無機ハイブリッド材料
と接触しない。従って、基材の劣化が防止されるだけで
なく、有機−無機ハイブリッド材料に含まれる有機鎖部
分が光触媒作用層によって劣化されることも防止され
る。その結果、有機−無機多層材料の耐用寿命がより延
長される。In this case, the photocatalytic layer is in contact with the second intermediate layer made of a metal oxide, and is not in contact with the organic-inorganic hybrid material. Therefore, not only is the deterioration of the base material prevented, but also the organic chain portion contained in the organic-inorganic hybrid material is prevented from being deteriorated by the photocatalytic layer. As a result, the useful life of the organic-inorganic multilayer material is further extended.
【００２６】ゾルーゲル法による加水分解、重縮合と
は、金属アルコキシド化合物あるいは金属アルコキシ基
を有する重合体を水と反応させることでアルコキシ基を
水酸基に変換し、次いでこの水酸基を同時進行的に重縮
合させることによりヒドロキシ金属基（例えば−ＳｉＯ
Ｈ）を有する化合物あるいは重合体が脱水反応あるいは
隣接した分子と脱アルコール反応を生じ、無機的な共有
結合を介して３次元的に架橋する反応を言う。この際、
重縮合反応はふたつのヒドロキシ金属基の脱水反応が最
も起こりやすいが、それだけではなく、他の水酸基やア
ミノ基、カルボキシル基等の活性水素を有する官能基と
も起こりうる。The hydrolysis and polycondensation by the sol-gel method means that a metal alkoxide compound or a polymer having a metal alkoxy group is reacted with water to convert the alkoxy group into a hydroxyl group, and then the hydroxyl group is simultaneously polycondensed. To form a hydroxy metal group (e.g., -SiO
H) is a reaction in which a compound or polymer having H) undergoes a dehydration reaction or a dealcoholization reaction with an adjacent molecule and crosslinks three-dimensionally through an inorganic covalent bond. On this occasion,
In the polycondensation reaction, dehydration of two hydroxy metal groups is most likely to occur, but not only that, but also other functional groups having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group.
【００２７】加水分解反応に用いられる水は、全てのア
ルコキシ基を水酸基に変換するために必要な量を添加し
ても良いし、反応系中の水分を利用したり、大気中の水
分を吸湿させて行っても良い。The water used in the hydrolysis reaction may be added in an amount necessary to convert all the alkoxy groups to hydroxyl groups, may utilize water in the reaction system, or absorb moisture in the atmosphere. You may let me go.
【００２８】反応条件としては、室温〜１００℃で０．
５〜２４時間程度が望ましい。またその際、塩酸、硫
酸、酢酸、ベンゼンスルホン酸、ｐ−トルエンスルホン
酸等の酸性触媒や水酸化ナトリウム、水酸化カリウム、
アンモニア、トリエチルアミン、ピペリジン、１，８−
ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢ
Ｕ）等の塩基性触媒を用いても良い。The reaction conditions are as follows: room temperature to 100 ° C .;
About 5 to 24 hours are desirable. At that time, acid catalysts such as hydrochloric acid, sulfuric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid and sodium hydroxide, potassium hydroxide,
Ammonia, triethylamine, piperidine, 1,8-
Diazabicyclo [5,4,0] -7-undecene (DB
A basic catalyst such as U) may be used.
【００２９】本発明における全ての加水分解過程では強
度、硬度、耐候性、耐薬品性、難燃性、帯電防止性等の
機能を向上または新たに付与する目的で無機物含有量や
重合体間の架橋密度を調整するためにＳｉ、Ｔｉ、Ｚ
ｒ、Ｆｅ、Ｃｕ、Ｓｎ、Ｂ、Ａｌ、Ｇｅ、Ｃｅ、Ｔａ、
Ｗ等の金属、金属酸化物、金属錯体や無機塩等を共存さ
せても良い。また、ゲル化、乾燥、熱処理の際に生じる
可能性があるクラックを抑制するためにホルムアミドや
ジメチルホルムアミド、ジオキサン、シュウ酸等を乾燥
抑制剤として加えても良いし、添加物としてアセチルア
セトン等を加えても良い。In all the hydrolysis processes in the present invention, the inorganic content or the polymer content is improved in order to improve or newly impart functions such as strength, hardness, weather resistance, chemical resistance, flame retardancy and antistatic property. Si, Ti, Z to adjust crosslink density
r, Fe, Cu, Sn, B, Al, Ge, Ce, Ta,
A metal such as W, a metal oxide, a metal complex, an inorganic salt, or the like may coexist. Further, in order to suppress cracking that may occur during gelation, drying, and heat treatment, formamide, dimethylformamide, dioxane, oxalic acid, and the like may be added as a drying inhibitor, or acetylacetone or the like may be added as an additive. May be.
【００３０】中間層の乾燥厚さは一般に０．０１〜１０
００μｍ、好ましくは０．１〜１００μｍとする。この
層厚が１０００μｍを上回ると層の形成に労力を要し、
大量の材料が必要となるためコストがかかる。また、
０．０１μｍを下回ると層中にピンホールが生じ易くな
り、所望の性能が得られない怖れがある。The dry thickness of the intermediate layer is generally from 0.01 to 10
00 μm, preferably 0.1 to 100 μm. When this layer thickness exceeds 1000 μm, labor is required for forming the layer,
The cost is high because a large amount of material is required. Also,
When the thickness is less than 0.01 μm, pinholes are easily formed in the layer, and there is a fear that desired performance cannot be obtained.
【００３１】中間層を、第１中間層と第２中間層とで成
る２層構造とする場合は、第１中間層の乾燥厚さは、上
記と同様の理由で、一般に０．０１〜１０００μｍ、好
ましくは０．１〜１００μｍとする。第２中間層の乾燥
厚さは一般に０．０１〜１００μｍ、好ましくは０．１
〜１０μｍとする。この層厚が１００μｍを上回ると層
に亀裂が生じたり剥離する怖れがある。また、０．０１
μｍを下回ると層中にピンホールが生じ易くなり、所望
の性能が得られない怖れがある。When the intermediate layer has a two-layer structure comprising a first intermediate layer and a second intermediate layer, the first intermediate layer generally has a dry thickness of 0.01 to 1000 μm for the same reason as described above. , Preferably 0.1 to 100 μm. The dry thickness of the second intermediate layer is generally from 0.01 to 100 μm, preferably from 0.1 to 100 μm.
To 10 μm. If this layer thickness exceeds 100 μm, there is a risk of cracking or peeling of the layer. Also, 0.01
When the thickness is less than μm, pinholes are easily generated in the layer, and there is a fear that desired performance cannot be obtained.
【００３２】光触媒作用層 光触媒作用層とは光触媒作用を示す材料で成る層をい
う。光触媒性は強いほど良い。光触媒作用を示す材料の
形状については特に制限はないが、光触媒作用を高める
ためには表面積が大きいことが好ましい。例えば、光触
媒作用を示す材料を粒子状とする場合は、粒径が大きす
ぎると基材の外観や触感を損なうことより１００μｍ以
下とすることが望ましい。また光触媒作用は微粒子ほど
活性に富む傾向があることより粒径は小さくすることが
望ましい。 Photocatalytic layer The photocatalytic layer is a layer made of a material having a photocatalytic action. The stronger the photocatalytic property, the better. There is no particular limitation on the shape of the material exhibiting photocatalysis, but it is preferable that the surface area is large in order to enhance the photocatalysis. For example, when the material having a photocatalytic effect is in the form of particles, it is preferable that the particle size be 100 μm or less because an excessively large particle diameter impairs the appearance and tactile sensation of the substrate. Also, the photocatalytic action tends to be more active as the fine particles are finer, so that the particle size is desirably small.
【００３３】光触媒作用を示す材料の一例は、光触媒作
用を示す金属酸化物（Ｃ）を含む材料である。金属酸化
物（Ｃ）は１種類だけでも良く、２種以上を併用しても
良いし、１分子内に２個以上の金属元素が含まれている
ようなものでも良い。更に、光触媒性を強める、機械的
強度を高める、柔軟性を付与する等の目的で他の無機物
を含んでも良い。One example of a material having a photocatalytic action is a material containing a metal oxide (C) having a photocatalytic action. The metal oxide (C) may be only one kind, two or more kinds may be used in combination, or one in which two or more metal elements are contained in one molecule. Further, other inorganic substances may be included for the purpose of enhancing photocatalytic properties, increasing mechanical strength, imparting flexibility, and the like.
【００３４】光触媒作用層中の金属酸化物の（Ｃ）の含
有量は、一般に１０〜１００重量％程度、好ましくは２
０〜１００重量％程度である。金属酸化物（Ｃ）として
は、酸化チタンや酸化銅（Ｉ）等を用いることが好まし
い。The content of the metal oxide (C) in the photocatalytic layer is generally about 10 to 100% by weight, preferably 2 to 100% by weight.
It is about 0 to 100% by weight. As the metal oxide (C), it is preferable to use titanium oxide, copper oxide (I), or the like.
【００３５】酸化チタンは硫酸チタニル、四塩化チタン
やチタン酸エステルを中和または加水分解する方法や四
塩化チタンを気相酸化する方法等の公知の方法で得られ
るもので良い。アナターゼ型酸化チタン、ルチル型酸化
チタン、無定形酸化チタン、水和酸化チタン等やこれら
の混合物が例示される。The titanium oxide may be obtained by a known method such as a method of neutralizing or hydrolyzing titanyl sulfate, titanium tetrachloride or titanate, and a method of vapor-phase oxidation of titanium tetrachloride. Examples thereof include anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, hydrated titanium oxide and the like, and mixtures thereof.
【００３６】酸化銅（Ｉ）は塩化銅（Ｉ）の加水分解や
酸化銅（II）や水酸化銅（II）を還元する方法等で得ら
れる。Copper (I) oxide can be obtained by a method such as hydrolysis of copper (I) chloride or reduction of copper (II) oxide or copper (II) hydroxide.
【００３７】金属酸化物（Ｃ）は、金属酸化物とされた
場合に光触媒作用を示す金属の金属アルコキシド化合
物、又はそれを含む金属アルコキシド混合物を加水分解
及び重縮合させて得られる無機材料であってもよい。光
触媒作用を示す金属アルコキシド化合物としては、中心
金属（Ｍ）としてＴｉ、Ｃｕ等の金属元素を有する式
（１）で表される金属アルコキシド化合物を用いること
が好ましい。The metal oxide (C) is an inorganic material obtained by hydrolyzing and polycondensing a metal alkoxide compound of a metal which exhibits a photocatalytic action when converted to a metal oxide, or a metal alkoxide mixture containing the compound. You may. As the metal alkoxide compound exhibiting a photocatalytic action, it is preferable to use a metal alkoxide compound represented by the formula (1) having a metal element such as Ti or Cu as a central metal (M).
【００３８】具体的には、テトラメトキシチタン、テト
ラエトキシチタン、テトラｎ−プロポキシチタン、テト
ライソプロポキシチタン、テトラブトキシチタン等のテ
トラアルコキシチタン類；及びジメトキシ銅、ジエトキ
シ銅、ジｎ−プロポキシ銅、ジイソプロポキシ銅、ジブ
トキシ銅等のジアルコキシ銅類が挙げられる。Specifically, tetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium; dimethoxycopper, diethoxycopper, din-propoxycopper; Dialkoxy coppers such as copper diisopropoxy and copper dibutoxy;
【００３９】また他の例として、中心金属（Ｍ）として
Ｔｉ、Ｃｕ等の金属元素を有する式（２）で表される金
属アルコキシド化合物でもよい。As another example, a metal alkoxide compound represented by the formula (2) having a metal element such as Ti or Cu as a central metal (M) may be used.
【００４０】これらの金属アルコキシド化合物は１種類
だけでも良く、２種以上を併用しても良い。また、１分
子内に２種以上の金属元素が含まれているような金属ア
ルコキシド化合物や１分子内に２個以上の繰り返し単位
を有するオリゴマータイプの金属アルコキシド化合物を
用いても良い。また、アルコキシ基がアセトキシ基やア
セチルアセトキシ基であっても良い。These metal alkoxide compounds may be used alone or in combination of two or more. Further, a metal alkoxide compound containing two or more metal elements in one molecule or an oligomer-type metal alkoxide compound having two or more repeating units in one molecule may be used. Further, the alkoxy group may be an acetoxy group or an acetylacetoxy group.
【００４１】光触媒作用層の乾燥厚さは一般に０．０１
〜１００μｍ、好ましくは０．１〜１０μｍとする。層
厚が１００μｍを上回ると層に亀裂が生じたり剥離する
怖れがある。また、０．０１μｍを下回ると層中にピン
ホールが生じ易くなり、所望の性能が得られない怖れが
ある。The dry thickness of the photocatalytic layer is generally 0.01
To 100 μm, preferably 0.1 to 10 μm. If the layer thickness exceeds 100 μm, there is a fear that the layer may crack or peel off. On the other hand, when the thickness is less than 0.01 μm, pinholes are easily formed in the layer, and there is a fear that desired performance cannot be obtained.
【００４２】有機−無機多層材料の製造 本発明の有機−無機多層材料は、金属アルコキシド化合
物と反応可能な官能基を有する有機重合体、金属アルコ
キシド化合物、及び光触媒作用を示す材料を主原料と
し、ゾル−ゲル反応を利用して形成する。 Production of Organic-Inorganic Multilayer Material The organic-inorganic multilayer material of the present invention comprises, as main raw materials, an organic polymer having a functional group capable of reacting with a metal alkoxide compound, a metal alkoxide compound, and a material having a photocatalytic action. It is formed using a sol-gel reaction.
【００４３】まず、官能基として金属アルコキシド基を
有する有機重合体、又は金属アルコキシド化合物と反応
可能な官能基を有する有機重合体と金属アルコキシド化
合物との混合物を適当な溶媒に溶解し、場合によっては
酸又は塩基を触媒として加え、加水分解する。次いで、
表面を有する基材を提供し、基材の表面上に得られた溶
液もしくは湿潤ゲルを塗布した後、溶媒の一部を蒸発さ
せることによって中間層を形成する。First, an organic polymer having a metal alkoxide group as a functional group or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound is dissolved in an appropriate solvent, and in some cases, An acid or base is added as a catalyst and hydrolyzed. Then
A substrate having a surface is provided, and an intermediate layer is formed by applying the obtained solution or wet gel on the surface of the substrate and then evaporating a part of the solvent.
【００４４】この上に形成される層（第２中間層又は光
触媒作用層）との密着性を高めるためには乾燥は必要最
低限に止めることが好ましい。乾燥させる場合は室温下
で放置して乾燥させてもよいし、加熱して乾燥させても
よい。In order to enhance the adhesion to the layer formed thereon (the second intermediate layer or the photocatalytic layer), it is preferable to limit the drying to the minimum necessary. When drying, it may be left to dry at room temperature, or may be dried by heating.
【００４５】この層の上に第２中間層を形成してもよ
い。その場合は、この層の表面上に金属アルコキシド化
合物を含む溶液もしくは湿潤ゲルを更に塗布する。A second intermediate layer may be formed on this layer. In that case, a solution or wet gel containing a metal alkoxide compound is further applied on the surface of this layer.
【００４６】次いで、中間層の表面上に、光触媒作用を
示す材料で成る光触媒作用層を形成する。光触媒作用を
示す材料としては光触媒作用を示す金属酸化物（Ｃ）を
含む材料を用いることが好ましい。光触媒作用層の形成
は、例えば、金属酸化物（Ｃ）を含む金属酸化物の粉末
（粒子）を揮発性溶媒に分散させ、得られる分散体を中
間層の表面に塗布する方法で行いうる。金属酸化物
（Ｃ）を含む金属酸化物の粉末（粒子）を湿潤ゲルの状
態の中間層の表面に直接塗布する方法で行ってもよい。
また、金属酸化物とされた場合に光触媒作用を示す金属
の金属アルコキシド化合物、又はこれを含む金属アルコ
キシドの混合物を溶液もしくは湿潤ゲルとし、これを中
間層の表面に塗布する方法で行ってもよい。Next, a photocatalytic layer made of a material having a photocatalytic action is formed on the surface of the intermediate layer. As the material having a photocatalytic action, it is preferable to use a material containing a metal oxide (C) having a photocatalytic action. The photocatalytic layer can be formed by, for example, dispersing a metal oxide powder (particles) containing the metal oxide (C) in a volatile solvent, and applying the resulting dispersion to the surface of the intermediate layer. The method may be carried out by directly applying powder (particles) of the metal oxide containing the metal oxide (C) to the surface of the intermediate layer in a wet gel state.
Alternatively, a method of applying a metal alkoxide compound of a metal exhibiting a photocatalytic action when formed into a metal oxide, or a mixture of metal alkoxides containing the metal alkoxide compound to a solution or a wet gel, and applying this to the surface of the intermediate layer may be used. .
【００４７】この工程を複数回繰り返して光触媒作用層
を複層構造としてもよく、その際に、例えば、金属酸化
物（Ｃ）の含有率を増加させる等、光触媒作用を示す材
料の組成を変化させてもよい。This step may be repeated a plurality of times to form a photocatalytic layer having a multilayer structure. In this case, the composition of the photocatalytic material is changed, for example, by increasing the content of metal oxide (C). May be.
【００４８】その後、形成した層を乾燥させる。乾燥
は、室温で放置することにより行ってもよいが、更に縮
合反応を進め、架橋をより強固なものとしたい場合に
は、５０〜５００℃で５分〜４８時間程度、熱処理を行
う。Thereafter, the formed layer is dried. The drying may be carried out by leaving it at room temperature. However, if it is desired to further promote the condensation reaction and to make the crosslinking stronger, heat treatment is carried out at 50 to 500 ° C. for about 5 minutes to 48 hours.
【００４９】このような方法で作製した有機−無機多層
材料は、有機重合体成分と金属酸化物成分がミクロ的に
均質でありながらかつ共有結合したものが得られ、有機
重合体成分と金属酸化物成分の界面強度が上昇すること
によってクラックや表層面だけの剥離等の変形が生じ難
い材料となる。また、表面層部分には光触媒作用を示す
材料を備え、より一層高機能な材料となる。The organic-inorganic multilayer material produced by such a method has a microscopically homogeneous and covalent bond between an organic polymer component and a metal oxide component. When the interface strength of the component increases, the material hardly undergoes deformation such as cracks or peeling of only the surface layer. In addition, a material having a photocatalytic action is provided in the surface layer portion, and the material has a much higher function.
【００５０】本発明の有機−無機多層材料では無機材料
が有する耐熱性、耐候性、表面硬度、剛性、耐水性、耐
薬品性、耐汚染性、機械的強度、難燃性等の特性が有機
重合体に良好に付与されている。逆に言えば、有機重合
体が有する耐衝撃性、柔軟性、加工性及び軽量性等の特
性が無機材料に良好に付与されている。In the organic-inorganic multilayer material of the present invention, the properties of the inorganic material such as heat resistance, weather resistance, surface hardness, rigidity, water resistance, chemical resistance, stain resistance, mechanical strength, flame retardancy and the like are organic. It is well applied to polymers. Conversely, properties such as impact resistance, flexibility, processability, and light weight of the organic polymer are favorably imparted to the inorganic material.
【００５１】しかも光触媒作用を示す材料を金属酸化物
を用いることによって、有機材料と極めて接触し難い形
で表面層部分に含有することより、基材を劣化させずに
光触媒特性を最大限活用することができる。In addition, by using a metal oxide as a material exhibiting a photocatalytic action, the photocatalytic property is maximized without deteriorating the base material by containing the material in the surface layer in a form that is extremely difficult to contact the organic material. be able to.
【００５２】また、表面層に含まれる金属酸化物と共有
結合することが可能であり、相互作用によって基材との
接着性も極めて良好な有機重合体を表面層と基材との間
に用いることによって、クラックや表層面だけの剥離等
の変形が生じ難い材料とすることができる。An organic polymer capable of covalently bonding with the metal oxide contained in the surface layer and having extremely good adhesion to the substrate by interaction is used between the surface layer and the substrate. This makes it possible to use a material that is unlikely to cause deformation such as cracks or peeling of only the surface layer.
【００５３】[0053]
【発明の効果】本発明で提供される有機−無機多層材料
は、表面層として光触媒作用を示す材料を備えながら、
それを担持する基材の劣化が効果的に防止されている。
従って、担体として有機材料を用いた場合でも有機−無
機多層材料の耐用寿命が延長される。つまり、様々な臭
い、汚れの除去や除菌、防汚を目的とした高性能及び高
機能プラスチック材料、プラスチック成形品もしくはフ
ィルム、構造材料、光学材料、表面改質剤、ハードコー
ト剤、電気もしくは電子材料、医療材料等に用いるのに
適した有機−無機多層材料が提供される。The organic-inorganic multilayer material provided by the present invention has a photocatalytic material as a surface layer.
Deterioration of the base material carrying it is effectively prevented.
Therefore, even when an organic material is used as the carrier, the useful life of the organic-inorganic multilayer material is extended. In other words, high-performance and high-performance plastic materials, plastic molded products or films, structural materials, optical materials, surface modifiers, hard coat agents, electric or An organic-inorganic multilayer material suitable for use in electronic materials, medical materials and the like is provided.
【００５４】[0054]
【実施例】以下の実施例により本発明を更に詳細に説明
するが、本発明はこれらに限定されない。The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
【００５５】合成例１ 数平均分子量３９００、及び水酸基当量１．８のポリカ
ーボネートジオール７０．０ｇをクロロホルム５００ｍ
Ｌに溶解させ、その後この溶液に３−イソシアネートプ
ロピルトリエトキシシラン１３．３ｇを添加し、還流下
で１０時間加熱した後、室温に冷却した。この反応液を
メタノール７Ｌ中に滴下し、生成物を析出させた。析出
物をろ別し、メタノールで洗浄した後、減圧乾燥した
（収率９７％）。 Synthesis Example 1 70.0 g of a polycarbonate diol having a number average molecular weight of 3,900 and a hydroxyl equivalent of 1.8 was added to chloroform 500 m
Then, 13.3 g of 3-isocyanatopropyltriethoxysilane was added to this solution, heated under reflux for 10 hours, and then cooled to room temperature. This reaction solution was dropped into 7 L of methanol to precipitate a product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield 97%).
【００５６】1Ｈ−ＮＭＲ測定により、得られた生成物
は両末端にアルコキシシリル基が導入された両末端トリ
エトキシシリル化ポリカーボネート（ＰＣＳ）であるこ
とを確認した。この生成物のアルコキシシリル基当量は
１．８であった。またＧＰＣ分析の結果、この生成物の
数平均分子量は４４００であった。By 1 H-NMR measurement, it was confirmed that the obtained product was a triethoxysilylated polycarbonate (PCS) having both ends into which an alkoxysilyl group was introduced. The alkoxysilyl group equivalent of this product was 1.8. As a result of GPC analysis, the number-average molecular weight of this product was 4,400.
【００５７】合成例２ 数平均分子量５２００、及び水酸基当量１．７のポリサ
ルホンジオール２６．０ｇをクロロホルム３００ｍＬに
溶解し、その後この溶液に３−イソシアネートプロピル
トリエトキシシラン３．５ｇを添加し、還流下で１１時
間加熱した後、室温に冷却した。この反応液をメタノー
ル３Ｌ中に滴下し、生成物を析出させた。析出物をろ別
し、メタノールで洗浄した後、減圧乾燥した（収率９６
％）。 Synthesis Example 2 26.0 g of polysulfonediol having a number average molecular weight of 5200 and a hydroxyl equivalent of 1.7 was dissolved in 300 mL of chloroform, and then 3.5 g of 3-isocyanatopropyltriethoxysilane was added to this solution, and the mixture was refluxed. And then cooled to room temperature. This reaction solution was dropped into 3 L of methanol to precipitate a product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (yield: 96).
%).
【００５８】1Ｈ−ＮＭＲ測定より、得られた生成物は
両末端にアルコキシシリル基が導入された両末端トリエ
トキシシリル化ポリサルホン（ＰＳＳ）であることを確
認した。この生成物のアルコキシシリル基当量は１．７
であった。またＧＰＣ分析の結果、この生成物の数平均
分子量は６０００であった。From 1 H-NMR measurement, it was confirmed that the obtained product was a triethoxysilylated polysulfone (PSS) having alkoxysilyl groups introduced at both ends. The alkoxysilyl group equivalent of this product is 1.7.
Met. As a result of GPC analysis, the number-average molecular weight of this product was 6,000.
【００５９】合成例３ 数平均分子量６１００、及び水酸基当量１．６のポリア
リーレートジオール３０．５ｇをクロロホルム３００ｍ
Ｌに溶解し、その後この溶液に３−イソシアネートプロ
ピルトリエトキシシラン３．２ｇを添加し、還流下で１
５時間加熱した後、室温に冷却した。この反応液をメタ
ノール３Ｌ中に滴下し、生成物を析出させた。析出物を
ろ別し、メタノールで洗浄した後、減圧乾燥した（収率
９６％）。 Synthesis Example 3 30.5 g of a polyarylate diol having a number average molecular weight of 6,100 and a hydroxyl equivalent of 1.6 was added to 300 ml of chloroform.
Then, 3.2 g of 3-isocyanatopropyltriethoxysilane was added to the solution, and the solution was refluxed under reflux for 1 hour.
After heating for 5 hours, it was cooled to room temperature. This reaction solution was dropped into 3 L of methanol to precipitate a product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure (96% yield).
【００６０】1Ｈ−ＮＭＲ測定より得られた生成物は両
末端にアルコキシシリル基が導入された両末端トリエト
キシシリル化ポリアリーレート（ＰＡＳ）であることを
確認した。この生成物のアルコキシシリル基当量は１．
６であった。またＧＰＣ分析の結果、この生成物の数平
均分子量は６７００であった。From the 1 H-NMR measurement, it was confirmed that the obtained product was a triethoxysilylated polyarylate (PAS) having alkoxysilyl groups introduced at both ends. The alkoxysilyl group equivalent of this product is 1.
It was 6. As a result of GPC analysis, the number average molecular weight of this product was 6,700.
【００６１】実施例１ 合成例１で作製した数平均分子量４４００のＰＣＳ５．
０ｇをテトラヒドロフラン（ＴＨＦ）５０ｍｌに溶解
し、１Ｎ−塩酸水０．１５ｇを用いて室温で加水分解を
行った後、スピンコータを用いてポリカーボネート基板
にコーティングした。この湿潤ゲルの上に、テトラエト
キシシラン（ＴＥＯＳ）５．０ｇをＴＨＦ２５ｍｌに溶
解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分解を
行なって得た溶液をスピンコータを用いてコーティング
した。更にこの湿潤ゲルの上に、平均粒子系５μｍのア
ナターゼ型酸化チタン５．０ｇをＴＨＦ２５ｍｌによく
分散させた分散液をスピンコータを用いてコーティング
した。その後、室温下で１日放置した後、１００℃で１
０時間加熱した。 Example 1 PCS5 having a number average molecular weight of 4,400 produced in Synthesis Example 1
0 g was dissolved in 50 ml of tetrahydrofuran (THF), hydrolyzed at room temperature using 0.15 g of 1N hydrochloric acid, and then coated on a polycarbonate substrate using a spin coater. A solution obtained by dissolving 5.0 g of tetraethoxysilane (TEOS) in 25 ml of THF and hydrolyzing it at room temperature with 2.0 g of 1N aqueous hydrochloric acid was coated on the wet gel using a spin coater. Further, a dispersion liquid in which 5.0 g of anatase-type titanium oxide having an average particle size of 5 μm was well dispersed in 25 ml of THF was coated on the wet gel using a spin coater. Then, after leaving at room temperature for one day,
Heated for 0 hours.
【００６２】かかる操作によって、図１に示すような、
ポリカーボネート基材（１０１）の上に第１中間層とし
て架橋ＰＣＳ（１０２）を有し、第２中間層として架橋
シリカ（１０３）を有し、光触媒作用層として酸化チタ
ン粒子（１０４）を有する有機−無機多層材料（１０
０）を得た。By such an operation, as shown in FIG.
Organic having a crosslinked PCS (102) as a first intermediate layer, a crosslinked silica (103) as a second intermediate layer, and titanium oxide particles (104) as a photocatalytic layer on a polycarbonate substrate (101). -Inorganic multilayer materials (10
0) was obtained.
【００６３】実施例２ 合成例１で作製した数平均分子量４４００のＰＣＳ５．
０ｇをＴＨＦ５０ｍｌに溶解し、１Ｎ−塩酸水０．１５
ｇを用いて室温で加水分解を行った後、スピンコータを
用いてポリカーボネート基板にコーティングした。この
湿潤ゲルの上に、ＴＥＯＳ５．０ｇをＴＨＦ２５ｍｌに
溶解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分解
を行って得た溶液をスピンコータを用いてコーティング
した。更にこの湿潤ゲルの上に、テトラブトキシチタン
５．０ｇをＴＨＦ２５ｍｌに溶解し、１Ｎ−塩酸水１．
０ｇを用いて室温で加水分解を行って得た溶液をスピン
コータを用いてコーティングした。その後、室温下で１
日放置し、１００℃で１０時間加熱した。 Example 2 PCS having a number average molecular weight of 4,400 prepared in Synthesis Example 1
0 g was dissolved in 50 ml of THF, and 0.1N aqueous hydrochloric acid 0.15 was added.
g was hydrolyzed at room temperature, and then coated on a polycarbonate substrate using a spin coater. A solution obtained by dissolving 5.0 g of TEOS in 25 ml of THF and performing hydrolysis at room temperature using 2.0 g of 1N hydrochloric acid solution was coated on the wet gel by using a spin coater. Further, 5.0 g of tetrabutoxytitanium was dissolved in 25 ml of THF on the wet gel, and 1N-hydrochloric acid solution was added.
A solution obtained by performing hydrolysis at room temperature using 0 g was coated using a spin coater. Then, at room temperature,
It was left for a day and heated at 100 ° C. for 10 hours.
【００６４】かかる操作によって、ポリカーボネート基
材の上に第１中間層として架橋ＰＣＳを有し、第２中間
層として架橋シリカを有し、光触媒作用層として架橋酸
化チタンを有する有機−無機多層材料を得た。By this operation, an organic-inorganic multilayer material having a crosslinked PCS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked titanium oxide as a photocatalytic layer on a polycarbonate substrate. Obtained.
【００６５】実施例３ 合成例１で作製した数平均分子量４４００のＰＣＳ２．
５ｇとＴＥＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＥＯＳ２．５ｇ
と平均粒子系５μｍのアナターゼ型酸化チタン２．５ｇ
をＴＨＦ２５ｍｌ中で１Ｎ−塩酸水１．０ｇを用いて処
理した分散液をスピンコータを用いてコーティングし
た。その後、室温下で１日放置した後、１００℃で１０
時間加熱した。 Example 3 PCS having a number average molecular weight of 4,400 prepared in Synthesis Example 1
5 g and 2.5 g of TEOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. 2.5 g of TEOS on this wet gel
And 2.5 g of anatase type titanium oxide having an average particle size of 5 μm
Was treated with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF and coated with a spin coater. Then, after standing at room temperature for one day,
Heated for hours.
【００６６】かかる操作によって、図２に示すような、
ポリカーボネート基材（２０１）の上に中間層として架
橋シリカ／ＰＣＳ（２０２）を有し、光触媒作用層とし
て架橋シリカ／酸化チタン（２０３）を有する有機−無
機多層材料（２００）を得た。By such an operation, as shown in FIG.
An organic-inorganic multilayer material (200) having crosslinked silica / PCS (202) as an intermediate layer on a polycarbonate substrate (201) and crosslinked silica / titanium oxide (203) as a photocatalytic layer was obtained.
【００６７】実施例４ 合成例１で作製した数平均分子量４４００のＰＣＳ２．
５ｇとＴＥＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＥＯＳ２．５ｇ
と酸化銅（Ｉ）２．５ｇをＴＨＦ２５ｍｌ中で１Ｎ−塩
酸水１．０ｇを用いて処理した分散液をスピンコータを
用いてコーティングした。その後、室温下で１日放置し
た後、１００℃で１０時間加熱した。 Example 4 PCS having a number average molecular weight of 4,400 prepared in Synthesis Example 1
5 g and 2.5 g of TEOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. 2.5 g of TEOS on this wet gel
And a dispersion obtained by treating 2.5 g of copper oxide (I) with 1.0 g of 1N aqueous hydrochloric acid in 25 ml of THF was coated using a spin coater. Then, after leaving at room temperature for 1 day, it heated at 100 degreeC for 10 hours.
【００６８】かかる操作によって、ポリカーボネート基
材の上に中間層として架橋シリカ／ＰＣＳを有し、光触
媒作用層として架橋シリカ／酸化銅（Ｉ）を有する有機
−無機多層材料を得た。By this operation, an organic-inorganic multilayer material having crosslinked silica / PCS as an intermediate layer on a polycarbonate substrate and crosslinked silica / copper (I) as a photocatalytic layer was obtained.
【００６９】実施例５ 合成例２で作製した数平均分子量６０００のＰＳＳ５．
０ｇをＴＨＦ５０ｍｌに溶解し、１Ｎ−塩酸水０．１０
ｇを用いて室温で加水分解を行った後、スピンコータを
用いてポリカーボネート基板にコーティングした。この
湿潤ゲルの上に、数平均分子量１０００の三菱化学
（株）製テトラメトキシシランオリゴマーＭＫＣシリケ
ートＭＳ−５６（ＴＭＯＳ）５．０ｇをＴＨＦ２５ｍｌ
に溶解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分
解を行って得た溶液をスピンコータを用いてコーティン
グした。更にこの湿潤ゲルの上に、平均粒子系５μｍの
アナターゼ型酸化チタン５．０ｇをＴＨＦ２５ｍｌによ
く分散させた分散液をスピンコータを用いてコーティン
グした。その後、室温下で１日放置した後、１００℃で
１０時間加熱した。 Example 5 A PSS having a number average molecular weight of 6000 and prepared in Synthesis Example 2
0 g was dissolved in 50 ml of THF.
g was hydrolyzed at room temperature, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of tetramethoxysilane oligomer MKC silicate MS-56 (TMOS) having a number average molecular weight of 1000 and manufactured by Mitsubishi Chemical Corporation in 25 ml of THF was added.
And hydrolyzed at room temperature with 2.0 g of 1N hydrochloric acid at room temperature, and coated with a spin coater. Further, a dispersion liquid in which 5.0 g of anatase-type titanium oxide having an average particle size of 5 μm was well dispersed in 25 ml of THF was coated on the wet gel using a spin coater. Then, after leaving at room temperature for 1 day, it heated at 100 degreeC for 10 hours.
【００７０】かかる操作によって、ポリカーボネート基
材の上に第１中間層として架橋ＰＳＳを有し、第２中間
層として架橋シリカを有し、光触媒作用層として酸化チ
タン粒子を有する有機−無機多層材料を得た。By this operation, an organic-inorganic multilayer material having a crosslinked PSS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and titanium oxide particles as a photocatalytic layer on a polycarbonate substrate. Obtained.
【００７１】実施例６ 合成例２で作製した数平均分子量６０００のＰＳＳ５．
０ｇをＴＨＦ５０ｍｌに溶解し、１Ｎ−塩酸水０．１０
ｇを用いて室温で加水分解を行った後、スピンコータを
用いてポリカーボネート基板にコーティングした。この
湿潤ゲルの上に、ＴＭＯＳ５．０ｇをＴＨＦ２５ｍｌに
溶解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分解
を行って得た溶液をスピンコータを用いてコーティング
した。更にこの湿潤ゲルの上に、数平均分子量９７０の
テトラブトキシチタンオリゴマー５．０ｇをＴＨＦ２５
ｍｌに溶解し、１Ｎ−塩酸水０．９０ｇを用いて室温で
加水分解を行った溶液をスピンコータを用いてコーティ
ングした。その後、室温下で１日放置した後、１００℃
で１０時間加熱した。 Example 6 A PSS having a number average molecular weight of 6000 produced in Synthesis Example 2
0 g was dissolved in 50 ml of THF.
g was hydrolyzed at room temperature, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, a solution obtained by dissolving 5.0 g of TMOS in 25 ml of THF and hydrolyzing at room temperature with 2.0 g of 1N hydrochloric acid was coated using a spin coater. Further, 5.0 g of a tetrabutoxytitanium oligomer having a number average molecular weight of 970 was placed on the wet gel in THF 25.
The resulting solution was dissolved in the same solution and hydrolyzed at room temperature using 1N-hydrochloric acid 0.90 g, and the solution was coated using a spin coater. Then, after standing at room temperature for one day,
For 10 hours.
【００７２】かかる操作によって、ポリカーボネート基
材の上に第１中間層として架橋ＰＳＳを有し、第２中間
層として架橋シリカを有し、光触媒作用層として架橋酸
化チタンを有する有機−無機多層材料を得た。By this operation, an organic-inorganic multilayer material having a crosslinked PSS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked titanium oxide as a photocatalytic layer on a polycarbonate substrate. Obtained.
【００７３】実施例７ 合成例２で作製した数平均分子量６０００のＰＳＳ２．
５ｇとＴＭＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＭＯＳ２．５ｇ
と平均粒子系５μｍのアナターゼ型酸化チタン２．５ｇ
をＴＨＦ２５ｍｌ中で１Ｎ−塩酸水１．０ｇを用いて処
理した分散液をスピンコータを用いてコーティングし
た。その後、室温下で１日放置した後、１００℃で１０
時間加熱した。 Example 7 A PSS having a number average molecular weight of 6000 produced in Synthesis Example 2
5 g and 2.5 g of TMOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. On this wet gel, TMOS 2.5g
And 2.5 g of anatase type titanium oxide having an average particle size of 5 μm
Was treated with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF and coated with a spin coater. Then, after standing at room temperature for one day,
Heated for hours.
【００７４】かかる操作によって、ポリカーボネート基
材の上に中間層として架橋シリカ／ＰＳＳを有し、光触
媒作用層として架橋シリカ／酸化チタンを有する有機−
無機多層材料を得た。By such an operation, an organic compound having crosslinked silica / PSS as an intermediate layer and a crosslinked silica / titanium oxide as a photocatalytic layer was formed on a polycarbonate substrate.
An inorganic multilayer material was obtained.
【００７５】実施例８ 合成例２で作製した数平均分子量６０００のＰＳＳ２．
５ｇとＴＭＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＭＯＳ２．５ｇ
と酸化銅（Ｉ）２．５ｇをＴＨＦ２５ｍｌ中で１Ｎ−塩
酸水１．０ｇを用いて処理した分散液をスピンコータを
用いてコーティングした。その後、室温下で１日放置し
た後、１００℃で１０時間加熱した。 Example 8 A PSS having a number average molecular weight of 6000 and prepared in Synthesis Example 2
5 g and 2.5 g of TMOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. On this wet gel, TMOS 2.5g
And a dispersion obtained by treating 2.5 g of copper oxide (I) with 1.0 g of 1N aqueous hydrochloric acid in 25 ml of THF was coated using a spin coater. Then, after leaving at room temperature for 1 day, it heated at 100 degreeC for 10 hours.
【００７６】かかる操作によって、ポリカーボネート基
材の上に中間層として架橋シリカ／ＰＳＳを有し、光触
媒作用層として架橋シリカ／酸化銅（Ｉ）を有する有機
−無機多層材料を得た。By the above operation, an organic-inorganic multilayer material having crosslinked silica / PSS as an intermediate layer and a crosslinked silica / copper (I) as a photocatalytic layer was obtained on a polycarbonate substrate.
【００７７】実施例９ 合成例３で作製した数平均分子量６７００のＰＡＳ５．
０ｇをＴＨＦ５０ｍｌに溶解し、１Ｎ−塩酸水０．１０
ｇを用いて室温で加水分解を行った後、スピンコータを
用いてポリカーボネート基板にコーティングした。この
湿潤ゲルの上に、ＴＭＯＳ５．０ｇをＴＨＦ２５ｍｌに
溶解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分解
を行った溶液をスピンコータを用いてコーティングし
た。更にこの湿潤ゲルの上に、酸化銅（Ｉ）５．０ｇを
ＴＨＦ２５ｍｌによく分散させた分散液をスピンコータ
を用いてコーティングした。その後、室温下で１日放置
した後、１００℃で１０時間加熱した。 Example 9 PAS having a number average molecular weight of 6700 and produced in Synthesis Example 3
0 g was dissolved in 50 ml of THF.
g was hydrolyzed at room temperature, and then coated on a polycarbonate substrate using a spin coater. A solution obtained by dissolving 5.0 g of TMOS in 25 ml of THF and hydrolyzing at room temperature with 2.0 g of 1N hydrochloric acid was coated on the wet gel using a spin coater. Further, a dispersion liquid in which 5.0 g of copper (I) oxide was well dispersed in 25 ml of THF was coated on the wet gel using a spin coater. Then, after leaving at room temperature for 1 day, it heated at 100 degreeC for 10 hours.
【００７８】かかる操作によって、ポリカーボネート基
材の上に第１中間層として架橋ＰＡＳを有し、第２中間
層として架橋シリカを有し、光触媒作用層として酸化銅
（Ｉ）粒子を有する有機−無機多層材料を得た。According to the above operation, an organic-inorganic material having a crosslinked PAS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and copper (I) oxide particles as a photocatalytic layer on a polycarbonate substrate. A multilayer material was obtained.
【００７９】実施例１０ 合成例３で作製した数平均分子量６７００のＰＡＳ５．
０ｇをＴＨＦ５０ｍｌに溶解し、１Ｎ−塩酸水０．１０
ｇを用いて室温で加水分解を行った後、スピンコータを
用いてポリカーボネート基板にコーティングした。この
湿潤ゲルの上に、ＴＭＯＳ５．０ｇをＴＨＦ２５ｍｌに
溶解し、１Ｎ−塩酸水２．０ｇを用いて室温で加水分解
を行った溶液をスピンコータを用いてコーティングし
た。更にこの湿潤ゲルの上に、テトライソプロポキシチ
タン５．０ｇをＴＨＦ２５ｍｌに溶解し、１Ｎ−塩酸水
１．２ｇを用いて室温で加水分解を行った溶液をスピン
コータを用いてコーティングした。その後、室温下で１
日放置した後、１００℃で１０時間加熱した。 Example 10 PAS having a number average molecular weight of 6,700 prepared in Synthesis Example 3
0 g was dissolved in 50 ml of THF.
g was hydrolyzed at room temperature, and then coated on a polycarbonate substrate using a spin coater. A solution obtained by dissolving 5.0 g of TMOS in 25 ml of THF and hydrolyzing at room temperature with 2.0 g of 1N hydrochloric acid was coated on the wet gel using a spin coater. Further, on this wet gel, a solution obtained by dissolving 5.0 g of tetraisopropoxytitanium in 25 ml of THF and hydrolyzing at room temperature with 1.2 g of 1N hydrochloric acid water was coated using a spin coater. Then, at room temperature,
After standing for a day, it was heated at 100 ° C. for 10 hours.
【００８０】かかる操作によって、ポリカーボネート基
材の上に第１中間層として架橋ＰＡＳを有し、第２中間
層として架橋シリカを有し、光触媒作用層として架橋酸
化チタンを有する有機−無機多層材料を得た。By this operation, an organic-inorganic multilayer material having a crosslinked PAS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked titanium oxide as a photocatalytic layer on a polycarbonate substrate. Obtained.
【００８１】実施例１１ 合成例３で作製した数平均分子量６７００のＰＡＳ２．
５ｇとＴＭＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＭＯＳ２．５ｇ
と平均粒子系５μｍのアナターゼ型酸化チタン２．５ｇ
をＴＨＦ２５ｍｌ中で１Ｎ−塩酸水１．０ｇを用いて処
理した分散液をスピンコータを用いてコーティングし
た。その後、室温下で１日放置した後、１００℃で１０
時間加熱した。 Example 11 PAS having a number-average molecular weight of 6,700 prepared in Synthesis Example 3
5 g and 2.5 g of TMOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. On this wet gel, TMOS 2.5g
And 2.5 g of anatase type titanium oxide having an average particle size of 5 μm
Was treated with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF and coated with a spin coater. Then, after standing at room temperature for one day,
Heated for hours.
【００８２】かかる操作によって、ポリカーボネート基
材の上に中間層として架橋シリカ／ＰＡＳを有し、光触
媒作用層として架橋シリカ／酸化チタンを有する有機−
無機多層材料を得た。By this operation, an organic compound having crosslinked silica / PAS as an intermediate layer and a crosslinked silica / titanium oxide as a photocatalytic layer was formed on a polycarbonate substrate.
An inorganic multilayer material was obtained.
【００８３】実施例１２ 合成例３で作製した数平均分子量６７００のＰＡＳ２．
５ｇとＴＭＯＳ２．５ｇをＴＨＦ４０ｍｌに溶解し、１
Ｎ−塩酸水１．０ｇを用いて室温で加水分解を行った
後、スピンコータを用いてポリカーボネート基板にコー
ティングした。この湿潤ゲルの上に、ＴＭＯＳ２．５ｇ
と酸化銅（Ｉ）２．５ｇをＴＨＦ２５ｍｌ中で１Ｎ−塩
酸水１．０ｇを用いて処理した分散液をスピンコータを
用いてコーティングした。その後、室温下で１日放置し
た後、１００℃で１０時間加熱した。 Example 12 PAS having a number average molecular weight of 6,700 and produced in Synthesis Example 3
5 g and 2.5 g of TMOS are dissolved in 40 ml of THF.
After hydrolyzing at room temperature using 1.0 g of N-hydrochloric acid water, it was coated on a polycarbonate substrate using a spin coater. On this wet gel, TMOS 2.5g
And a dispersion obtained by treating 2.5 g of copper oxide (I) with 1.0 g of 1N aqueous hydrochloric acid in 25 ml of THF was coated using a spin coater. Then, after leaving at room temperature for 1 day, it heated at 100 degreeC for 10 hours.
【００８４】かかる操作によって、ポリカーボネート基
材の上に中間層として架橋シリカ／ＰＡＳを有し、光触
媒作用層として架橋シリカ／酸化銅（Ｉ）を有する有機
−無機多層材料を得た。By the above operation, an organic-inorganic multilayer material having crosslinked silica / PAS as an intermediate layer on a polycarbonate substrate and crosslinked silica / copper (I) as a photocatalytic layer was obtained.
【００８５】比較例１ ＴＥＯＳ２．５ｇと平均粒子系５μｍのアナターゼ型酸
化チタン２．５ｇをＴＨＦ２５ｍｌ中で１Ｎ−塩酸水
１．０ｇを用いて処理した分散液をスピンコータを用い
てポリカーボネート基板にコーティングした。COMPARATIVE EXAMPLE 1 A dispersion obtained by treating 2.5 g of TEOS and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm in 25 ml of THF using 1.0 g of 1N hydrochloric acid was coated on a polycarbonate substrate using a spin coater. .
【００８６】比較例２ ＴＭＯＳ２．５ｇと酸化銅（Ｉ）２．５ｇをＴＨＦ２５
ｍｌ中で１Ｎ−塩酸水１．０ｇを用いて処理した分散液
をスピンコータを用いてポリカーボネート基板にコーテ
ィングした。 Comparative Example 2 2.5 g of TMOS and 2.5 g of copper (I) oxide were added to THF 25
The dispersion liquid treated with 1.0 g of 1N-hydrochloric acid solution in 1 ml was coated on a polycarbonate substrate using a spin coater.
【００８７】比較例３ テトラブトキシチタン５．０ｇをＴＨＦ２５ｍｌに溶解
し、１Ｎ−塩酸水１．０ｇを用いて室温で加水分解した
溶液をスピンコータを用いてポリカーボネート基板にコ
ーティングした。 Comparative Example 3 A solution of 5.0 g of tetrabutoxytitanium dissolved in 25 ml of THF and hydrolyzed with 1.0 g of 1N aqueous hydrochloric acid at room temperature was coated on a polycarbonate substrate using a spin coater.
【００８８】比較例４ 数平均分子量４４００のＰＣＳ２．５ｇと平均粒子系５
μｍのアナターゼ型酸化チタン２．５ｇをＴＨＦ４０ｍ
ｌ中で１Ｎ−塩酸水０．１０ｇを用いて処理した分散液
をスピンコータを用いてポリカーボネート基板にコーテ
ィングした。 Comparative Example 4 2.5 g of PCS having a number average molecular weight of 4,400 and an average particle system 5
2.5 g of anatase type titanium oxide having a thickness of 40 m
The dispersion treated with 0.10 g of 1N aqueous hydrochloric acid in 1 l was coated on a polycarbonate substrate using a spin coater.
【００８９】比較例５ 数平均分子量４４００のＰＣＳ２．５ｇと酸化銅（Ｉ）
２．５ｇをＴＨＦ４０ｍｌ中で１Ｎ−塩酸水０．１０ｇ
を用いて処理した分散液をスピンコータを用いてポリカ
ーボネート基板にコーティングした。 Comparative Example 5 2.5 g of PCS having a number average molecular weight of 4,400 and copper (I) oxide
2.5 g of 0.1 N aqueous hydrochloric acid in 40 ml of THF
Was coated on a polycarbonate substrate using a spin coater.
【００９０】碁盤目及び剥離試験 実施例１〜１２及び比較例１〜３で得られた有機−無機
多層材料を用いて、碁盤目及び剥離試験を行った。試験
方法としてはＪＩＳ Ｋ ５４００を参考として用い
た。 Cross-cut and peel test The organic and inorganic multilayer materials obtained in Examples 1 to 12 and Comparative Examples 1 to 3 were subjected to a cross- cut and peel test . JIS K 5400 was used as a reference as a test method.
【００９１】まず試験片（３０×３０ｍｍ）にカッター
ナイフを用いて直交する縦横１１本ずつの平行線を１ｍ
ｍ間隔で引き、碁盤目状に１００個のます目を作製し
た。次に、これらのます目の上に粘着テープ（ニチバン
社製「セロハンテープ」）を貼り付け密着させた後、粘
着テープを瞬時に引き剥がし、試験片の金属酸化物層の
剥離状態を観察した。First, 11 perpendicular and horizontal parallel lines each having a length of 1 m were cut on a test piece (30 × 30 mm) using a cutter knife.
By drawing at intervals of m, 100 squares were formed in a grid pattern. Next, an adhesive tape (Nichiban's “Cellophane tape”) was applied to and adhered to these squares, and then the adhesive tape was instantly peeled off, and the peeling state of the metal oxide layer of the test piece was observed. .
【００９２】その結果、比較例１〜３の試験片では、ま
す目の大半が剥離した。これに対して、実施例１〜１２
の試験片では、金属酸化物層の剥離は全く観察されなか
った。As a result, in the test pieces of Comparative Examples 1 to 3, most of the squares peeled off. In contrast, Examples 1 to 12
No peeling of the metal oxide layer was observed in the test piece of No.
【００９３】これらの結果より、本発明の有機−無機多
層材料が優れた界面強度を有していることが確認され
た。From these results, it was confirmed that the organic-inorganic multilayer material of the present invention had excellent interface strength.
【００９４】[0094]
【表１】 [Table 1]
【００９５】ウェザーメータを用いた促進耐候性試験 実施例１〜１２及び比較例４と５で得られた有機−無機
多層材料の促進耐候性試験をウェザーメータを用いて行
った。試験に際しては、試験片（１５０×７０ｍｍ）を
ウェザーメータで処理した後、基板の状態を目視観察し
た。 Accelerated Weathering Test Using a Weather Meter An accelerated weathering test of the organic-inorganic multilayer materials obtained in Examples 1 to 12 and Comparative Examples 4 and 5 was carried out using a weather meter. In the test, a test piece (150 × 70 mm) was treated with a weather meter, and the state of the substrate was visually observed.
【００９６】試験条件はＪＩＳ Ｄ ０２０５に準じて
設定し、平均放電電力は３９０Ｗ／ｍ2とした。また、
清水の噴射圧力１．０ｋｇｆ／ｃｍ2、水量２０００ｍ
ｌ／分、清水の噴射時間６０分中１２分とし、試験時間
は計２００時間とした。装置はスガイ試験機（株）製Ｗ
ＥＬ−７５ＸＳ−ＨＣ−ＢＥＣ型キセノンサンシャイン
ロングライフウェザーメータを用いた。The test conditions were set according to JIS D 0205, and the average discharge power was 390 W / m 2 . Also,
Injection pressure of fresh water 1.0kgf / cm 2 , water volume 2000m
1 / min, 12 minutes out of 60 minutes of injection time of fresh water, and the test time was 200 hours in total. The device is manufactured by Sugai Testing Machine Co., Ltd.
An EL-75XS-HC-BEC type xenon sunshine long life weather meter was used.
【００９７】その結果、比較例４と５の試験片について
は基板に変色が観られたものの、実施例１〜１２の試験
片の基板は試験前とほとんど変わりなかった。比較例４
と５の試験片では酸化チタン及び酸化銅（Ｉ）とＰＣＳ
及びポリカーボネート基板が接していたために基板の有
機材料が酸化され、変色したものと考えられる。これに
対して実施例１〜１２の試験片では、酸化チタン及び酸
化銅（Ｉ）とポリカーボネート基板とがシリカ相によっ
て隔てられているために有機材料が酸化を受けなかった
と考えられる。As a result, the test pieces of Comparative Examples 4 and 5 showed discoloration on the substrate, but the substrates of the test pieces of Examples 1 to 12 were almost the same as before the test. Comparative Example 4
And 5 specimens were titanium oxide and copper (I) oxide and PCS
It is considered that the organic material of the substrate was oxidized and discolored because the substrate was in contact with the polycarbonate substrate. On the other hand, in the test pieces of Examples 1 to 12, it is considered that the organic material was not oxidized because the titanium oxide and the copper (I) oxide and the polycarbonate substrate were separated by the silica phase.
【００９８】これらの結果より、本発明の有機−無機多
層材料では、基材や接着剤、バインダー等の有機材料が
光触媒性を有する材料から酸化を受けて劣化するという
従来からの問題点が克服されていると言える。From these results, the organic-inorganic multilayer material of the present invention overcomes the conventional problem that organic materials such as base materials, adhesives and binders are oxidized and deteriorated by photocatalytic materials. It can be said that.
【００９９】[0099]
【表２】 [Table 2]
【０１００】タバコ消臭性試験 実施例１〜１２で得られた有機−無機多層材料及びポリ
カーボネート基板を用いてタバコ臭の消臭性試験を行っ
た。方法としては９００ｍｌ容ガラス製マヨネーズビン
を入口を下にして、入口の真下に発煙している紙巻きタ
バコを５秒間置いた後、素早く試験片（３０×３０ｍ
ｍ）を投入し、密栓した。その後、屋外の太陽光の下で
１時間放置した後開封し、内部の臭いを評価した。結果
を表３に示した。 Tobacco deodorant test Using the organic-inorganic multilayer material obtained in Examples 1 to 12 and a polycarbonate substrate, a deodorant test for tobacco odor was performed. The method is as follows. A 900 ml glass mayonnaise bottle is placed with the inlet facing down, and a smoking cigarette is placed immediately below the inlet for 5 seconds, and then the test piece (30 × 30 m
m) was charged and sealed. Then, after leaving for 1 hour under the sunlight of the outdoors, it was opened and the inside odor was evaluated. The results are shown in Table 3.
【０１０１】その結果、未処理のポリカーボネート基板
ではタバコの残臭が確認されたものの、実施例１〜１２
の有機−無機多層材料では残臭は感じられなかった。As a result, although a residual odor of tobacco was confirmed on the untreated polycarbonate substrate, Examples 1-12
No residual odor was felt with the organic-inorganic multilayer material.
【０１０２】これらの結果より本発明の有機−無機多層
材料は、タバコ臭の消臭に対して有効なことが確認され
た。From these results, it was confirmed that the organic-inorganic multilayer material of the present invention was effective for deodorizing tobacco odor.
【０１０３】[0103]
【表３】 [Table 3]
【０１０４】アンモニア消臭性試験 実施例１〜１２で得られた有機−無機多層材料及びポリ
カーボネート基板を用いてアンモニアの消臭性試験を行
った。方法としては、試験片（３０×３０ｍｍ）とガス
検知管をセットしたガラス製デシケータにアンモニアガ
スを導入し、屋内の蛍光灯下において経時でガス濃度を
測定した。結果を表４に示した。 Ammonia deodorization test Ammonia deodorization test was carried out using the organic-inorganic multilayer material obtained in Examples 1 to 12 and a polycarbonate substrate. As a method, ammonia gas was introduced into a glass desiccator in which a test piece (30 × 30 mm) and a gas detection tube were set, and the gas concentration was measured over time under an indoor fluorescent lamp. The results are shown in Table 4.
【０１０５】その結果、本発明の有機−無機多層材料は
良好なアンモニア消臭性を示した。As a result, the organic-inorganic multilayer material of the present invention exhibited good ammonia deodorizing properties.
【０１０６】[0106]
【表４】 [Table 4]
【０１０７】メチルメルカプタン消臭性試験 実施例１〜１２で得られた有機−無機多層材料及びポリ
カーボネート基板を用いてメチルメルカプタンの消臭性
試験を行った。方法としては、試験片（３０×３０ｍ
ｍ）とガス検知管をセットしたガラス製デシケータにメ
チルメルカプタンガスを導入し、屋内の蛍光灯下におい
て経時でガス濃度を測定した。結果を表５に示した。 Methyl Mercaptan Deodorizing Test Using the organic-inorganic multilayer materials obtained in Examples 1 to 12 and a polycarbonate substrate, a methyl mercaptan deodorizing test was conducted. As a method, a test piece (30 × 30 m
m) and a gas detector tube, a methyl mercaptan gas was introduced into a glass desiccator, and the gas concentration was measured over time under an indoor fluorescent lamp. Table 5 shows the results.
【０１０８】その結果、本発明の有機−無機多層材料は
良好なメチルメルカプタン消臭性を示した。As a result, the organic-inorganic multilayer material of the present invention showed good methyl mercaptan deodorizing properties.
【０１０９】[0109]
【表５】 [Table 5]
【図１】 本発明の有機−無機多層材料の構造の一例を
示す模式断面図である。FIG. 1 is a schematic sectional view showing an example of the structure of an organic-inorganic multilayer material of the present invention.
【図２】 本発明の有機−無機多層材料の構造の一例を
示す模式断面図である。 １００、２００…有機−無機多層材料、 １０１…基材、 １０２…第１中間層、 １０３…第２中間層、 １０４…光触媒作用層、 ２０１…基材、 ２０２…中間層、 ２０３…光触媒作用層。FIG. 2 is a schematic sectional view showing an example of the structure of the organic-inorganic multilayer material of the present invention. 100, 200: Organic-inorganic multilayer material, 101: Base material, 102: First intermediate layer, 103: Second intermediate layer, 104: Photocatalytic layer, 201: Base material, 202: Intermediate layer, 203: Photocatalytic layer .
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｄ 183/00 Ｃ０９Ｄ 183/00 185/00 185/00 (72)発明者 須方 一明 大阪府寝屋川市讃良東町８番１号 オリヱ ント化学工業株式会社研究所内 (72)発明者 上利 泰幸 大阪府大阪市中央区東平１丁目１番53の 1001号 (72)発明者 島田 雅之 大阪府堺市高倉台３丁11番６号 Ｆターム(参考） 4F100 AA21 AA21C AA40C AH06 AH08B AH08D AK17C AK31B AK43B AK45 AK45B AK55B AK79B AK79D AK80B AT00A BA04 BA07 BA10A BA10C DE01 EA011 EH46 EH462 EH463 EJ42 GB07 JB13B JB16B JL08 JL08C JL09 JM012 JM013 4G069 AA01 AA03 AA08 BA02A BA02B BA04A BA04B BA05A BA05B BA22A BA22B BA48A BB04A BB04B BC13A BC16A BC17A BC21A BC22A BC23A BC31A BC31B BC43A BC50A BC51A BC56A BC60A BC66A BD03A BD05A BE06A BE06B CA01 CA10 CA11 CA17 DA05 EC28 EE06 FA06 4J038 DD061 DE001 DK011 EA011 HA216 JA23 KA04 KA20──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09D 183/00 C09D 183/00 185/00 185/00 (72) Inventor Kazuaki Sugata Neyagawa, Osaka No. 8-1, Sanrahigashi-cho, Orient Chemical Industry Co., Ltd. (72) Inventor Yasuyuki Yasuyuki 1-3-11-13-1 Higashidaira, Chuo-ku, Osaka-shi, Osaka (72) Inventor Masayuki Shimada Takakura, Sakai-shi, Osaka Stand 3-11 No. 6 F term (reference) 4F100 AA21 AA21C AA40C AH06 AH08B AH08D AK17C AK31B AK43B AK45 AK45B AK55B AK79B AK79D AK80B AT00A BA04 BA07 BA10A BA10C DE01 EA01EHB J082 462 AA08 BA02A BA02B BA04A BA04B BA05A BA05B BA22A BA22B BA48A BB04A BB04B BC13A BC16A BC17A BC21A BC22A BC23A BC31A BC31B BC43A BC50A BC51A BC56A BC60A BC66A BD03A BD05 A BE06A BE06B CA01 CA10 CA11 CA17 DA05 EC28 EE06 FA06 4J038 DD061 DE001 DK011 EA011 HA216 JA23 KA04 KA20
Claims (21)
間層と光触媒作用層とを有する有機−無機多層材料にお
いて、 該中間層が、官能基として金属アルコキシド基を有する
有機重合体、又は金属アルコキシド化合物と反応可能な
官能基を有する有機重合体と金属アルコキシド化合物と
の混合物を、加水分解及び重縮合することにより架橋し
て得られる有機−無機ハイブリッド材料で成り、 該光触媒作用層が、光触媒作用を示す金属酸化物を含む
材料で成る、有機−無機多層材料。1. An organic-inorganic multilayer material having a substrate and an intermediate layer and a photocatalytic layer formed sequentially on the surface of the substrate, wherein the intermediate layer has a metal alkoxide group as a functional group. Or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound, and an organic-inorganic hybrid material obtained by crosslinking by hydrolysis and polycondensation. Is an organic-inorganic multilayer material comprising a material containing a metal oxide exhibiting photocatalysis.
１中間層と第２中間層と光触媒作用層とを有する有機−
無機多層材料において、 該第１中間層が、官能基として金属アルコキシド基を有
する有機重合体、又は金属アルコキシド化合物と反応可
能な官能基を有する有機重合体と金属アルコキシド化合
物との混合物を、加水分解及び重縮合することにより架
橋して得られる有機−無機ハイブリッド材料で成り、 該第２中間層が金属アルコキシド化合物を加水分解及び
重縮合することにより架橋して得られる無機材料で成
り、 該光触媒作用層が、光触媒作用を示す金属酸化物を含む
材料で成る、有機−無機多層材料。2. An organic material comprising a substrate, a first intermediate layer, a second intermediate layer, and a photocatalytic layer formed sequentially on the surface of the substrate.
In the inorganic multilayer material, the first intermediate layer hydrolyzes an organic polymer having a metal alkoxide group as a functional group, or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound. And the organic-inorganic hybrid material obtained by crosslinking by polycondensation; and the second intermediate layer is made of an inorganic material obtained by crosslinking by hydrolysis and polycondensation of a metal alkoxide compound; An organic-inorganic multilayer material, wherein the layers are made of a material containing a photocatalytic metal oxide.
である請求項１又は２記載の有機−無機多層材料。3. The organic-inorganic multilayer material according to claim 1, wherein the main skeleton of the organic polymer is a thermosetting resin.
である請求項１又は２記載の有機−無機多層材料。4. The organic-inorganic multilayer material according to claim 1, wherein the main skeleton of the organic polymer is a thermoplastic resin.
ート、ポリアリーレート、又はポリサルホンである請求
項１又は２記載の有機−無機多層材料。5. The organic-inorganic multilayer material according to claim 1, wherein the main skeleton of the organic polymer is polycarbonate, polyarylate, or polysulfone.
な官能基が金属アルコキシド基、水酸基、アミノ基、及
びカルボキシル基からなる群から選択される少なくとも
１種である請求項１又は２記載の有機−無機多層材料。6. The organic-inorganic composition according to claim 1, wherein the functional group capable of reacting with the metal alkoxide compound is at least one selected from the group consisting of a metal alkoxide group, a hydroxyl group, an amino group, and a carboxyl group. Multi-layer material.
な官能基が金属アルコキシド基である請求項１又は２記
載の有機−無機多層材料。7. The organic-inorganic multilayer material according to claim 1, wherein the functional group capable of reacting with the metal alkoxide compound is a metal alkoxide group.
化物とされた場合に光触媒作用を示さないものである請
求項１又は２記載の有機−無機多層材料。8. The organic-inorganic multilayer material according to claim 1, wherein the metal element of the metal alkoxide does not exhibit photocatalysis when converted to an oxide.
ｉ、及びＺｒからなる群から選択される少なくとも１種
である請求項１又は２記載の有機−無機多層材料。9. The method according to claim 9, wherein the metal element of the metal alkoxide is S
3. The organic-inorganic multilayer material according to claim 1, which is at least one selected from the group consisting of i and Zr.
ｉである請求項１又は２記載の有機−無機多層材料。10. The method according to claim 10, wherein the metal element of the metal alkoxide is S
The organic-inorganic multilayer material according to claim 1 or 2, which is i.
有量が１０〜１００重量％である請求項１又は２記載の
有機−無機多層材料。11. The organic-inorganic multilayer material according to claim 1, wherein the content of the photocatalytic metal oxide is 10 to 100% by weight.
酸化チタン及び酸化銅（Ｉ）からなる群から選択される
少なくとも１種である請求項１又は２記載の有機−無機
多層材料。12. The metal oxide exhibiting a photocatalytic action,
3. The organic-inorganic multilayer material according to claim 1, which is at least one member selected from the group consisting of titanium oxide and copper (I) oxide.
金属酸化物の粒子を含む材料で成る請求項１又は２記載
の有機−無機多層材料。13. The organic-inorganic multilayer material according to claim 1, wherein the photocatalytic layer is made of a material containing particles of a metal oxide exhibiting photocatalysis.
場合に光触媒作用を示す金属の金属アルコキシド化合物
又はそれを含む金属アルコキシド混合物を加水分解及び
重縮合させて得られる材料で成る請求項１又は２記載の
有機−無機多層材料。14. The photocatalytic layer is made of a material obtained by hydrolyzing and polycondensing a metal alkoxide compound of a metal having a photocatalytic action when converted to an oxide or a metal alkoxide mixture containing the metal alkoxide compound. Or the organic-inorganic multilayer material according to 2.
は２記載の有機−無機多層材料。15. The organic-inorganic multilayer material according to claim 1, wherein the substrate is an organic material.
用、防汚作用、抗菌作用、及び除菌作用からなる群から
選択される少なくとも１種である請求項１又は２記載の
有機−無機多層材料。16. The organic-inorganic multilayer according to claim 1, wherein the photocatalytic action is at least one selected from the group consisting of a deodorizing action, a decolorizing action, an antifouling action, an antibacterial action, and a disinfecting action. material.
材の表面上に、官能基として金属アルコキシド基を有す
る有機重合体、又は金属アルコキシド化合物と反応可能
な官能基を有する有機重合体と金属アルコキシド化合物
との混合物を含む溶液もしくは湿潤ゲルを塗布して中間
層を形成する工程；及び中間層の表面上に、光触媒作用
を示す金属酸化物を含む材料で成る光触媒作用層を形成
する工程；を包含する、有機−無機多層材料の製造方
法。17. A step of providing a substrate having a surface; an organic polymer having a metal alkoxide group as a functional group or an organic polymer having a functional group capable of reacting with a metal alkoxide compound on the surface of the substrate. A step of applying a solution or a wet gel containing a mixture with a metal alkoxide compound to form an intermediate layer; and a step of forming a photocatalytic layer made of a material containing a photocatalytic metal oxide on the surface of the intermediate layer A method for producing an organic-inorganic multilayer material, comprising:
材の表面上に、官能基として金属アルコキシド基を有す
る有機重合体、又は金属アルコキシド化合物と反応可能
な官能基を有する有機重合体と金属アルコキシド化合物
との混合物を含む溶液もしくは湿潤ゲルを塗布して第１
中間層を形成する工程；第１中間層の表面上に、金属ア
ルコキシド化合物を含む溶液もしくは湿潤ゲルを塗布し
て第２中間層を形成する工程；第２中間層の表面上に、
光触媒作用を示す金属酸化物を含む材料で成る光触媒作
用層を形成する工程；を包含する、有機−無機多層材料
の製造方法。18. A step of providing a substrate having a surface; an organic polymer having a metal alkoxide group as a functional group or an organic polymer having a functional group capable of reacting with a metal alkoxide compound on the surface of the substrate. First, a solution or a wet gel containing a mixture with a metal alkoxide compound is applied.
A step of forming an intermediate layer; a step of applying a solution or a wet gel containing a metal alkoxide compound on the surface of the first intermediate layer to form a second intermediate layer;
Forming a photocatalytic layer made of a material containing a metal oxide exhibiting a photocatalytic action.
す金属酸化物の粒子を含む材料を直接中間層の表面に塗
布して形成される、請求項１７又は１８記載の方法。19. The method according to claim 17, wherein the photocatalytic layer is formed by directly applying a material containing particles of a metal oxide having photocatalysis to the surface of the intermediate layer.
す金属酸化物の粒子を含む材料を揮発性溶媒に分散さ
せ、得られる分散体を中間層の表面に塗布して形成され
る、請求項１７又は１８記載の方法。20. The photocatalytic layer is formed by dispersing a material containing metal oxide particles exhibiting photocatalysis in a volatile solvent, and applying the resulting dispersion to the surface of the intermediate layer. 19. The method according to 17 or 18.
に光触媒作用を示す金属アルコキシド化合物又はその低
縮合物を含む金属アルコキシド混合物の溶液もしくは湿
潤ゲル塗布して形成される、請求項１７又は１８記載の
方法。21. The photocatalytic layer is formed by applying a solution or a wet gel of a metal alkoxide compound having a photocatalytic action or a metal alkoxide mixture containing a low condensate thereof on the surface of the intermediate layer. 19. The method according to 18.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37273298A JP3550035B2 (en) | 1998-12-28 | 1998-12-28 | Organic-inorganic multilayer material and method for producing the same |
| DE1999620642 DE69920642T2 (en) | 1998-12-28 | 1999-12-28 | Organic / inorganic hybrid materials and process for their preparation |
| US09/472,975 US6228796B1 (en) | 1998-12-28 | 1999-12-28 | Organic-inorganic hybrid materials and processes for preparing the same |
| EP20040005970 EP1437176A1 (en) | 1998-12-28 | 1999-12-28 | Multilayered organic-inorganic hybrid material and processes for preparing the same |
| EP19990125982 EP1016458B1 (en) | 1998-12-28 | 1999-12-28 | Photocatalyst comprising organic-inorganic hybrid materials, and processes for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37273298A JP3550035B2 (en) | 1998-12-28 | 1998-12-28 | Organic-inorganic multilayer material and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000190415A true JP2000190415A (en) | 2000-07-11 |
| JP3550035B2 JP3550035B2 (en) | 2004-08-04 |
Family
ID=18500957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37273298A Expired - Lifetime JP3550035B2 (en) | 1998-12-28 | 1998-12-28 | Organic-inorganic multilayer material and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3550035B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000246114A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Organic-inorganic hybrid material and its production |
| JP2000248065A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Production of organic-inorganic component-gradient component composite material |
| JP2002060689A (en) * | 2000-08-21 | 2002-02-26 | Nihon Yamamura Glass Co Ltd | Process and composition for fixing photocatalyst |
| JP2002137322A (en) * | 2000-11-02 | 2002-05-14 | Nippon Paint Co Ltd | Method for forming photocatalyst structure and photocatalyst structure obtained thereby |
| JP2002542325A (en) * | 1999-04-08 | 2002-12-10 | ゼネラル・エレクトリック・カンパニイ | Weather resistant multilayer resin article and method for producing the same |
| JP2008007610A (en) * | 2006-06-28 | 2008-01-17 | Nippon Soda Co Ltd | Organic/inorganic composite and its production process |
| JP2008101230A (en) * | 2008-01-21 | 2008-05-01 | Orient Chem Ind Ltd | Method for manufacturing organic-inorganic component gradient composite material |
| JP2008126153A (en) * | 2006-11-21 | 2008-06-05 | Matsushita Electric Works Ltd | Antifouling coated article |
| JP2008221094A (en) * | 2007-03-10 | 2008-09-25 | Japan Science & Technology Agency | Capillary, microreactor using the same and solid phase/liquid phase/gas phase reaction method by means of the microreactor |
| WO2010047195A1 (en) * | 2008-10-24 | 2010-04-29 | 関西ペイント株式会社 | Coating composition and method for forming coating film |
| JP2011084074A (en) * | 2011-01-04 | 2011-04-28 | Nippon Steel Corp | Surface treating metal |
-
1998
- 1998-12-28 JP JP37273298A patent/JP3550035B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000248065A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Production of organic-inorganic component-gradient component composite material |
| JP2000246114A (en) * | 1999-02-26 | 2000-09-12 | Orient Chem Ind Ltd | Organic-inorganic hybrid material and its production |
| JP2002542325A (en) * | 1999-04-08 | 2002-12-10 | ゼネラル・エレクトリック・カンパニイ | Weather resistant multilayer resin article and method for producing the same |
| JP4653877B2 (en) * | 2000-08-21 | 2011-03-16 | 日本山村硝子株式会社 | Method and composition for immobilizing photocatalyst |
| JP2002060689A (en) * | 2000-08-21 | 2002-02-26 | Nihon Yamamura Glass Co Ltd | Process and composition for fixing photocatalyst |
| JP2002137322A (en) * | 2000-11-02 | 2002-05-14 | Nippon Paint Co Ltd | Method for forming photocatalyst structure and photocatalyst structure obtained thereby |
| JP2008007610A (en) * | 2006-06-28 | 2008-01-17 | Nippon Soda Co Ltd | Organic/inorganic composite and its production process |
| JP2008126153A (en) * | 2006-11-21 | 2008-06-05 | Matsushita Electric Works Ltd | Antifouling coated article |
| JP2008221094A (en) * | 2007-03-10 | 2008-09-25 | Japan Science & Technology Agency | Capillary, microreactor using the same and solid phase/liquid phase/gas phase reaction method by means of the microreactor |
| JP4734544B2 (en) * | 2007-03-10 | 2011-07-27 | 独立行政法人科学技術振興機構 | Capillary, microreactor using the same, and solid-liquid-gas phase reaction method using the microreactor |
| JP2008101230A (en) * | 2008-01-21 | 2008-05-01 | Orient Chem Ind Ltd | Method for manufacturing organic-inorganic component gradient composite material |
| WO2010047195A1 (en) * | 2008-10-24 | 2010-04-29 | 関西ペイント株式会社 | Coating composition and method for forming coating film |
| GB2479075A (en) * | 2008-10-24 | 2011-09-28 | Kansai Paint Co Ltd | Coating composition and method for forming coating film |
| JP2011084074A (en) * | 2011-01-04 | 2011-04-28 | Nippon Steel Corp | Surface treating metal |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3550035B2 (en) | 2004-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1016458B1 (en) | Photocatalyst comprising organic-inorganic hybrid materials, and processes for preparing the same | |
| JP3953649B2 (en) | Organic-inorganic hybrid component gradient polymer material and method for producing the same | |
| JP5599134B2 (en) | Organic / inorganic composite composition using polyfunctional silane | |
| JP2000327930A (en) | Organic-inorganic composite and its production | |
| WO1997045502A1 (en) | Antifouling member and antifouling coating composition | |
| JP3550035B2 (en) | Organic-inorganic multilayer material and method for producing the same | |
| JP2009019072A (en) | Aqueous organic-inorganic composite composition | |
| WO2009051271A1 (en) | Photocatalytic film, method for production of photocatalytic film, article, and hydrophilization method | |
| TWI280920B (en) | High durable photocatalyst film and structure having surface exhibiting photocatalytic function | |
| JP2003181299A (en) | Production method of photocatalyst material | |
| JP2003275597A (en) | Modified photocatalyst and photocatalyst composition using the same | |
| JP3784981B2 (en) | Organic-inorganic hybrid material and method for producing the same | |
| JP2007085118A (en) | Interior finish member | |
| JP2001152130A (en) | Photocatalytically hydrophilizable member and its manufacturing method | |
| JP2004344724A (en) | Photocatalyst composition and photocatalyst body formed from the composition | |
| JP4884646B2 (en) | Adhesive layer forming composition and photocatalyst carrying structure | |
| KR101142369B1 (en) | Plastic structure with photocatalyst layer on inorganic silica binder and its fabrication method | |
| JPH11291408A (en) | Article having hydrophilic coat film | |
| TW202104528A (en) | Coating and production method therefor | |
| JP2002361807A (en) | Antistaining polycarbonate sheet | |
| JP4947678B2 (en) | Method for producing titanium oxide thin film and method for producing organic-inorganic composite gradient material | |
| JP2004123907A (en) | Coating liquid for forming hydrophilic coating film, its manufacturing method, method of using coating liquid and base material with coating film formed using the coating liquid | |
| JP4108405B2 (en) | Photocatalyst laminate | |
| JP3889615B2 (en) | Method for producing silica-based thin film and organic-inorganic composite gradient material | |
| JP2002320917A (en) | Production method for photocatalytic coating film and photocatalytic material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040120 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040312 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040413 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040422 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090430 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090430 Year of fee payment: 5 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090430 Year of fee payment: 5 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100430 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110430 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120430 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130430 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130430 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130430 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140430 Year of fee payment: 10 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |