JPH11188270A - Coating solution for forming transparent coating film having photocatalytic activity and substrate with transparent coating film - Google Patents
Coating solution for forming transparent coating film having photocatalytic activity and substrate with transparent coating filmInfo
- Publication number
- JPH11188270A JPH11188270A JP9361211A JP36121197A JPH11188270A JP H11188270 A JPH11188270 A JP H11188270A JP 9361211 A JP9361211 A JP 9361211A JP 36121197 A JP36121197 A JP 36121197A JP H11188270 A JPH11188270 A JP H11188270A
- Authority
- JP
- Japan
- Prior art keywords
- composite
- coating
- titanium oxide
- fine particles
- oxide fine
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 121
- 239000011248 coating agent Substances 0.000 title claims abstract description 120
- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 184
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000011230 binding agent Substances 0.000 claims abstract description 52
- 239000010936 titanium Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims description 136
- 239000010419 fine particle Substances 0.000 claims description 79
- 239000007788 liquid Substances 0.000 claims description 29
- 229920000620 organic polymer Polymers 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 23
- -1 compound titanium oxide Chemical class 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000002360 preparation method Methods 0.000 description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- 150000002978 peroxides Chemical class 0.000 description 13
- 239000000499 gel Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 238000000149 argon plasma sintering Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 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 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- BCVJTNGSZHSBPG-UHFFFAOYSA-N CC(C)O[Zr] Chemical compound CC(C)O[Zr] BCVJTNGSZHSBPG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- UCSUOYMTZRJAIH-UHFFFAOYSA-N iron(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Fe+2] UCSUOYMTZRJAIH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、セラミック基材、プラス
チック基材およびガラスなどの防汚、防菌または脱臭を
目的として、これら基材の表面に光触媒作用を有する透
明被膜を形成するための塗布液、およびそのような透明
被膜が形成された防汚、防菌または脱臭機能を有する基
材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating for forming a transparent film having a photocatalytic action on the surface of a ceramic substrate, a plastic substrate and glass for the purpose of antifouling, sterilization or deodorization. The present invention relates to a liquid, and a substrate having such a transparent film and having an antifouling, antibacterial or deodorizing function.
【０００２】[0002]
【発明の技術的背景】最近、チタニアの光触媒作用を利
用した製品が注目を集めている。たとえば、表面にチタ
ニア膜を形成したタイル、チタニアを含有したカーテ
ン、活性炭やゼオライトにチタニアを担持した脱臭剤な
どが市販され評判を集めている。BACKGROUND OF THE INVENTION Recently, products utilizing the photocatalysis of titania have attracted attention. For example, tiles having a titania film formed on the surface thereof, curtains containing titania, deodorants having titania supported on activated carbon or zeolite, etc. are commercially available and have gained reputation.
【０００３】これらは、いずれもチタニアの光触媒作用
により、表面に付着した汚染物、微生物あるいは臭気物
質が分解されることによる防汚、防菌あるいは脱臭効果
をねらったものである。[0003] These are all intended to have an antifouling, antibacterial or deodorizing effect due to the decomposition of contaminants, microorganisms or odorous substances attached to the surface by the photocatalytic action of titania.
【０００４】このチタニアの光触媒作用は、チタニア粒
子に紫外線が照射されると粒子内部で電子またはホール
が発生し、これが粒子表面に拡散されて酸化剤または還
元剤として作用し、この酸化作用または還元作用による
ものといわれている。When the titania particles are irradiated with ultraviolet rays, electrons or holes are generated inside the titania particles, which are diffused on the surface of the particles and act as an oxidizing agent or a reducing agent. It is said to be due to action.
【０００５】このような光触媒作用を有するチタニア被
膜は、光触媒活性を高めるため、膜厚を厚くする必要が
ある。また、光を照射したときに粒子内部に発生した電
子またはホールが被膜の表面まで速やかに移動するため
には、被膜が緻密であることが必要である。このため、
通常、製膜時に高温で処理することによって、粒子間の
融着を促進して被膜の緻密化を図るとともに、被膜の硬
度を高めているが、被膜の処理温度を高くすると、チタ
ニアの結晶構造がアナターゼ型からルチル型に変化し、
光触媒活性が低くなるという問題があった。[0005] Such a titania film having a photocatalytic action needs to be thick in order to enhance photocatalytic activity. Further, in order for electrons or holes generated inside the particles upon light irradiation to quickly move to the surface of the film, the film needs to be dense. For this reason,
Usually, high temperature treatment during film formation promotes fusion between particles to increase the density of the film and increase the hardness of the film. However, when the processing temperature of the film is increased, the crystal structure of titania is increased. Changes from anatase type to rutile type,
There was a problem that the photocatalytic activity was reduced.
【０００６】また、このような光触媒作用を有するチタ
ニア被膜は、製膜時に高温で処理するため、耐熱性のな
いガラス、プラスチック、木材、繊維、布などの上に形
成するのが困難であるという問題点もあった。[0006] Further, such a titania film having a photocatalytic action is treated at a high temperature at the time of film formation, and thus it is difficult to form it on glass, plastic, wood, fiber, cloth or the like which does not have heat resistance. There were also problems.
【０００７】このため、高温処理したチタニア粒子を用
いて被膜形成用塗布液を調製し、この塗布液を基材上に
塗布して被膜を形成することによって、比較的低温で硬
化被膜を形成することが試みられている。[0007] Therefore, a coating solution for forming a film is prepared using titania particles that have been subjected to high temperature treatment, and this coating solution is applied on a substrate to form a film, thereby forming a cured film at a relatively low temperature. Have been tried.
【０００８】しかしながら、高温処理されたチタニア粒
子は、一般に粒子径が大きく、屈折率が高いため、被膜
中でのチタニア粒子による光の散乱が大きく、高透明性
の被膜が得られないという欠点があった。However, the titania particles treated at a high temperature generally have a large particle diameter and a high refractive index, so that light scattering by the titania particles in the coating is large, and a high transparency coating cannot be obtained. there were.
【０００９】本出願人は、先に上記の問題点を解決する
ために、高い光触媒活性を有し、かつ透明性に優れた被
膜を低温処理で形成できるコーティング組成物を開発
し、提案している（特願平８−３２１８５７号）。しか
しながら、このコーティング組成物から得られる被膜
は、光触媒活性の点で、まだ満足できるものではなかっ
た。The present applicant has previously developed and proposed a coating composition capable of forming a film having high photocatalytic activity and excellent transparency by low-temperature treatment in order to solve the above problems. (Japanese Patent Application No. 8-321857). However, the coatings obtained from this coating composition have not yet been satisfactory in terms of photocatalytic activity.
【００１０】[0010]
【発明の目的】本発明は、上記のような従来技術に伴う
問題点を解決しようとするものであって、基材との密着
性が強く、より高い光触媒活性を有し、かつ透明性に優
れた被膜を低温処理で形成できる透明被膜形成用塗布液
およびこのような透明被膜が形成された透明被膜付基材
を提供することを目的としている。SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and has a strong adhesion to a substrate, a higher photocatalytic activity and a higher transparency. An object of the present invention is to provide a coating solution for forming a transparent film, which can form an excellent film by low-temperature treatment, and a substrate with a transparent film on which such a transparent film is formed.
【００１１】[0011]
【発明の概要】本発明に係る第１の透明被膜形成用塗布
液は、複合酸化チタン微粒子と、バインダーとが、水お
よび／または有機溶媒からなる溶媒に溶解または分散し
てなる透明被膜形成用塗布液であって、［Ａ］前記複合
酸化チタン微粒子が、Ｃu,Ａg,Ｚn,Ｃd,Ｖ,Ｂi,Ｃr,Ｍ
o,ＭnおよびＦeからなる群から選ばれる１種または２種
以上の元素と、Ｔiとからなる複合酸化チタン微粒子で
あり、［Ｂ］前記バインダーが、(b-1) チタン過酸化物
または(b-2) Ｃu,Ａg,Ｚn,Ｃd,Ａl,Ｚr,Ｓi,Ｓn,Ｖ,
Ｎb,Ｓb,Ｂi,Ｃr,Ｍo,Ｗ,ＭnおよびＦeからなる群から
選ばれる１種または２種以上の元素と、Ｔiとからなる
複合チタン過酸化物と、(b-3) 有機高分子化合物とから
なることを特徴とする透明被膜形成用塗布液。SUMMARY OF THE INVENTION A first coating liquid for forming a transparent coating according to the present invention is a coating liquid for forming a transparent coating, wherein composite titanium oxide fine particles and a binder are dissolved or dispersed in a solvent comprising water and / or an organic solvent. [A] the composite titanium oxide fine particles are Cu, Ag, Zn, Cd, V, Bi, Cr, M
composite titanium oxide fine particles comprising one or more elements selected from the group consisting of o, Mn and Fe, and Ti; and [B] the binder comprises (b-1) titanium peroxide or ( b-2) Cu, Ag, Zn, Cd, Al, Zr, Si, Sn, V,
A composite titanium peroxide composed of one or more elements selected from the group consisting of Nb, Sb, Bi, Cr, Mo, W, Mn, and Fe, Ti, and (b-3) an organic polymer A coating solution for forming a transparent film, comprising a compound.
【００１２】本発明に係る第２の透明被膜形成用塗布液
は、複合酸化チタン微粒子と、バインダーとが、水およ
び／または有機溶媒からなる溶媒に溶解または分散して
なる透明被膜形成用塗布液であって、［Ｃ］前記複合酸
化チタン微粒子が、Ａl,Ｚr,Ｓi,Ｓn,Ｎb,ＳbおよびＷ
からなる群から選ばれる１種または２種以上の元素と、
Ｔiとからなる複合酸化チタン微粒子であり、［Ｄ］前
記バインダーが、(d-1) Ｃu,Ａg,Ｚn,Ｃd,Ｖ,Ｂi,Ｃr,
Ｍo,ＭnおよびＦeからなる群から選ばれる１種または２
種以上の元素と、Ｔiとからなる複合チタン過酸化物
と、(d-2) 有機高分子化合物とからなることを特徴とし
ている。[0012] The second coating liquid for forming a transparent coating according to the present invention is a coating liquid for forming a transparent coating, wherein the composite titanium oxide fine particles and a binder are dissolved or dispersed in a solvent comprising water and / or an organic solvent. [C] The composite titanium oxide fine particles are composed of Al, Zr, Si, Sn, Nb, Sb and W
One or more elements selected from the group consisting of:
Composite titanium oxide fine particles comprising Ti and [D] wherein the binder is (d-1) Cu, Ag, Zn, Cd, V, Bi, Cr,
One or two selected from the group consisting of Mo, Mn and Fe
It is characterized by comprising a composite titanium peroxide comprising at least one or more elements and Ti, and (d-2) an organic polymer compound.
【００１３】前記有機高分子化合物は、多糖類であるこ
とが好ましい。本発明に係る透明被膜付基材は、前記透
明被膜形成用塗布液を用いて形成された透明被膜を有す
ることを特徴としている。The organic polymer compound is preferably a polysaccharide. The substrate with a transparent film according to the present invention is characterized by having a transparent film formed using the coating liquid for forming a transparent film.
【００１４】[0014]
【発明の具体的説明】以下、本発明に係る第１および第
２の透明被膜形成用塗布液および被膜付基材についてよ
り具体的に説明する。DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the first and second coating solutions for forming a transparent film and the substrate with a film according to the present invention will be described more specifically.
【００１５】［第１の透明被膜形成用塗布液］本発明に
係る第１の透明被膜形成用塗布液は、[A] 複合酸化チタ
ン微粒子、および、チタン過酸化物(b-1)または複合チ
タン過酸化物(b-2)と、有機高分子化合物(b-3)とからな
るバインダー[B] が、水および／または有機溶媒からな
る溶媒に、溶解または分散している。[First Coating Solution for Forming a Transparent Film] The first coating solution for forming a transparent film according to the present invention comprises [A] composite titanium oxide fine particles and titanium peroxide (b-1) or a composite. A binder [B] composed of titanium peroxide (b-2) and an organic polymer compound (b-3) is dissolved or dispersed in a solvent composed of water and / or an organic solvent.
【００１６】まず複合酸化チタン微粒子について説明す
る。複合酸化チタン微粒子[A] 本発明で使用される複合酸化チタン微粒子[A] とは、Ｃ
u,Ａg,Ｚn,Ｃd,Ｖ,Ｂi,Ｃr,Ｍo,ＭnおよびＦeとからな
る群から選ばれる１種または２種以上の元素（以下、Ｔ
i以外の元素(a)という）とＴi元素との複合酸化物から
なる微粒子である。First, the composite titanium oxide fine particles will be described. Composite titanium oxide fine particles [A] The composite titanium oxide fine particles [A] used in the present invention are C
u, Ag, Zn, Cd, V, Bi, Cr, Mo, Mn and Fe, one or more elements selected from the group consisting of
fine particles made of a composite oxide of an element (a) other than i) and the Ti element.
【００１７】このような複合酸化物は、(1) 酸化チタン
とＴi以外の元素(a)とが化学的に結合した複合酸化物、
(2) 酸化チタンとＴi以外の元素(a)の酸化物との固溶
体、(3) 酸化チタンとＴi以外の元素(a)のクラスターと
の混合物、(4) 酸化チタンとＴi以外の元素(a)の酸化物
との均一な混合物などを意味している。なお、前記クラ
スターとは、Ｔi以外の元素(a)の髭状の結晶酸化物をい
う。Such composite oxides include (1) a composite oxide in which titanium oxide and an element (a) other than Ti are chemically bonded,
(2) a solid solution of titanium oxide and an oxide of element (a) other than Ti; (3) a mixture of titanium oxide and a cluster of element (a) other than Ti; (4) an element other than titanium oxide and Ti ( It means a homogeneous mixture with the oxide of a). The cluster refers to a whisker-like crystalline oxide of the element (a) other than Ti.
【００１８】また、複合酸化物は、上記(1)〜(4)の混合
物であってもよく、さらにこのような複合酸化物からな
る微粒子の表面が、Ｔi以外の元素(a)の１種または２種
以上の酸化物で被覆された構造のもの、または、それぞ
れの酸化物が順次積層された構造のものも上記複合酸化
物に含まれる。Further, the composite oxide may be a mixture of the above (1) to (4), and the surface of the fine particles composed of such a composite oxide may be one of the elements (a) other than Ti. Alternatively, the composite oxide includes a structure covered with two or more kinds of oxides or a structure in which each oxide is sequentially stacked.
【００１９】このような複合酸化物におけるＴiとＴi以
外の元素(a)との複合割合は、それぞれの酸化物をＴiＯ
2、ＭＯxとして、ＴiＯ2／ＭＯx（重量比）が５０／５
０〜９９.９／０.１の範囲にあることが好ましい。Ｔi
Ｏ2／ＭＯxが９９.９／０.１を越えると、複合化の効果
が少なく、ＴiＯ2／ＭＯxが５０／５０未満では酸化チ
タンの量が少なすぎて複合酸化物の光吸収特性、化学反
応性などが劣り、本発明の目的とする光触媒作用の効果
が少なくなることがある。The composite ratio of Ti and the element (a) other than Ti in such a composite oxide is such that each oxide is made of TiO 2
As 2, MO x, TiO 2 / MO x ( weight ratio) 50/5
It is preferably in the range of 0 to 99.9 / 0.1. Ti
When O 2 / MO x exceeds 99.9 / 0.1, the effect of compounding is small, and when TiO 2 / MO x is less than 50/50, the amount of titanium oxide is too small and the light absorption characteristics of the composite oxide. , The chemical reactivity is poor, and the effect of the photocatalytic action aimed at by the present invention may be reduced.
【００２０】本発明で使用する複合酸化チタン微粒子
[A]は、特に３００〜４５０nmの範囲の波長の光の吸収
に優れており、導電性、化学的活性および有機溶剤との
親和性が高い。The composite titanium oxide fine particles used in the present invention
[A] is particularly excellent in absorbing light having a wavelength in the range of 300 to 450 nm, and has high conductivity, chemical activity, and affinity with an organic solvent.
【００２１】このような複合酸化チタン微粒子[A]の平
均粒径は、０.４μｍ以下、好ましくは０.００５〜０.
２μｍの範囲が望ましい。この範囲の微粒子であれば、
粒子による光の散乱が少なく、透明性の高い被膜が得ら
れる。The average particle diameter of the composite titanium oxide fine particles [A] is 0.4 μm or less, preferably 0.005 to 0.5 μm.
A range of 2 μm is desirable. If the particles are in this range,
Light scattering by the particles is small, and a highly transparent coating film can be obtained.
【００２２】このような複合酸化チタン微粒子[A]の製
造方法としては、特に制限なく、従来の微粒子の製造法
が採用される。たとえば、塩化チタンなどのチタン塩と
チタン以外の金属の塩の混合水溶液にアルカリを加え
て、中和、加水分解して複合水酸化物（または水和酸化
物）を得たのち、これを２００〜９００℃の温度で高温
処理して複合酸化チタン微粒子を得ることができる。The method for producing such composite titanium oxide fine particles [A] is not particularly limited, and a conventional method for producing fine particles is employed. For example, an alkali is added to a mixed aqueous solution of a titanium salt such as titanium chloride and a salt of a metal other than titanium, and the mixture is neutralized and hydrolyzed to obtain a composite hydroxide (or hydrated oxide). The composite titanium oxide fine particles can be obtained by high-temperature treatment at a temperature of about 900 ° C.
【００２３】また、チタンのアルコキシドおよびチタン
以外の金属のアルコキシドを水−アルコール混合溶媒中
で加水分解することにより、複合水酸化物を得たのち同
様に焼成することによっても、複合酸化チタン微粒子を
得ることができる。このようなアルコキシドの加水分解
によって複合酸化チタン微粒子を製造すると、高純度の
複合酸化チタン微粒子を得ることができる。The titanium oxide alkoxide and the metal alkoxide other than titanium are hydrolyzed in a water-alcohol mixed solvent to obtain a composite hydroxide, which is then calcined to obtain composite titanium oxide fine particles. Obtainable. When composite titanium oxide fine particles are produced by such hydrolysis of alkoxide, high-purity composite titanium oxide fine particles can be obtained.
【００２４】こうして得られた複合酸化チタン微粒子
[A]は、必要に応じて粉砕処理、分級操作等により所望
の粒径に調整してもよい。上記方法では、高温処理を行
って複合酸化物の結晶性を高めるているが、上記方法で
得られた複合水酸化物を乾燥することなく、複合水酸化
物の分散液（ゾルまたはヒドロゲル分散液）を水熱処理
することによっても、上記高温処理した場合と同じ結晶
性の高い複合酸化チタン微粒子を得ることもできる。具
体的には、上記の分散液に解膠剤としての酸、アミンま
たは過酸化物などを添加してオートクレーブなどの耐圧
容器中で加熱処理する。水熱処理温度は、約５０℃以
上、溶媒の臨界温度未満の範囲が好ましい。このような
水熱処理を行うことによって、結晶性の高い複合酸化チ
タン微粒子の単分散液が得られる。本発明では、この単
分散液を乾燥することなく、そのまま塗布液の配合材料
として用いることができる。このとき、分散媒が水であ
る場合は、必要に応じて有機溶媒に溶媒置換してもよ
い。また、前記単分散液にシランカップリング剤を添加
して、微粒子を表面処理してもよい。このようなシラン
カップリング処理によって、塗布液の安定性が向上し、
かつ塗布液中での分散性も向上するため、透明被膜の触
媒機能も向上する。The composite titanium oxide fine particles thus obtained
[A] may be adjusted to a desired particle size by a pulverizing treatment, a classification operation, or the like, if necessary. In the above method, high-temperature treatment is performed to increase the crystallinity of the composite oxide. However, without drying the composite hydroxide obtained by the above method, a composite hydroxide dispersion (sol or hydrogel dispersion ) Can also be used to obtain composite titanium oxide fine particles having the same high crystallinity as in the case of the high-temperature treatment. Specifically, an acid, an amine, a peroxide, or the like as a deflocculant is added to the above-described dispersion, and the dispersion is heated in a pressure vessel such as an autoclave. The temperature of the hydrothermal treatment is preferably in the range of about 50 ° C. or higher and lower than the critical temperature of the solvent. By performing such a hydrothermal treatment, a monodispersed liquid of composite titanium oxide fine particles having high crystallinity can be obtained. In the present invention, this monodispersed liquid can be used as it is as a compounding material of the coating liquid without drying. At this time, when the dispersion medium is water, the solvent may be replaced with an organic solvent as needed. Further, the fine particles may be surface-treated by adding a silane coupling agent to the monodispersed liquid. By such a silane coupling treatment, the stability of the coating solution is improved,
In addition, since the dispersibility in the coating solution is also improved, the catalytic function of the transparent film is also improved.
【００２５】さらに、このような複合酸化チタン微粒子
の製造方法としては、先に本出願人の出願に係る特開昭
６３−２２９１３９号公報に記載された方法でも製造す
ることができる。Further, as a method for producing such composite titanium oxide fine particles, a method described in Japanese Patent Application Laid-Open No. 63-229139, filed by the present applicant, can be used.
【００２６】すなわち、酸化チタン水和物および上記の
金属酸化物の水和物の混合物の分散液を調製し、これに
過酸化水素を加えて上記水和物を均一な水溶液としたの
ち、水溶液を６０℃以上に加熱することによっても複合
酸化チタン微粒子を得ることができる。That is, a dispersion of a mixture of a hydrate of titanium oxide and a hydrate of the above-mentioned metal oxide is prepared, and hydrogen peroxide is added thereto to form a uniform aqueous solution of the hydrate. Is heated to 60 ° C. or more, composite titanium oxide fine particles can be obtained.
【００２７】バインダー[B] 本発明では、複合酸化チタン微粒子[A]に対して、(b-1)
チタン過酸化物または(b-2)複合チタン過酸化物と、(b-
3)有機高分子化合物とからなるバインダー[B]が使用さ
れる。 Binder [B] In the present invention, (b-1)
Titanium peroxide or (b-2) composite titanium peroxide, and (b-
3) A binder [B] composed of an organic polymer compound is used.
【００２８】チタン過酸化物(b-1)とは、通常ＴiＯ3・n
Ｈ2Ｏで表される化合物である。このようなチタン過酸
化物(b-1)は、四塩化チタンなどの塩、水酸化チタン、
チタンアルコキシドまたはアセチルアセトナートのチタ
ン錯体などのチタン化合物と、過酸化水素などの過酸化
物とを反応させることによって得ることができる。Titanium peroxide (b-1) is usually TiO 3 .n
It is a compound represented by H 2 O. Such titanium peroxide (b-1) is a salt such as titanium tetrachloride, titanium hydroxide,
It can be obtained by reacting a titanium compound such as a titanium complex of titanium alkoxide or acetylacetonate with a peroxide such as hydrogen peroxide.
【００２９】また、複合チタン過酸化物(b-2)は、Ｔi
と、Ｃu,Ａg,Ｚn,Ｃd,Ａl,Ｚr,Ｓi,Ｓn,Ｖ,Ｎb,Ｓb,Ｂ
i,Ｃr,Ｍo,Ｗ,ＭnおよびＦeからなる群から選ばれる１
種または２種以上の元素（以下、チタン以外の元素(b)
という）とからなる複合金属の過酸化物であり、前記チ
タン過酸化物(b-1)の一部のＴiをチタン以外の元素(b)
で置換したものである。The composite titanium peroxide (b-2) is Ti
And Cu, Ag, Zn, Cd, Al, Zr, Si, Sn, V, Nb, Sb, B
1 selected from the group consisting of i, Cr, Mo, W, Mn and Fe
Species or two or more elements (hereinafter, elements other than titanium (b)
) And a part of Ti of the titanium peroxide (b-1) is replaced with an element (b) other than titanium.
Is replaced by
【００３０】このような複合チタン過酸化物(b-2)は、
前記チタン化合物と、チタン以外の元素の塩、水酸化
物、アルコキシドまたはアセチルアセトナート錯体など
の化合物と、過酸化水素などの過酸化物とを反応させる
ことによって得ることができる。たとえば、イソプロポ
キシチタンとイソプロポキシジルコニウムの水−アルコ
ール溶液に過酸化水素を添加し、加熱処理すると、チタ
ンとジルコニウムの複合過酸化物が得られる。このよう
なチタン過酸化物(b-1)または複合チタン過酸化物(b-1-
2)は、通常溶液状態にある。The composite titanium peroxide (b-2) is
The titanium compound can be obtained by reacting a compound such as a salt, hydroxide, alkoxide or acetylacetonate complex of an element other than titanium with a peroxide such as hydrogen peroxide. For example, when hydrogen peroxide is added to a water-alcohol solution of isopropoxytitanium and isopropoxyzirconium and then heat-treated, a composite peroxide of titanium and zirconium is obtained. Such titanium peroxide (b-1) or composite titanium peroxide (b-1-
2) is usually in a solution state.
【００３１】このようなチタン過酸化物(b-1)または複
合チタン過酸化物(b-2)は、前記複合酸化チタン微粒子
[A]と同程度の屈折率を有しているので、被膜構成成分
による光散乱が少なく、透明性に優れた被膜を形成する
ことができる。The titanium peroxide (b-1) or the composite titanium peroxide (b-2) is used as the composite titanium oxide fine particles.
Since it has a refractive index similar to that of [A], light scattering due to the film constituents is small, and a film having excellent transparency can be formed.
【００３２】特に、チタン過酸化物または複合チタン過
酸化物として、Ｔiと、Ｚrおよび／またはＳiとの複合
過酸化物を用いると、基材との密着性および有機溶媒と
の親和性などが大幅に向上するので好ましい。In particular, when a composite peroxide of Ti, Zr and / or Si is used as the titanium peroxide or the composite titanium peroxide, the adhesion to the base material and the affinity to the organic solvent are improved. It is preferable because it greatly improves.
【００３３】また、上記チタン過酸化物または複合チタ
ン過酸化物は、有機アミンまたはアセチルアセトンなど
と反応させて使用してもよい。上記のような過酸化物を
バインダーとして含む塗布液を用いて透明被膜を形成す
ると、形成工程の加熱処理において過酸化物が分解し
て、被膜の緻密化を促進することができる。また、バイ
ンダーとして、上記のようなチタン過酸化物または複合
チタン過酸化物を含んでいると、バインダー自体が光触
媒活性および導電性を有することになるため、光触媒活
性が促進され、被膜の光触媒活性を高くすることができ
る。さらに、バインダーの屈折率が複合酸化チタン微粒
子の屈折率とほぼ同じであるため、透明性が高く、ヘイ
ズが小さい被膜を形成することが可能である。さらにま
た約１５０℃程度の低温度で処理しても、被膜の高硬度
化が可能なため、ガラス、プラスチックなどの基材との
密着性に優れた被膜を形成することが可能であり、かつ
約１μｍ程度の厚膜がワンコートで容易に形成すること
ができる。The above-mentioned titanium peroxide or composite titanium peroxide may be used by reacting it with an organic amine or acetylacetone. When a transparent coating is formed using a coating solution containing a peroxide as a binder as described above, the peroxide is decomposed in the heat treatment in the formation step, and the densification of the coating can be promoted. Further, when the above-mentioned titanium peroxide or composite titanium peroxide is contained as a binder, the binder itself has photocatalytic activity and conductivity, so that the photocatalytic activity is promoted, and the photocatalytic activity of the coating film is enhanced. Can be higher. Further, since the refractive index of the binder is almost the same as the refractive index of the composite titanium oxide fine particles, it is possible to form a film having high transparency and small haze. Furthermore, even if the treatment is performed at a low temperature of about 150 ° C., since the hardness of the film can be increased, it is possible to form a film having excellent adhesion to a substrate such as glass and plastic, and A thick film of about 1 μm can be easily formed with one coat.
【００３４】バインダー中に含まれる有機高分子化合物
(b-3)としては、キトサン、セルローズなどの多糖類が
好ましい。バインダー中にこのような有機高分子化合物
(b-3)を含んでいると、被膜形成時の乾燥工程での被膜
の収縮に伴う応力が緩和され、被膜のクラックが防止さ
れ、厚膜化が可能となる。また、基材に対する塗布液の
濡れ性が向上し、しかも塗布液の粘度が上昇するため塗
布時の作業性を向上することができる。Organic polymer compound contained in binder
As (b-3), polysaccharides such as chitosan and cellulose are preferable. Such an organic polymer compound in the binder
When (b-3) is contained, stress accompanying shrinkage of the film in the drying step at the time of film formation is alleviated, cracks of the film are prevented, and the film can be made thicker. Further, the wettability of the coating liquid to the base material is improved, and the viscosity of the coating liquid is increased, so that the workability during coating can be improved.
【００３５】透明被膜形成用塗布液の調製 本発明に係る透明被膜形成用塗布液は、上記複合酸化チ
タン微粒子とバインダーとを、水および／または有機溶
媒からなる溶媒に、溶解または分散させて調製すること
ができる。Preparation of Transparent Film Forming Coating Solution The transparent film forming coating solution according to the present invention is prepared by dissolving or dispersing the above composite titanium oxide fine particles and a binder in a solvent comprising water and / or an organic solvent. can do.
【００３６】有機溶媒としては、メタノール、エタノー
ル、プロパノール、ブタノール、ジアセトンアルコー
ル、フルフリルアルコール、エチレングリコール、ヘキ
シレングリコールなどのアルコール類、酢酸メチルエス
テル、酢酸エチルエステルなどのエステル類、ジエチル
エーテル、エチレングリコールモノメチルエーテル、エ
チレングリコールモノエチルエーテル、エチレングリコ
ールモノブチルエーテル、ジエチレングリコールモノメ
チルエーテル、ジエチレングリコールモノエチルエーテ
ルなどのエーテル類、アセトン、メチルエチルケトン、
アセチルアセトン、アセト酢酸エステルなどのケトン類
等が挙げられる。これらは１種、または２種以上混合し
て使用することができる。Examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, ethylene glycol and hexylene glycol; esters such as methyl acetate, ethyl acetate; diethyl ether; Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone,
Ketones such as acetylacetone and acetoacetate are exemplified. These can be used alone or in combination of two or more.
【００３７】塗布液中の固形分（複合酸化チタン微粒子
[A]と、バインダー中のチタン過酸化物(b-1)または複合
チタン過酸化物(b-2)とを合わせたもの）濃度は、１〜
４０重量％、好ましくは２〜３０重量％の範囲にあるこ
とが好ましい。Solid content in the coating solution (composite titanium oxide fine particles
[A] and the combination of titanium peroxide (b-1) or composite titanium peroxide (b-2) in the binder)
It is preferably in the range of 40% by weight, preferably 2-30% by weight.
【００３８】また、塗布液中の複合酸化チタン微粒子
[A]と、チタン過酸化物(b-1)または複合チタン過酸化物
(b-2)（過酸化物）との重量比は、複合酸化チタン微粒
子／過酸化物が５／１〜１／５、好ましくは５／１〜１
／２にあることが望ましい。Further, composite titanium oxide fine particles in the coating solution
[A] and titanium peroxide (b-1) or composite titanium peroxide
(b-2) The weight ratio to (peroxide) is such that the composite titanium oxide fine particles / peroxide is 5/1 to 1/5, preferably 5/1 to 1/5.
/ 2 is desirable.
【００３９】さらにまた、前記有機高分子化合物(b-3)
は、塗布液に対して、０.１〜５.０重量％、好ましくは
０.２〜４.０重量％の量で含まれていることが望まし
い。これらの透明被膜形成用塗布液の調製法としては、
特に制限はなく、たとえば上記の複合酸化チタン微粒子
とバインダーを適宜の溶媒または分散媒と混合すること
によって得られる。Further, the organic polymer compound (b-3)
Is contained in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, based on the coating solution. As a method of preparing these coating liquids for forming a transparent film,
There is no particular limitation, and for example, it can be obtained by mixing the above composite titanium oxide fine particles and a binder with an appropriate solvent or dispersion medium.
【００４０】［第２の透明被膜形成用塗布液］次に、第
２の透明被膜形成用塗布液について説明する。複合酸化
チタン微粒子[C] 、および、複合チタン過酸化物(d-1)
と有機高分子化合物(d-2)とからなるバインダー[D]が、
水および／または有機溶媒からなる溶媒に、溶解または
分散している。[Second Transparent Film Forming Coating Solution] Next, the second transparent film forming coating solution will be described. Composite titanium oxide fine particles [C] and composite titanium peroxide (d-1)
And a binder [D] composed of an organic polymer compound (d-2) and
It is dissolved or dispersed in a solvent composed of water and / or an organic solvent.
【００４１】まず複合酸化チタン微粒子について説明す
る。複合酸化チタン微粒子[C] 本発明で使用される複合酸化チタン微粒子[C]とは、Ａ
l,Ｚr,Ｓi,Ｓn,Ｎb,ＳbおよびＷからなる群から選ばれ
る１種または２種以上の元素（以下、Ｔi以外の元素(c)
という）とＴi元素とからなる複合酸化物からなる微粒
子である。First, the composite titanium oxide fine particles will be described. Composite titanium oxide fine particles [C] The composite titanium oxide fine particles [C] used in the present invention are A
one or more elements selected from the group consisting of l, Zr, Si, Sn, Nb, Sb and W (hereinafter, the element (c) other than Ti)
) And a Ti oxide.
【００４２】このような複合酸化物は、(1) 酸化チタン
とＴi以外の元素(c)とが化学的に結合した複合酸化物、
(2) 酸化チタンとＴi以外の元素(c)の酸化物との固溶
体、(3) 酸化チタンとＴi以外の元素(c)のクラスターと
の混合物、(4) 酸化チタンとＴi以外の元素(c)の酸化物
との均一な混合物などを意味している。Such composite oxides include (1) a composite oxide in which titanium oxide and an element (c) other than Ti are chemically bonded,
(2) a solid solution of titanium oxide and an oxide of element (c) other than Ti; (3) a mixture of titanium oxide and a cluster of element (c) other than Ti; (4) an element other than titanium oxide and Ti ( It means a homogeneous mixture with the oxide of c).
【００４３】また、複合酸化物は、上記(1)〜(4)の混合
物であってもよく、さらにこのような複合酸化物からな
る微粒子の表面が、たとえばシリカ、シリカ・アルミ
ナ、シリカ・ジルコニアなどで被覆された構造のものも
含まれる。さらにまた、たとえばシリカのコアに酸化チ
タン、酸化チタン・酸化ジルコニウム複合酸化物がこの
順序で積層された構造の複合酸化物、あるいは酸化チタ
ンのコアに酸化チタン・酸化ジルコニウム複合酸化物、
シリカ・アルミナ複合酸化物がこの順序で積層された構
造の複合酸化物、さらには酸化チタン微粒子の表面がＴ
i以外の元素(c)の１種または２種以上の酸化物で被覆さ
れた構造のものも上記複合酸化物に含まれる。The composite oxide may be a mixture of the above (1) to (4), and the surface of the fine particles composed of such a composite oxide may be, for example, silica, silica-alumina, silica-zirconia. The structure covered with etc. is also included. Furthermore, for example, a titanium oxide, a titanium oxide / zirconium oxide composite oxide is laminated on a silica core in this order, or a titanium oxide / zirconium oxide composite oxide is deposited on a titanium oxide core.
The composite oxide having a structure in which the silica-alumina composite oxide is laminated in this order, and the surface of the titanium oxide fine particles are T
The composite oxide includes a structure coated with one or more oxides of the element (c) other than i.
【００４４】このような複合酸化物におけるＴiとＴi以
外の元素(c)との複合割合は、それぞれの酸化物をＴiＯ
2、ＭＯxとして、ＴiＯ2／ＭＯx（重量比）が５０／５
０〜９９.９／０.１の範囲にあることが好ましい。Ｔi
Ｏ2／ＭＯxが９９.９／０.１を越えると、複合化の効果
が少なく、ＴiＯ2／ＭＯxが５０／５０未満では酸化チ
タンの量が少なすぎて、複合酸化物の光吸収特性、化学
反応性などが劣り、本発明の目的とする光触媒作用の効
果が少なくなることがある。The composite ratio of Ti and the element (c) other than Ti in such a composite oxide is determined by the fact that each oxide is made of TiO 2
As 2, MO x, TiO 2 / MO x ( weight ratio) 50/5
It is preferably in the range of 0 to 99.9 / 0.1. Ti
When O 2 / MO x exceeds 99.9 / 0.1, the effect of compounding is small, and when TiO 2 / MO x is less than 50/50, the amount of titanium oxide is too small and the light absorption of the composite oxide is small. The properties, chemical reactivity, etc. are poor, and the effect of the photocatalytic action aimed at by the present invention may be reduced.
【００４５】本発明で使用する複合酸化チタン微粒子
[C]は、前記複合酸化チタン微粒子[A]と同様に、特に３
００〜４５０nmの範囲の波長の光の吸収に優れており、
導電性、化学的活性および有機溶剤との親和性が高い。Composite titanium oxide fine particles used in the present invention
[C] is the same as the above-mentioned composite titanium oxide fine particles [A], especially 3.
Excellent absorption of light in the wavelength range of 00 to 450 nm,
High conductivity, chemical activity and affinity with organic solvents.
【００４６】このような複合酸化チタン微粒子[C]の平
均粒径は、０.４μｍ以下、好ましくは０.００５〜０.
２μｍの範囲が望ましい。この範囲の微粒子であれば、
粒子による光の散乱が少なく、透明性の高い被膜が得ら
れる。The average particle size of the composite titanium oxide fine particles [C] is 0.4 μm or less, preferably 0.005 to 0.5 μm.
A range of 2 μm is desirable. If the particles are in this range,
Light scattering by the particles is small, and a highly transparent coating film can be obtained.
【００４７】このような複合酸化チタン微粒子の製造方
法としては、前記複合酸化チタン微粒子[A]と同様であ
る。バインダー[D] 本発明では、複合酸化チタン微粒子[C]に対して、複合
チタン過酸化物(d-1)と、有機高分子化合物(d-2)とから
なるバインダー[D]が使用される。The method for producing such composite titanium oxide fine particles is the same as that for the composite titanium oxide fine particles [A]. Binder [D] In the present invention, a binder [D] comprising a composite titanium peroxide (d-1) and an organic polymer compound (d-2) is used for the composite titanium oxide fine particles [C]. You.
【００４８】複合チタン過酸化物(d-1)は、Ｔiと、Ｃu,
Ａg,Ｚn,Ｃd,Ｖ,Ｂi,Ｃr,Ｍo,ＭnおよびＦeからなる群
から選ばれる１種または２種以上の元素（チタン以外の
元素）とからなる複合金属の過酸化物である。The composite titanium peroxide (d-1) is composed of Ti, Cu,
It is a peroxide of a composite metal comprising one or more elements (elements other than titanium) selected from the group consisting of Ag, Zn, Cd, V, Bi, Cr, Mo, Mn and Fe.
【００４９】このような複合チタン過酸化物(d-1)は、
前記複合チタン過酸化物(b-2)と同様に、チタン化合物
と、チタン以外の元素の塩、水酸化物、アルコキシドま
たはアセチルアセトナート錯体などの化合物と、過酸化
水素などの過酸化物とを反応することによって得ること
ができる。このような複合チタン過酸化物は、単量体ま
たは重合体で使用され、通常、液状である。Such a composite titanium peroxide (d-1)
Like the composite titanium peroxide (b-2), a titanium compound, a salt of an element other than titanium, a hydroxide, a compound such as an alkoxide or an acetylacetonate complex, and a peroxide such as hydrogen peroxide. Can be obtained by reacting Such a composite titanium peroxide is used as a monomer or a polymer, and is usually in a liquid state.
【００５０】このような複合チタン過酸化物(d-1)は、
前記複合酸化チタン微粒子[C]と同程度の屈折率を有し
ているので、このような複合チタン過酸化物(d-1)を透
明被膜形成用塗布液のバインダーとして用いると、被膜
構成成分による光散乱が少なく、透明性に優れた被膜を
形成することができる。Such a composite titanium peroxide (d-1) is
Since the composite titanium oxide fine particles [C] have a refractive index similar to that of the composite titanium oxide fine particles [C], when such a composite titanium peroxide (d-1) is used as a binder in a coating liquid for forming a transparent coating, the coating component Scattered light, and a film excellent in transparency can be formed.
【００５１】また、上記複合チタン過酸化物は、有機ア
ミンまたはアセチルアセトンなどと反応させて使用して
もよい。上記のような複合チタン過酸化物をバインダー
として含む塗布液を用いて透明被膜を形成すると、形成
工程の加熱処理において過酸化物が分解して、被膜の緻
密化を促進することができる。また、バインダーとし
て、上記のようなチタン過酸化物または複合チタン過酸
化物を含んでいると、バインダー自体が光触媒活性およ
び導電性を有することになるため、光触媒活性が促進さ
れ、被膜の光触媒活性を高くすることができる。さら
に、バインダーの屈折率が複合酸化チタン微粒子の屈折
率とほぼ同じであるため、透明性が高く、ヘイズが小さ
い被膜を形成することが可能である。さらにまた約１５
０℃程度の低温度で処理しても、被膜の高硬度化が可能
なため、ガラス、プラスチックなどの基材との密着性に
優れた被膜を形成することが可能であり、かつ約１μｍ
程度の厚膜がワンコートで容易に形成することができ
る。The above-mentioned composite titanium peroxide may be used by reacting it with an organic amine or acetylacetone. When a transparent coating is formed using a coating solution containing the above-described composite titanium peroxide as a binder, the peroxide is decomposed in the heat treatment in the forming step, and the densification of the coating can be promoted. Further, when the above-mentioned titanium peroxide or composite titanium peroxide is contained as a binder, the binder itself has photocatalytic activity and conductivity, so that the photocatalytic activity is promoted, and the photocatalytic activity of the coating film is enhanced. Can be higher. Further, since the refractive index of the binder is almost the same as the refractive index of the composite titanium oxide fine particles, it is possible to form a film having high transparency and small haze. About 15
Even when treated at a low temperature of about 0 ° C., the hardness of the film can be increased, so that a film having excellent adhesion to a substrate such as glass or plastic can be formed, and about 1 μm
A thick film of about a degree can be easily formed by one coat.
【００５２】バインダー中に含まれる有機高分子化合物
(d-2)としては、前記したものと同様のものが挙げられ
る。透明被膜形成用塗布液の調製 本発明に係る透明被膜形成用塗布液は、上記複合酸化チ
タン微粒子[C]とバインダー[D]とを、水および／または
有機溶媒からなる溶媒に溶解または分散させて調製する
ことができる。Organic polymer compound contained in binder
Examples of (d-2) include the same as those described above. Preparation of Transparent Film Forming Coating Solution The transparent film forming coating solution according to the present invention is obtained by dissolving or dispersing the composite titanium oxide fine particles [C] and the binder [D] in a solvent composed of water and / or an organic solvent. Can be prepared.
【００５３】有機溶媒としては、前記と同様のものが挙
げられる。塗布液中の固形分（複合酸化チタン微粒子
[C]とバインダー中の複合チタン過酸化物(d-1)とを合わ
せたもの）濃度は、１〜４０重量％、好ましくは２〜３
０重量％の範囲にあることが好ましい。Examples of the organic solvent include the same ones as described above. Solid content in coating solution (composite titanium oxide fine particles
[C] and the composite titanium peroxide (d-1) in the binder) concentration is 1 to 40% by weight, preferably 2 to 3% by weight.
It is preferably in the range of 0% by weight.
【００５４】また、塗布液中の複合酸化チタン微粒子
[C]と、複合チタン過酸化物(d-1)との重量比は、複合酸
化チタン微粒子／複合チタン過酸化物が５／１〜１／
５、好ましくは５／１〜１／２にあることが望ましい。Further, composite titanium oxide fine particles in the coating solution
The weight ratio of [C] to the composite titanium peroxide (d-1) is such that the composite titanium oxide fine particles / the composite titanium peroxide are 5/1 to 1/1.
5, preferably 5/1 to 1/2.
【００５５】さらにまた、前記有機高分子化合物(d-2)
は、塗布液に対して、０.１〜５.０重量％、好ましくは
０.２〜４.０重量％の量で含まれていることが望まし
い。これらの透明被膜形成用塗布液の調製法としては、
特に制限はなく、たとえば上記の複合酸化チタン微粒子
とバインダーを適宜の溶媒または分散媒と混合すること
によって得られる。Further, the organic polymer compound (d-2)
Is contained in an amount of 0.1 to 5.0% by weight, preferably 0.2 to 4.0% by weight, based on the coating solution. As a method of preparing these coating liquids for forming a transparent film,
There is no particular limitation, and for example, it can be obtained by mixing the above composite titanium oxide fine particles and a binder with an appropriate solvent or dispersion medium.
【００５６】［透明被膜付基材］本発明に係る透明被膜
付基材は、前記のような第１または第２の透明被膜形成
用塗布液をガラス、プラスチック、セラミックまたは繊
維などの基材の表面に、スピナー法、バーコーター法、
スプレー法、ディップ法あるいはフレキソ法などの通常
の方法で塗布したのち乾燥し、１５０〜４００℃で加熱
硬化することによって得られる。硬化処理は、紫外線照
射などの方法を併用することも可能である。透明被膜の
膜厚は、約０.１〜１０μｍ、好ましくは０.２〜５μｍ
の範囲にあることが望ましい。[Substrate with Transparent Coating] The substrate with a transparent coating according to the present invention is obtained by applying the above-mentioned first or second coating liquid for forming a transparent coating to a substrate such as glass, plastic, ceramic or fiber. Spinner method, bar coater method,
It is obtained by coating by a usual method such as a spray method, a dipping method or a flexo method, followed by drying and heat curing at 150 to 400 ° C. For the curing treatment, a method such as ultraviolet irradiation can be used in combination. The thickness of the transparent coating is about 0.1 to 10 μm, preferably 0.2 to 5 μm.
Is desirably within the range.
【００５７】このようにして得られた透明被膜付基材
は、その表面に高い光触媒活性を有する透明被膜を有す
るので、防汚、抗菌、防黴および脱臭等の作用を有し、
さらにハードコート性、耐熱性、紫外線遮蔽性等の効果
を有している。また、基材が透明であれば透明性に優れ
た透明被膜付基材が得られる。The substrate with a transparent film thus obtained has a transparent film having a high photocatalytic activity on its surface, and thus has an effect such as antifouling, antibacterial, antifungal and deodorizing.
Further, it has effects such as hard coat property, heat resistance, and ultraviolet ray shielding property. Further, if the substrate is transparent, a substrate with a transparent coating having excellent transparency can be obtained.
【００５８】[0058]
【発明の効果】本発明に係る透明被膜形成用塗布液を用
いて基材上に透明被膜を形成すると、約１５０℃程度の
低温度で加熱しても硬度が高く、しかも緻密性に優れた
透明被膜が得られる。このためプラスチック、ガラスな
どの基材の表面にも光触媒活性の高い被膜が形成でき
る。According to the present invention, when a transparent film is formed on a substrate by using the coating solution for forming a transparent film according to the present invention, the hardness is high even when heated at a low temperature of about 150 ° C., and the compactness is excellent. A transparent coating is obtained. Therefore, a film having high photocatalytic activity can be formed on the surface of a substrate such as plastic and glass.
【００５９】また、バインダーの屈折率が複合酸化チタ
ン微粒子の屈折率とほぼ同じであるため、透明性が高
く、ヘイズが小さい被膜が得られる。しかも、バインダ
ー自身が光触媒機能を有し、かつ導電性であるため、複
合酸化チタン微粒子の光触媒能が促進され、被膜の光触
媒活性が高くなる。Further, since the refractive index of the binder is almost the same as that of the composite titanium oxide fine particles, a film having high transparency and small haze can be obtained. Moreover, since the binder itself has a photocatalytic function and is conductive, the photocatalytic ability of the composite titanium oxide fine particles is promoted, and the photocatalytic activity of the coating film is enhanced.
【００６０】さらに、本発明によれば、透明被膜を容易
に厚膜化することができる。Further, according to the present invention, the thickness of the transparent film can be easily increased.
【００６１】[0061]
【実施例】以下、本発明を実施例に基づき説明するが、
本発明はこれらの実施例に何ら限定されるものではな
い。Hereinafter, the present invention will be described based on examples.
The present invention is not limited to these examples.
【００６２】[0062]
【実施例１】酸化鉄・酸化チタン複合酸化物微粒子ゾル
の調製 Ｆｅ2Ｏ3に換算して０.４ｇの塩化第二鉄と、ＴiＯ2に
換算して９９.６ｇの四塩化チタンとを純水に溶解し、
１０ｋｇの混合水溶液を調製した。この混合水溶液に、
４℃の２８％のアンモニア水溶液を、液温が１０℃以上
にならないように冷却しながら急激に添加し、ｐＨが
７.５になった時点で添加を終了した。この時生成した
水和酸化鉄と水和酸化チタンの共沈ゲルの温度は９.８
℃であった。Example 1 Iron oxide / titanium oxide composite oxide fine particle sol
Dissolved ferric chloride 0.4g in terms of preparing Fe 2 O 3 of a titanium tetrachloride 99.6g in terms of TiO 2 in pure water,
10 kg of a mixed aqueous solution was prepared. In this mixed aqueous solution,
A 28% aqueous ammonia solution at 4 ° C. was rapidly added while cooling so that the liquid temperature did not exceed 10 ° C., and the addition was stopped when the pH reached 7.5. The temperature of the coprecipitated gel of hydrated iron oxide and hydrated titanium oxide formed at this time was 9.8.
° C.
【００６３】得られた共沈ゲルを脱水・洗浄した後、共
沈ゲル８８０ｇに、H2O2濃度３５重量％の過酸化水素水
９１０ｇおよび純水２００ｇを添加し、８０℃で３時間
加熱して黄橙色の溶液（Ａ液）１９９０ｇを得た。After the obtained coprecipitated gel was dehydrated and washed, 910 g of hydrogen peroxide having a H 2 O 2 concentration of 35% by weight and 200 g of pure water were added to 880 g of the coprecipitated gel, and heated at 80 ° C. for 3 hours. As a result, 1990 g of a yellow-orange solution (Solution A) was obtained.
【００６４】このＡ液９９５ｇに、３００５ｇの水を加
え、オートクレーブにて２００℃で２０時間加熱処理し
て、酸化鉄・酸化チタン複合酸化物微粒子が分散したゾ
ルを得た。To 995 g of the solution A, 3005 g of water was added, and the mixture was heated in an autoclave at 200 ° C. for 20 hours to obtain a sol in which iron oxide / titanium oxide composite oxide fine particles were dispersed.
【００６５】このゾルにメタノール４０００ｍｌを加え
た後、メチルトリメトキシシランを２ｇ加え、５０℃で
１時間熟成した後、溶媒置換により水を除去して固形分
濃度２０重量％の酸化鉄・酸化チタン複合酸化物微粒子
分散メタノールゾル２００ｇを得た。複合酸化物微粒子
の平均粒子径は、透過型電子顕微鏡写真により測定した
ところ、８ｎｍであった。After adding 4000 ml of methanol to the sol, adding 2 g of methyltrimethoxysilane, aging at 50 ° C. for 1 hour, removing water by solvent replacement to remove iron oxide / titanium oxide having a solid concentration of 20% by weight. 200 g of a mixed oxide fine particle-dispersed methanol sol was obtained. The average particle diameter of the composite oxide fine particles was 8 nm as measured by a transmission electron microscope photograph.
【００６６】バインダーの調製 前記Ａ液９９５ｇにキトサン５ｇを加え、８０℃で２時
間加熱してバインダーを調製した。 Preparation of Binder 5 g of chitosan was added to 995 g of the solution A, and the mixture was heated at 80 ° C. for 2 hours to prepare a binder.
【００６７】透明被膜形成用塗布液の調製 前記酸化鉄・酸化チタン複合酸化物微粒子が分散したメ
タノールゾル５０ｇと上記バインダー１００ｇを混合し
て透明被膜形成用塗布液を調製した。[0067] Preparation of transparent film-forming coating liquid wherein the iron oxide-titanium oxide composite oxide fine particles to prepare a dispersion methanol sol 50g and the transparent film-forming coating liquid by mixing the above binder 100 g.
【００６８】透明被膜付基材の作製 上記塗布液をガラス基材（５０ｍｍ×５０ｍｍ）上にス
ピナーで塗布し、８０℃で予備乾燥した後１２０℃で乾
燥した後、２００℃で加熱硬化して透明被膜付基材を作
製した。被膜の厚さは１μｍであり、被膜の硬度は鉛筆
硬度で６Ｈであった。 Preparation of Substrate with Transparent Coating The above coating solution was applied on a glass substrate (50 mm × 50 mm) with a spinner, preliminarily dried at 80 ° C., dried at 120 ° C., and cured by heating at 200 ° C. A substrate with a transparent coating was produced. The thickness of the coating was 1 μm, and the hardness of the coating was 6H in pencil hardness.
【００６９】光触媒活性の測定 石英製容器（縦１５０ｍｍ×横１５０ｍｍ×高さ６０ｍ
ｍ）に上記の被膜付基材を入れ、窒素ガスで置換した後
密閉し、次いで濃度が５０ｐｐｍとなるようにアセトア
ルデヒドを注入し、被膜の表面からの距離が１００ｍｍ
の高さよりブラックライト（紫外線波長 ３６５ｎｍ、
強度 ０.６ｍＷ／ｃｍ2）を１時間照射した。次いで容
器中に残存するアセトアルデヒドの濃度をガスクロマト
グラフィーにより測定し、アセトアルデヒドの減少率に
より光触媒活性を評価した。結果を表１に示す。 Measurement of Photocatalytic Activity A quartz container (150 mm long × 150 mm wide × 60 m high)
m), the substrate with the above-mentioned film was put therein, replaced with nitrogen gas, and then sealed. Then, acetaldehyde was injected so that the concentration became 50 ppm, and the distance from the surface of the film was 100 mm.
Black light (ultraviolet wavelength 365 nm,
Irradiation at an intensity of 0.6 mW / cm 2 ) was performed for 1 hour. Next, the concentration of acetaldehyde remaining in the container was measured by gas chromatography, and the photocatalytic activity was evaluated based on the reduction rate of acetaldehyde. Table 1 shows the results.
【００７０】[0070]
【実施例２】酸化バナジウム・酸化チタン複合酸化物微
粒子ゾルの調製 Ｖ2Ｏ5に換算して１.０ｇの硫酸バナジウムと、ＴiＯ2
に換算して９９.０ｇの四塩化チタンとを純水に溶解
し、１０ｋｇの混合水溶液を調製した。この混合水溶液
に、４℃の２８％アンモニア水溶液を、液温が１０℃以
上にならないように冷却しながら急激に添加し、ｐＨが
７.７になった時点で添加を終了した。この時生成した
水和酸化バナジウムと水和酸化チタンの共沈ゲルの温度
は９.５℃であった。Example 2 Vanadium oxide / titanium oxide composite oxide fine
Preparation of particle sol 1.0 g of vanadium sulfate in terms of V 2 O 5 and TiO 2
Then, 99.0 g of titanium tetrachloride was dissolved in pure water to prepare 10 kg of a mixed aqueous solution. To this mixed aqueous solution, a 28% aqueous ammonia solution at 4 ° C. was rapidly added while cooling so that the liquid temperature did not become 10 ° C. or higher. When the pH reached 7.7, the addition was terminated. The temperature of the coprecipitated gel of hydrated vanadium oxide and hydrated titanium oxide formed at this time was 9.5 ° C.
【００７１】こうして得られた水和酸化バナジウムと水
和酸化チタンの共沈ゲルを脱水・洗浄した後、共沈ゲル
８８０ｇに、３５％の過酸化水素水９１０ｇと純水２０
０ｇを加え、次いで８０℃で３時間加熱して緑色の溶液
（Ｂ液）１９９０ｇを得た。After the thus obtained coprecipitated gel of hydrated vanadium oxide and hydrated titanium oxide was dehydrated and washed, 910 g of 35% hydrogen peroxide solution and 920 g of pure water were added to 880 g of the coprecipitated gel.
0 g was added, followed by heating at 80 ° C. for 3 hours to obtain 1990 g of a green solution (Solution B).
【００７２】このＢ液９９５ｇに、３００５ｇの水を加
え、オートクレーブにて２００℃で２０時間加熱処理し
て酸化バナジウム・酸化チタン複合酸化物微粒子が分散
したゾルを得た。3005 g of water was added to 995 g of the solution B, and the mixture was heated at 200 ° C. for 20 hours in an autoclave to obtain a sol in which vanadium oxide / titanium oxide composite oxide fine particles were dispersed.
【００７３】このゾルにメタノール４０００ｍｌを加え
た後、メチルトリメトキシシランを２ｇ加え、５０℃で
１時間熟成した後、溶媒置換により水を除去して固形分
濃度２０重量％の酸化バナジウム・酸化チタン複合酸化
物微粒子分散メタノールゾル２００ｇを得た。複合酸化
物微粒子の平均粒子径を、透過型電子顕微鏡写真で測定
したところ、９ｎｍであった。After adding 4000 ml of methanol to the sol, adding 2 g of methyltrimethoxysilane and aging at 50 ° C. for 1 hour, water was removed by solvent replacement to remove vanadium oxide / titanium oxide having a solid concentration of 20% by weight. 200 g of a mixed oxide fine particle-dispersed methanol sol was obtained. The average particle size of the composite oxide fine particles was measured by a transmission electron microscope photograph, and was 9 nm.
【００７４】バインダーの調製 四塩化チタン７１.４ｇおよびオキシ塩化ジルコニウム
１５ｇを、５重量％の塩酸水溶液４００ｇに溶解した。
この水溶液に、５重量％のアンモニア水を添加してヒド
ロゲルを得た。これを濾過、洗浄し、得られた固形分濃
度１０重量％のケーキ１００ｇを純水で希釈して３重量
％の懸濁液としたのち、２８重量％の過酸化水素水３６
ｇを加え、９０℃、５時間加熱してチタンとジルコニウ
ムの複合過酸化物を含む液を得た。この液にキトサン３
ｇを添加し、８０℃、２時間加熱してバインダーを調製
した。 Preparation of Binder 71.4 g of titanium tetrachloride and 15 g of zirconium oxychloride were dissolved in 400 g of a 5% by weight aqueous hydrochloric acid solution.
To this aqueous solution, 5% by weight of aqueous ammonia was added to obtain a hydrogel. This was filtered and washed, and 100 g of the obtained cake having a solid content of 10% by weight was diluted with pure water to form a 3% by weight suspension.
g and heated at 90 ° C. for 5 hours to obtain a liquid containing a composite peroxide of titanium and zirconium. Chitosan 3
g was added and heated at 80 ° C. for 2 hours to prepare a binder.
【００７５】透明被膜形成用塗布液の調製 前記酸化バナジウム・酸化チタン複合酸化物微粒子分散
メタノールゾル５０ｇと上記バインダー１８６ｇを混合
して、透明被膜形成用塗布液を調製した。Preparation of Transparent Film Forming Coating Solution A transparent film forming coating solution was prepared by mixing 50 g of the above-mentioned vanadium oxide / titanium oxide composite oxide fine particle-dispersed methanol sol and 186 g of the binder described above.
【００７６】透明被膜付基材の作製 上記塗布液をガラス基材（５０ｍｍ×５０ｍｍ）上にス
ピナー法で塗布し、８０℃で予備乾燥した後１２０℃で
乾燥したのち、２００℃で加熱硬化して透明被膜付基材
を作製した。被膜の厚さは１μｍであり、被膜の硬度は
鉛筆硬度で６Ｈであった。作製した透明被膜付基材につ
いて、実施例１と同様にして光触媒活性を測定した。 Preparation of Substrate with Transparent Coating The above coating solution was applied to a glass substrate (50 mm × 50 mm) by a spinner method, preliminarily dried at 80 ° C., dried at 120 ° C., and then heat-cured at 200 ° C. Thus, a substrate with a transparent coating was produced. The thickness of the coating was 1 μm, and the hardness of the coating was 6H in pencil hardness. The photocatalytic activity of the prepared substrate with a transparent film was measured in the same manner as in Example 1.
【００７７】結果を表１に示す。Table 1 shows the results.
【００７８】[0078]
【実施例３】酸化ジルコニウム・酸化チタン複合酸化物
微粒子ゾルの調製 テトライソプロピルチタネート１００ｇとジルコニウム
ノルマルプロピレート１１.４ｇをイソプロピルアルコ
ール２８８.６ｇで希釈した。この溶液へ１７.５％の過
酸化水素水３８４ｇを添加したのち、５０℃で２時間加
熱した。さらに、溶液を８０℃１時間水熱処理し、複合
酸化物微粒子が分散したゾルを調製した。次に、ロータ
リーエバポレーターでイソプロピルアルコールおよび水
を蒸発させ、固形分濃度１０％まで濃縮して、酸化ジル
コニウム・酸化チタン複合酸化物微粒子ゾルを調製し
た。複合酸化物微粒子の平均粒子径を過型電子顕微鏡写
真で測定したところ、２６ｎｍであった。Embodiment 3 Zirconium oxide / titanium oxide composite oxide
Preparation of fine particle sol 100 g of tetraisopropyl titanate and 11.4 g of zirconium normal propylate were diluted with 288.6 g of isopropyl alcohol. After adding 384 g of 17.5% hydrogen peroxide solution to this solution, the solution was heated at 50 ° C. for 2 hours. Further, the solution was hydrothermally treated at 80 ° C. for 1 hour to prepare a sol in which the composite oxide fine particles were dispersed. Next, isopropyl alcohol and water were evaporated by a rotary evaporator and concentrated to a solid content of 10% to prepare a zirconium oxide / titanium oxide composite oxide fine particle sol. It was 26 nm when the average particle diameter of the composite oxide fine particles was measured by a scanning electron microscope photograph.
【００７９】透明被膜形成用塗布液の調製 上記複合酸化物微粒子が分散したゾル１００ｇと実施例
１と同様のバインダー１００ｇを混合して透明被膜形成
用塗布液を調製した。Preparation of Transparent Film Forming Coating Solution A transparent film forming coating solution was prepared by mixing 100 g of the sol in which the composite oxide fine particles were dispersed and 100 g of the same binder as in Example 1.
【００８０】透明被膜付基材の作製 上記で得た塗布液をガラス基材（５０ｍｍ×５０ｍｍ）
上にスピナーで塗布し、８０℃で予備乾燥した後１２０
℃で乾燥し、ついで２００℃で加熱硬化して透明被膜付
基材を作製した。被膜の厚さは１μｍであり、被膜の硬
度は鉛筆硬度で６Ｈであった。作製した透明被膜付基材
について、実施例１と同様にして光触媒活性を測定し
た。Preparation of Transparent Coated Substrate The coating solution obtained above was applied to a glass substrate (50 mm × 50 mm).
After spin-coating on the top and pre-drying at 80 ° C,
C., and then heat-cured at 200.degree. C. to produce a substrate with a transparent coating. The thickness of the coating was 1 μm, and the hardness of the coating was 6H in pencil hardness. The photocatalytic activity of the prepared substrate with a transparent film was measured in the same manner as in Example 1.
【００８１】結果を表１に示す。Table 1 shows the results.
【００８２】[0082]
【実施例４】酸化鉄・酸化ジルコニウム・酸化チタン複
合酸化物微粒子ゾルの調製 Ｆｅ2Ｏ3に換算して０.４ｇの塩化第二鉄と、ＺｒＯ2に
換算して０.４ｇのオキシ塩化ジルコニウムと、ＴiＯ2
に換算して９９.２ｇの四塩化チタンとを純水に溶解
し、１０ｋｇの混合水溶液を調製した。この混合水溶液
に、４℃の２８％のアンモニア水溶液を、液温が１０℃
以上にならないように冷却しながら急激に添加し、ｐＨ
が７.７になった時点で添加を終了した。この時生成し
た水和酸化鉄と水和ジルコニウムと水和酸化チタンの共
沈ゲルの温度は９.６℃であった。Embodiment 4 Iron oxide / zirconium oxide / titanium oxide double
Preparation of mixed oxide fine particle sol 0.4 g of ferric chloride in terms of Fe 2 O 3 , 0.4 g of zirconium oxychloride in terms of ZrO 2 , and TiO 2
Then, 99.2 g of titanium tetrachloride was dissolved in pure water to prepare 10 kg of a mixed aqueous solution. A 28% aqueous ammonia solution of 4 ° C. was added to the mixed aqueous solution at a liquid temperature of 10 ° C.
Add rapidly while cooling so that it does not exceed
When the value of 7.7 reached 7.7, the addition was terminated. The temperature of the co-precipitated gel of hydrated iron oxide, hydrated zirconium and hydrated titanium oxide formed at this time was 9.6 ° C.
【００８３】得られた共沈ゲルを脱水・洗浄した後、共
沈ゲル８８０ｇに、H2O2濃度３５重量％の過酸化水素水
９１０ｇおよび純水２００ｇを添加し、８０℃で３時間
加熱して黄橙色の溶液（Ｃ液）１９９０ｇを得た。After dehydrating and washing the obtained coprecipitated gel, 910 g of hydrogen peroxide solution having a H 2 O 2 concentration of 35% by weight and 200 g of pure water were added to 880 g of the coprecipitated gel, and heated at 80 ° C. for 3 hours. As a result, 1990 g of a yellow-orange solution (Solution C) was obtained.
【００８４】このＣ液９９５ｇに、３００５ｇの水を加
え、オートクレーブにて２００℃で２０時間加熱処理し
て、酸化鉄・酸化ジルコニウム・酸化チタン複合酸化物
微粒子が分散したゾルを得た。3005 g of water was added to 995 g of this solution C, and the mixture was heated in an autoclave at 200 ° C. for 20 hours to obtain a sol in which iron oxide / zirconium oxide / titanium oxide composite oxide fine particles were dispersed.
【００８５】このゾルにメタノール４０００ｍｌを加え
た後、メチルトリメトキシシランを２ｇ加え、５０℃で
１時間熟成した後、溶媒置換により水を除去して固形分
濃度２０重量％の酸化鉄・酸化ジルコニウム・酸化チタ
ン複合酸化物微粒子分散メタノールゾル２００ｇを得
た。複合酸化物微粒子の平均粒子径は、透過型電子顕微
鏡写真により測定したところ、８.５ｎｍであった。After adding 4000 ml of methanol to the sol, adding 2 g of methyltrimethoxysilane and aging at 50 ° C. for 1 hour, water was removed by solvent replacement to obtain an iron oxide / zirconium oxide having a solid content of 20% by weight. -200 g of titanium oxide composite oxide fine particle-dispersed methanol sol was obtained. The average particle size of the composite oxide fine particles was 8.5 nm as measured by a transmission electron micrograph.
【００８６】バインダーの調製 前記Ｃ液９９５ｇにキトサン５ｇを加え、８０℃で２時
間加熱してバインダーを調製した。 Preparation of Binder 5 g of chitosan was added to 995 g of Solution C, and the mixture was heated at 80 ° C. for 2 hours to prepare a binder.
【００８７】透明被膜形成用塗布液の調製 前記複合酸化物微粒子が分散したメタノールゾル５０ｇ
と前記バインダー１００ｇを混合して透明被膜形成用塗
布液を調製した。 Preparation of Coating Solution for Transparent Film Formation 50 g of methanol sol in which the composite oxide fine particles were dispersed
And 100 g of the binder were mixed to prepare a coating solution for forming a transparent film.
【００８８】透明被膜付基材の作製 上記で得た塗布液をガラス基材（５０ｍｍ×５０ｍｍ）
上にスピナーで塗布し、８０℃で予備乾燥した後１２０
℃で乾燥し、ついで２００℃で加熱硬化して透明被膜付
基材を作製した。被膜の厚さは１μｍであり、被膜の硬
度は鉛筆硬度で６Ｈであった。作製した透明被膜付基材
について、実施例１と同様にして光触媒活性を測定し
た。 Preparation of Substrate with Transparent Coating The coating solution obtained above was coated on a glass substrate (50 mm × 50 mm).
After spin-coating on the top and pre-drying at 80 ° C,
C., and then heat-cured at 200.degree. C. to produce a substrate with a transparent coating. The thickness of the coating was 1 μm, and the hardness of the coating was 6H in pencil hardness. The photocatalytic activity of the prepared substrate with a transparent film was measured in the same manner as in Example 1.
【００８９】結果を表１に示す。Table 1 shows the results.
【００９０】[0090]
【実施例５】バインダーの調製 ＴiＯ2に換算して１００ｇの四塩化チタンを純水に溶解
し、１０ｋｇの水溶液を調製した。この水溶液に、４℃
の２８％のアンモニア水溶液を、液温が１０℃以上にな
らないように冷却しながら急激に添加し、ｐＨが７.７
になった時点で添加を終了した。この時生成した水和酸
化チタンゲルの温度は９.５℃であった。Example 5 Preparation of Binder 100 g of titanium tetrachloride in terms of TiO 2 was dissolved in pure water to prepare a 10 kg aqueous solution. 4 ° C
Of 28% aqueous ammonia was rapidly added while cooling so that the temperature of the solution did not exceed 10 ° C., and the pH was adjusted to 7.7.
When it became, the addition was terminated. The temperature of the hydrated titanium oxide gel formed at this time was 9.5 ° C.
【００９１】得られたゲルを脱水・洗浄した後、共沈ゲ
ル８８０ｇに、H2O2濃度３５重量％の過酸化水素水９１
０ｇおよび純水２００ｇを添加し、８０℃で３時間加熱
して黄橙色の溶液（Ｄ液）１９９０ｇを得た。このＤ液
９９５ｇにキトサン５ｇを加え、８０℃で２時間加熱し
てバインダーを調製した。After the obtained gel was dehydrated and washed, 880 g of the coprecipitated gel was mixed with a hydrogen peroxide solution having a H 2 O 2 concentration of 35% by weight.
0 g and 200 g of pure water were added, and the mixture was heated at 80 ° C. for 3 hours to obtain 1990 g of a yellow-orange solution (Solution D). 5 g of chitosan was added to 995 g of the solution D, and the mixture was heated at 80 ° C. for 2 hours to prepare a binder.
【００９２】透明被膜形成用塗布液の調製 実施例１で調製した複合酸化物微粒子分散メタノールゾ
ル５０ｇと前記バインダー１００ｇを混合して透明被膜
形成用塗布液を調製した。Preparation of Transparent Film Forming Coating Solution A transparent film forming coating solution was prepared by mixing 50 g of the composite oxide fine particle-dispersed methanol sol prepared in Example 1 and 100 g of the binder described above.
【００９３】透明被膜付基材の作製 上記で得た塗布液をガラス基材（５０ｍｍ×５０ｍｍ）
上にスピナーで塗布し、８０℃で予備乾燥した後１２０
℃で乾燥し、ついで２００℃で加熱硬化して透明被膜付
基材を作製した。被膜の厚さは１μｍであり、被膜の硬
度は鉛筆硬度で６Ｈであった。作製した透明被膜付基材
について、実施例１と同様にして光触媒活性を測定し
た。 Preparation of Substrate with Transparent Coating The coating solution obtained above was coated on a glass substrate (50 mm × 50 mm).
After spin-coating on the top and pre-drying at 80 ° C,
C., and then heat-cured at 200.degree. C. to produce a substrate with a transparent coating. The thickness of the coating was 1 μm, and the hardness of the coating was 6H in pencil hardness. The photocatalytic activity of the prepared substrate with a transparent film was measured in the same manner as in Example 1.
【００９４】結果を表１に示す。Table 1 shows the results.
【００９５】[0095]
【比較例１】酸化ジルコニウム・酸化チタン複合酸化物
微粒子ゾルの調製 実施例３と同様にして、固形分濃度１０％の複合酸化物
微粒子を調製した。複合酸化物微粒子の平均粒子径は、
透過型電子顕微鏡写真により測定したところ、２５ｎｍ
であった。[Comparative Example 1] Zirconium oxide / titanium oxide composite oxide
Preparation of Fine Particle Sol In the same manner as in Example 3, composite oxide fine particles having a solid content of 10% were prepared. The average particle diameter of the composite oxide fine particles is
When measured by a transmission electron micrograph, 25 nm
Met.
【００９６】バインダーの調製 テトライソプロピルチタネート１００ｇをイソプロピル
アルコール２８８.６ｇで溶解し、この溶液にアセチル
アセトン２１ｇを添加し、チタンアセチルアセトネート
溶液を得た。このチタンアセチルアセトネート溶液に、
H2O2濃度２８重量％の過酸化水素水１０ｇを添加し、７
０℃で１時間加熱して、チタン過酸化物を含む液を得
た。この液と、キトサン１０ｇを純水１００ｇを溶解し
た水溶液とを混合し、８０℃で２時間加熱し、バインダ
ーを調製した。 Preparation of Binder 100 g of tetraisopropyl titanate was dissolved in 288.6 g of isopropyl alcohol, and 21 g of acetylacetone was added to this solution to obtain a titanium acetylacetonate solution. In this titanium acetylacetonate solution,
10 g of a hydrogen peroxide solution having an H 2 O 2 concentration of 28% by weight was added, and 7
The mixture was heated at 0 ° C. for 1 hour to obtain a liquid containing titanium peroxide. This solution was mixed with an aqueous solution in which 10 g of chitosan was dissolved in 100 g of pure water, and heated at 80 ° C. for 2 hours to prepare a binder.
【００９７】透明被膜形成用塗布液の調製 上記複合酸化チタンゾル（固形分１０重量％）１００ｇ
とバインダー１５３ｇとを混合して、透明被膜形成用塗
布液を調製した。 Preparation of coating liquid for forming transparent film 100 g of the above composite titanium oxide sol (solid content: 10% by weight)
And 153 g of a binder were mixed to prepare a coating solution for forming a transparent film.
【００９８】透明被膜付基材の作製 この透明被膜形成用塗布液をスピナーでガラス基板上に
塗布し、８０℃で予備乾燥したのち、１２０℃で乾燥
し、次いで２００℃で加熱硬化して、１μｍの膜厚を有
する透明被膜付基材を作製した。被膜の鉛筆硬度は、４
Ｈであった。作製した透明被膜付基材について、実施例
１と同様にして光触媒活性を測定した。Preparation of Transparent Coating Substrate This coating liquid for forming a transparent coating was applied on a glass substrate by a spinner, preliminarily dried at 80 ° C., dried at 120 ° C., and then heated and cured at 200 ° C. A substrate with a transparent coating having a thickness of 1 μm was prepared. The pencil hardness of the coating is 4
H. The photocatalytic activity of the prepared substrate with a transparent film was measured in the same manner as in Example 1.
【００９９】結果を表１に示す。Table 1 shows the results.
【０１００】[0100]
【表１】 [Table 1]
Claims (4)
が、水および／または有機溶媒からなる溶媒に溶解また
は分散してなる透明被膜形成用塗布液であって、［Ａ］
前記複合酸化チタン微粒子が、Ｃu,Ａg,Ｚn,Ｃd,Ｖ,Ｂ
i,Ｃr,Ｍo,ＭnおよびＦeからなる群から選ばれる１種ま
たは２種以上の元素と、Ｔiとからなる複合酸化チタン
微粒子であり、［Ｂ］前記バインダーが、 (b-1) チタン過酸化物 または (b-2) Ｃu,Ａg,Ｚn,Ｃd,Ａl,Ｚr,Ｓi,Ｓn,Ｖ,Ｎb,Ｓb,
Ｂi,Ｃr,Ｍo,Ｗ,ＭnおよびＦeからなる群から選ばれる
１種または２種以上の元素と、Ｔiとからなる複合チタ
ン過酸化物と、 (b-3) 有機高分子化合物とからなることを特徴とする透
明被膜形成用塗布液。1. A coating solution for forming a transparent film, wherein a composite titanium oxide fine particle and a binder are dissolved or dispersed in a solvent comprising water and / or an organic solvent, wherein [A]
The composite titanium oxide fine particles are composed of Cu, Ag, Zn, Cd, V, B
Composite titanium oxide fine particles comprising one or more elements selected from the group consisting of i, Cr, Mo, Mn and Fe, and Ti, and [B] the binder comprises (b-1) titanium oxide Oxide or (b-2) Cu, Ag, Zn, Cd, Al, Zr, Si, Sn, V, Nb, Sb,
A composite titanium peroxide comprising one or more elements selected from the group consisting of Bi, Cr, Mo, W, Mn and Fe, Ti, and (b-3) an organic polymer compound A coating solution for forming a transparent film, comprising:
が、水および／または有機溶媒からなる溶媒に溶解また
は分散してなる透明被膜形成用塗布液であって、［Ｃ］
前記複合酸化チタン微粒子が、Ａl,Ｚr,Ｓi,Ｓn,Ｎb,Ｓ
bおよびＷからなる群から選ばれる１種または２種以上
の元素と、Ｔiとからなる複合酸化チタン微粒子であ
り、［Ｄ］前記バインダーが、 (d-1) Ｃu,Ａg,Ｚn,Ｃd,Ｖ,Ｂi,Ｃr,Ｍo,ＭnおよびＦe
からなる群から選ばれる１種または２種以上の元素と、
Ｔiとからなる複合チタン過酸化物と、 (d-2) 有機高分子化合物とからなることを特徴とする透
明被膜形成用塗布液。2. A coating solution for forming a transparent film, wherein the composite titanium oxide fine particles and a binder are dissolved or dispersed in a solvent composed of water and / or an organic solvent, wherein [C]
The composite titanium oxide fine particles are composed of Al, Zr, Si, Sn, Nb, S
Composite titanium oxide fine particles comprising one or more elements selected from the group consisting of b and W, and Ti, and [D] the binder comprises (d-1) Cu, Ag, Zn, Cd, V, Bi, Cr, Mo, Mn and Fe
One or more elements selected from the group consisting of:
A coating liquid for forming a transparent film, comprising: a composite titanium peroxide composed of Ti; and (d-2) an organic polymer compound.
を特徴とする請求項１または２に記載の透明被膜形成用
塗布液。3. The coating liquid for forming a transparent film according to claim 1, wherein the organic polymer compound is a polysaccharide.
膜形成用塗布液を用いて形成された透明被膜を有するこ
とを特徴とする透明被膜付基材。4. A substrate with a transparent coating, comprising a transparent coating formed by using the coating liquid for forming a transparent coating according to claim 1.
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|---|---|---|---|
| JP36121197A JP3755852B2 (en) | 1997-12-26 | 1997-12-26 | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36121197A JP3755852B2 (en) | 1997-12-26 | 1997-12-26 | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11188270A true JPH11188270A (en) | 1999-07-13 |
| JP3755852B2 JP3755852B2 (en) | 2006-03-15 |
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ID=18472647
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|---|---|---|---|
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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