JPH10337478A - Titanium oxide sol for photocatalyst, production and utilization of photocatalytic polyfunctional member - Google Patents
Titanium oxide sol for photocatalyst, production and utilization of photocatalytic polyfunctional memberInfo
- Publication number
- JPH10337478A JPH10337478A JP9150756A JP15075697A JPH10337478A JP H10337478 A JPH10337478 A JP H10337478A JP 9150756 A JP9150756 A JP 9150756A JP 15075697 A JP15075697 A JP 15075697A JP H10337478 A JPH10337478 A JP H10337478A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- titanium
- compound
- photocatalyst
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 33
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 33
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- -1 aluminum compound Chemical class 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- 150000002363 hafnium compounds Chemical class 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 150000003752 zinc compounds Chemical class 0.000 claims description 3
- 150000003755 zirconium compounds Chemical class 0.000 claims description 3
- 238000010304 firing Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 31
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 16
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000003373 anti-fouling effect Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 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
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 3
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 3
- 239000004904 UV filter Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000002504 physiological saline solution Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 241000233866 Fungi Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 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 1
- HRJSLUPAMXKPPM-UHFFFAOYSA-N 5-methyl-2-(3-methylphenyl)pyrazol-3-amine Chemical compound N1=C(C)C=C(N)N1C1=CC=CC(C)=C1 HRJSLUPAMXKPPM-UHFFFAOYSA-N 0.000 description 1
- 241000186361 Actinobacteria <class> Species 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000510930 Brachyspira pilosicoli Species 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化チタン光触媒
の形成剤である酸化チタン光触媒用ゾル、このゾルから
光触媒作用を持つ多機能部材を製造する方法およびこの
多機能部材の持つ光触媒作用を利用する多機能部材の使
用方法に関する。The present invention relates to a sol for a titanium oxide photocatalyst which is a forming agent of a titanium oxide photocatalyst, a method for producing a multifunctional member having a photocatalytic action from the sol, and a photocatalytic action of the multifunctional member. The present invention relates to a method of using a multifunctional member.
【０００２】[0002]
【従来の技術】半導体に光が照射されると、その照射面
に強い還元作用を持つ電子と強い酸化作用を持つ正孔が
生じる。物質がこのような状態の半導体の表面に接触す
ると、半導体の強い酸化還元作用を受けて分解される。2. Description of the Related Art When a semiconductor is irradiated with light, electrons having a strong reducing action and holes having a strong oxidizing action are generated on the irradiated surface. When a substance comes into contact with the surface of a semiconductor in such a state, the substance is decomposed by a strong oxidation-reduction action of the semiconductor.
【０００３】近年、上述の半導体の光触媒作用が、空気
中および水中に含まれる有害物質の分解または無害化、
生活空間等における防臭、防汚、殺菌等、様々な環境浄
化技術に利用されるようになってきた。光触媒用の半導
体としては、主に酸化チタンが用いられている。[0003] In recent years, the photocatalytic action of the above-mentioned semiconductors has decomposed or detoxified harmful substances contained in air and water.
It has been used for various environmental purification technologies such as deodorization, antifouling, and sterilization in living spaces and the like. As a semiconductor for a photocatalyst, titanium oxide is mainly used.
【０００４】従来、光触媒として利用する場合には、酸
化チタン等の粉末を溶液に懸濁させて、その状態（以
下、酸化チタンゾルと記す）で使用してきた。しかし、
取り扱いの容易さ、幅広い応用性の観点からは、光触媒
を支持体に固定化した状態で使用する方が有利である。
したがって、実用性を考慮して、支持体に光触媒を固定
して用いる方法が開発されている。Conventionally, when used as a photocatalyst, a powder of titanium oxide or the like has been suspended in a solution and used in that state (hereinafter referred to as titanium oxide sol). But,
From the viewpoint of easiness of handling and wide applicability, it is more advantageous to use the photocatalyst immobilized on a support.
Therefore, in consideration of practicality, a method of using a photocatalyst fixed to a support has been developed.
【０００５】支持体に酸化チタンを固定化する方法とし
ては、酸化チタンゾルを支持体に付着させ、その後支持
体とともに加熱し、焼成する方法が一般的である。しか
し、酸化チタンゾルに含まれる酸化チタンの微粒子は、
焼成の際に粒成長を起こしやすい。そのために、光触媒
反応の反応性に重要な影響を及ぼす比表面積が低下し、
その結果、光触媒としての性能が著しく低下するという
ことが起こる。[0005] As a method of immobilizing titanium oxide on a support, a method of attaching a titanium oxide sol to the support, followed by heating with the support and baking is generally used. However, the fine particles of titanium oxide contained in the titanium oxide sol,
Grain growth tends to occur during firing. As a result, the specific surface area, which has a significant effect on the reactivity of the photocatalytic reaction, decreases,
As a result, the performance as a photocatalyst is significantly reduced.
【０００６】焼成の際の粒成長を防止する対策として、
支持体に塗布する前に、酸化チタンゾルを水熱処理する
ことによって、ゾル中の酸化チタンの微粒子を結晶化さ
せる方法が提案されている（特開平６−２９３５１９号
公報）。十分に結晶化した酸化チタン粒子は焼成の際に
粒成長を起こしにくく、また光照射により生成した電子
と正孔の分離効率が高いので、比較的高い光触媒活性が
得られるとされている。しかし、水熱処理は高温高圧下
での処理であるとともに、溶液濃度、温度、圧力、ＰＨ
等に微妙なコントロールが要求されるため、光触媒の量
産には不向きであった。[0006] As a measure for preventing grain growth during firing,
A method of crystallizing fine particles of titanium oxide in a sol by applying a hydrothermal treatment to the titanium oxide sol before coating on a support has been proposed (JP-A-6-293519). It is said that titanium oxide particles that are sufficiently crystallized hardly cause grain growth during firing and have a high efficiency of separating electrons and holes generated by light irradiation, so that relatively high photocatalytic activity can be obtained. However, the hydrothermal treatment is a treatment under high temperature and high pressure, and the solution concentration, temperature, pressure, PH
And so on, which are not suitable for mass production of photocatalysts.
【０００７】このほか、酸化チタンゾルに新たな物質を
添加する方法も提案されている（特開平８−９９０４１
号公報）。この方法の場合には、酸化チタンゾルにポリ
エチレングリコールを添加し、そのゾルを支持体に付着
させ、加熱焼成する処理が採られている。焼成後の酸化
チタン膜の性状は、多孔質状とされている。しかし、こ
の方法では、光触媒として十分な活性を得るためには膜
の多層化が必要である。また、焼成温度の上限が７００
℃に制限されているので、高温度での焼成ができない。
そのために、酸化チタン膜の強度を高くすることができ
ないので、光触媒としての耐久性に乏しい等の問題点が
ある。[0007] In addition, a method of adding a new substance to a titanium oxide sol has been proposed (JP-A-8-99041).
No.). In the case of this method, polyethylene glycol is added to a titanium oxide sol, the sol is adhered to a support, and a heat baking treatment is employed. The properties of the titanium oxide film after firing are porous. However, this method requires a multilayer film in order to obtain sufficient activity as a photocatalyst. Also, the upper limit of the firing temperature is 700
Since it is limited to ° C., it cannot be fired at a high temperature.
Therefore, since the strength of the titanium oxide film cannot be increased, there is a problem that the durability as a photocatalyst is poor.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、焼成により
酸化チタン膜を形成する際に、酸化チタンの粒成長を防
止することが可能な酸化チタン光触媒用ゾル、このゾル
から優れた光触媒作用を持つ多機能部材を製造する方法
および得られた多機能部材の使用方法を提供することを
目的とする。SUMMARY OF THE INVENTION The present invention relates to a sol for a titanium oxide photocatalyst capable of preventing the growth of titanium oxide grains when a titanium oxide film is formed by firing, and an excellent photocatalytic action from the sol. An object of the present invention is to provide a method of manufacturing a multifunctional member having the same and a method of using the obtained multifunctional member.
【０００９】[0009]
【課題を解決するための手段】本発明の酸化チタン光触
媒用ゾル、そのゾルを用いた光触媒作用を持つ多機能部
材の製造方法および多機能部材の使用方法の特徴は、そ
れぞれ下記（１）、（２）および（３）のとおりであ
る。The sol for titanium oxide photocatalyst of the present invention, the method for producing a multifunctional member having a photocatalytic activity using the sol, and the method for using the multifunctional member are as follows: (2) and (3).
【００１０】（１）ポリビニルピロリドンとチタン化合
物を含む酸化チタン光触媒用ゾル。(1) A titanium oxide photocatalyst sol containing polyvinylpyrrolidone and a titanium compound.
【００１１】このゾルには、ポリビニルピロリドンとチ
タン化合物の化学反応によって形成される有機チタン錯
体を含んでいてもよい。また、ジルコニウム化合物、亜
鉛化合物、珪素化合物、ハフニウム化合物、アルミニウ
ム化合物およびほう素化合物のうちの少なくとも１種を
含むことが好ましい。This sol may contain an organic titanium complex formed by a chemical reaction between polyvinylpyrrolidone and a titanium compound. Further, it is preferable to include at least one of a zirconium compound, a zinc compound, a silicon compound, a hafnium compound, an aluminum compound and a boron compound.
【００１２】（２）支持体の表面に、上記（１）の酸化
チタン触媒用ゾルを付着させた後焼成することにより、
支持体の表面に酸化チタン膜を形成させることによる光
触媒作用を持つ多機能部材の製造方法。(2) The titanium oxide catalyst sol of the above (1) is adhered to the surface of the support, followed by firing, whereby
A method for producing a multifunctional member having a photocatalytic action by forming a titanium oxide film on the surface of a support.
【００１３】（３）上記（２）の方法によって得られる
多機能部材により、光照射下で大気中または水中の物質
を処理する多機能部材の使用方法。(3) A method of using a multifunctional member for treating a substance in the air or water under light irradiation by using the multifunctional member obtained by the method (2).
【００１４】なお、本発明のゾルには、チタン化合物お
よびポリビニルピロリドンの基本構成成分のほかに、こ
れらの成分を溶解するための溶媒を含んでいる。The sol of the present invention contains, in addition to the basic components of the titanium compound and polyvinylpyrrolidone, a solvent for dissolving these components.
【００１５】本発明では、下記の〜により、焼成に
より酸化チタン膜を形成する際に、酸化チタンの粒成長
を防止し、比表面積が大きく、光触媒作用に優れた酸化
チタン膜を得ている。According to the present invention, when forming a titanium oxide film by firing, a titanium oxide film having a large specific surface area and excellent photocatalytic action is obtained by forming the titanium oxide film by firing as described below.
【００１６】 ゾルに、酸化チタン源として、酸化チ
タンの前駆体物質であるチタン化合物を配合し、おもに
加水分解を起こさせて酸化チタンまたは水酸化チタンと
した状態で、ポリビニルピロリドンと共存させる。その
ために、微細な酸化チタンなどの粒子がポリビニルピロ
リドンに保持された状態で、均一に分散したゾルが得ら
れる。A sol is mixed with a titanium compound, which is a precursor of titanium oxide, as a titanium oxide source, and is mainly co-existed with polyvinylpyrrolidone in a state where hydrolysis is caused to form titanium oxide or titanium hydroxide. Therefore, a sol in which fine particles such as titanium oxide are uniformly dispersed in a state of being held by polyvinylpyrrolidone can be obtained.
【００１７】 チタン化合物とポリビニルピロリドン
との反応によって、ゾル中に有機チタン錯体が生成する
場合もある。この有機チタン錯体は、チタン化合物がポ
リビニルピロリドンのピロリドン基に結合した状態にあ
るため、ゾル中で細かく分散して存在する。An organic titanium complex may be generated in a sol by a reaction between a titanium compound and polyvinylpyrrolidone. Since this titanium compound is in a state where the titanium compound is bonded to the pyrrolidone group of polyvinylpyrrolidone, it is finely dispersed in the sol.
【００１８】 ポリビニルピロリドンは、４００℃程
度まで熱分解を起こさない。したがって、ゾルが支持体
に塗布された状態で焼成された場合、酸化チタン等の微
粒子は約４００℃まで加熱される間に、微粒子状のまま
酸化チタンとして結晶化する。約４００℃を超える温度
から粒成長が始まるため、その結果として、粒が極めて
微細で、比表面積が大きい酸化チタン膜が得られる。[0018] Polyvinylpyrrolidone does not undergo thermal decomposition up to about 400 ° C. Therefore, when the sol is fired in a state of being applied to the support, the fine particles such as titanium oxide crystallize as titanium oxide in the form of fine particles while being heated to about 400 ° C. Since the grain growth starts from a temperature exceeding about 400 ° C., as a result, a titanium oxide film having extremely fine grains and a large specific surface area is obtained.
【００１９】[0019]
【発明の実施の形態】以下に本発明について具体的に説
明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.
【００２０】（ａ）ゾルの組成 本発明のゾルは、前述のように、おもに加水分解を起こ
した酸化チタン等のチタン化合物、ポリビニルピロリド
ンおよび溶媒で構成される。このゾルは、水、アルコー
ル等の溶媒中で前駆体物質としてのチタン化合物とポリ
ビニルピロリドンとをよく混合し、必要に応じて加熱す
ることによって調製することができる。本発明のゾル
は、水に対する安定性に優れているので、取り扱いが容
易という特長がある。(A) Composition of Sol As described above, the sol of the present invention is mainly composed of a hydrolyzed titanium compound such as titanium oxide, polyvinylpyrrolidone and a solvent. This sol can be prepared by thoroughly mixing a titanium compound as a precursor substance and polyvinylpyrrolidone in a solvent such as water or alcohol, and heating as necessary. The sol of the present invention has an advantage that it is easy to handle since it has excellent stability to water.
【００２１】上記の構成の本発明のゾル中には、有機チ
タン錯体が存在する場合がある。。この錯体は、焼成の
際の酸化チタンの粒成長の抑制に効果的である。ただ
し、有機チタン錯体が存在しない場合でも、実用上十分
に比表面積が大きい酸化チタン膜を得ることができる。An organic titanium complex may be present in the sol of the present invention having the above structure. . This complex is effective in suppressing the growth of titanium oxide grains during firing. However, even when an organic titanium complex does not exist, a titanium oxide film having a specific surface area sufficiently large for practical use can be obtained.
【００２２】本発明のゾルに配合されるチタン化合物と
しては、チタンイソプロポキシド、チタンブトキシド等
のチタンアルコキシド、硫酸チタン、４塩化チタン、チ
タンアセチルアセトネート等、加水分解などによって容
易に酸化チタンに変わる化合物が適当である。このほ
か、ＴｉＯ2 で表されるアナターゼ型酸化チタン、ルチ
ル型酸化チタン、非晶質酸化チタンのほか、水酸化チタ
ン、含水酸化チタン等の微粒子、さらには前駆体物質の
反応基（例えば、チタンアルコキシドではアルコキシド
部分）が加水分解などを起こし、酸化チタン粒子として
ネットワークを作った後も、その表面には未反応の反応
基が残った状態の酸化チタン粒子なども好適である。As the titanium compound to be incorporated in the sol of the present invention, titanium alkoxide such as titanium isopropoxide and titanium butoxide, titanium sulfate, titanium tetrachloride, titanium acetylacetonate and the like can be easily converted to titanium oxide by hydrolysis or the like. Varying compounds are suitable. In addition, in addition to anatase-type titanium oxide, rutile-type titanium oxide, and amorphous titanium oxide represented by TiO 2 , fine particles such as titanium hydroxide and hydrated titanium oxide, and a reactive group of a precursor substance (for example, titanium Even after the alkoxide portion of the alkoxide undergoes hydrolysis or the like to form a network as titanium oxide particles, titanium oxide particles in which unreacted reactive groups remain on the surface thereof are also suitable.
【００２３】ポリビニルピロリドンとチタン化合物とを
共存させるためには、これらのチタン化合物単独または
２種類以上を混合して用いてもよい。In order to allow polyvinylpyrrolidone and a titanium compound to coexist, these titanium compounds may be used alone or in combination of two or more.
【００２４】ゾル中のチタン化合物の含有率は、０．０
１ｍｏｌ／ｌ以上、２ｍｏｌ／ｌ以下が好ましい。チタ
ン化合物の含有率が０．０１ｍｏｌ／ｌ未満の場合に
は、ゾルを１回塗布した後の焼成では、光触媒活性を発
揮させるのに十分な膜厚の酸化チタン膜が得られない。
そのため、多層化が必要となり生産性が低下する傾向が
ある。一方、２ｍｏｌ／ｌを超えると、通常の塗布法で
は、焼成後の酸化チタン膜にクラックが発生したり、く
もりが生じることがある。The content of the titanium compound in the sol is 0.0
1 mol / l or more and 2 mol / l or less are preferable. When the content of the titanium compound is less than 0.01 mol / l, a titanium oxide film having a film thickness sufficient to exhibit photocatalytic activity cannot be obtained by baking after applying the sol once.
Therefore, multilayering is required and productivity tends to decrease. On the other hand, if it exceeds 2 mol / l, cracks or clouding may occur in the titanium oxide film after firing in a usual coating method.
【００２５】ゾル中のポリビニルピロリドンの含有率
は、０．１重量％以上、溶媒への溶解度以下が望まし
い。０．１重量％未満の場合には、ポリビニルピロリド
ンの効果が得られないので、焼成後の酸化チタンの比表
面積が十分大きくならない。そのために、光触媒活性の
高い酸化チタンが得られない。ポリビニルピロリドンの
含有率が溶解度を超える場合には、ゾル内に不溶のポリ
ビニルピロリドンが生じ凝集するために、製膜性が悪く
なること、焼成後の酸化チタン膜にむらやクラックが生
じやすいことなどの問題が起こる。The content of polyvinylpyrrolidone in the sol is desirably not less than 0.1% by weight and not more than the solubility in a solvent. When the amount is less than 0.1% by weight, the effect of polyvinylpyrrolidone cannot be obtained, so that the specific surface area of the fired titanium oxide does not become sufficiently large. Therefore, titanium oxide having high photocatalytic activity cannot be obtained. When the content of polyvinylpyrrolidone exceeds the solubility, insoluble polyvinylpyrrolidone is generated in the sol and agglomerated, so that the film forming property is deteriorated, and unevenness and cracks are easily generated in the titanium oxide film after firing. The problem arises.
【００２６】ポリビニルピロリドンの分子量は、１２０
万以下が望ましい。分子量が１２０万を超えると、ゾル
の粘度が高くなりすぎるので、支持体への塗布に支障を
きたす。また、支持体とともにゾルを焼成し酸化チタン
膜を得る際に、ポリビニルピロリドンの分解、揮発が起
こりにくいので、酸化チタン膜の中に有機物が残留しや
すい。その結果、光触媒としての性能が低下する。ポリ
ビニルピロリドンのより好ましい分子量は１０万以下で
ある。分子量の下限は約１千とするのがよい。ただし、
分子量が低い場合には、十分な光触媒活性を得るために
はゾル中のポリビニルピロリドンの割合を高くする必要
があるので、経済性の観点から１万以上がより好まし
い。上記の範囲内の分子量の場合には、ゾルの粘度も高
くないので取り扱い性にも優れ、焼成後の酸化チタンの
光触媒活性も高い。The molecular weight of polyvinylpyrrolidone is 120
It is desirable that it is less than 10,000. When the molecular weight exceeds 1.2 million, the viscosity of the sol becomes too high, which hinders the application to the support. Further, when the sol is fired together with the support to obtain a titanium oxide film, the decomposition and volatilization of polyvinylpyrrolidone hardly occur, so that an organic substance easily remains in the titanium oxide film. As a result, the performance as a photocatalyst decreases. The more preferred molecular weight of polyvinylpyrrolidone is 100,000 or less. The lower limit of the molecular weight is preferably about 1,000. However,
When the molecular weight is low, it is necessary to increase the proportion of polyvinylpyrrolidone in the sol in order to obtain a sufficient photocatalytic activity. When the molecular weight is in the above range, the viscosity of the sol is not high, so that the handleability is excellent and the photocatalytic activity of the calcined titanium oxide is high.
【００２７】なお、チタン化合物とポリビニルピロリド
ンの組成比は、ポリビニルピロリドンの含有率からモノ
マー部分をモル換算した値に対して、チタン化合物はモ
ル比で０．１から１０までの範囲が好ましい。この範囲
内の場合には、ゾルの焼成により、高い光触媒活性を持
った酸化チタンを得るのが容易である。The composition ratio of the titanium compound and polyvinylpyrrolidone is preferably in the range of 0.1 to 10 in terms of the molar ratio of the titanium compound to the value obtained by converting the monomer portion from the polyvinylpyrrolidone content to the molar ratio. When it is in this range, it is easy to obtain titanium oxide having high photocatalytic activity by baking the sol.
【００２８】また、本発明の酸化チタン光触媒形成用ゾ
ルには、ジルコニウム化合物、亜鉛化合物、珪素化合
物、ハフニウム化合物、アルミニウム化合物およびほう
素化合物のうちの少なくとも１種の金属化合物を含有さ
せてもよい。これらの金属化合物は、焼成後の酸化チタ
ンの光触媒活性を向上させる作用を持っている。これら
の金属化合物には、粒径３０ｎｍ以下の微粒子状の酸化
物または酸化物の前駆体となるアルコキシド類、塩化
物、硝酸塩などが適している。その中でも、高い光触媒
活性を得るには、チタン化合物と最もよく混合するアル
コキシド類が好ましい。The sol for forming a titanium oxide photocatalyst of the present invention may contain at least one metal compound of a zirconium compound, a zinc compound, a silicon compound, a hafnium compound, an aluminum compound and a boron compound. . These metal compounds have the effect of improving the photocatalytic activity of the calcined titanium oxide. As these metal compounds, oxides in the form of fine particles having a particle size of 30 nm or less, or alkoxides, chlorides, and nitrates that are precursors of the oxides are suitable. Among them, alkoxides that are most often mixed with a titanium compound are preferable for obtaining high photocatalytic activity.
【００２９】上記の金属化合物のゾル中の含有率は、チ
タン化合物に対して、モル比で ０．０１〜０．５が望
ましい。０．０１未満では金属化合物の効果が十分に発
揮されない。また、０．５を超えると、焼成の際酸化チ
タンの結晶化が起こりにくくなること、酸化チタンの構
造が失われることなどのために、光触媒としての性能が
低下しやすい。The content of the metal compound in the sol is desirably 0.01 to 0.5 in a molar ratio with respect to the titanium compound. If it is less than 0.01, the effect of the metal compound cannot be sufficiently exerted. On the other hand, if it exceeds 0.5, the performance as a photocatalyst is liable to be deteriorated because crystallization of titanium oxide hardly occurs during firing and the structure of titanium oxide is lost.
【００３０】これらの金属化合物をゾルに添加する場合
には、均一な組成のゾルにするために、加熱し環流処理
を施すことが好ましい。When these metal compounds are added to the sol, it is preferable to heat and carry out a reflux treatment in order to obtain a sol having a uniform composition.
【００３１】さらに、本発明のゾルには、必要に応じて
ジエタノールアミン、トリエタノールアミン等のアルコ
ールアミン類や、１．３−プロパンジオール、アセチル
アセトン等のゾル自体の乾燥の抑制およびゾルに含まれ
る酸化チタン微粒子の凝集の抑制等に効果のある添加剤
を含有させてもよい。これらの添加剤の量は、チタン化
合物のモル比に対して０．１〜２．０程度が適当であ
る。Further, the sol of the present invention may contain, if necessary, drying of the sol itself such as alcoholamines such as diethanolamine and triethanolamine and 1.3-propanediol and acetylacetone, and oxidation included in the sol. An additive which is effective in suppressing aggregation of the titanium fine particles may be contained. The amount of these additives is suitably about 0.1 to 2.0 with respect to the molar ratio of the titanium compound.
【００３２】（ｂ）焼成 本発明のゾルを支持体に塗布し、加熱焼成することによ
って光触媒作用を持つ多機能部材を製造する方法につい
て説明する。(B) Firing A method for producing a multifunctional member having a photocatalytic action by applying the sol of the present invention to a support and heating and firing the sol will be described.
【００３３】支持体の材質としては、ステンレス鋼、炭
素鋼、めっきされた鋼、アルミニウム、チタン等の金属
材料、セラミック、陶磁器、ガラス、石英等の無機材料
などが適している。また、これらの材料で構成された複
合材料でもよい。支持体の形状は、多機能部材としての
用途等に応じて決めるのがよい。厚板、薄板などの板
状、ビーズのような球状またはそのまま製品として使用
されるような複雑な形状であってよい。なお、支持体の
表面性状は多孔質でも緻密質でもよい。Suitable materials for the support include metal materials such as stainless steel, carbon steel, plated steel, aluminum and titanium, and inorganic materials such as ceramic, ceramics, glass and quartz. Further, a composite material composed of these materials may be used. The shape of the support is preferably determined according to the use as a multifunctional member. It may be in the form of a plate such as a thick plate or a thin plate, a spherical shape such as a bead, or a complicated shape such as used as a product as it is. The surface property of the support may be porous or dense.
【００３４】ゾルを支持体に塗布する方法には、スピン
コーティング、ディップコーティング、スプレーコーテ
ィング、バーコーティング、ロールコーティング等の方
法がある。塗布した後、オーブン加熱、温風等により必
要に応じて強制的に乾燥させるのもよい。The method of applying the sol to the support includes spin coating, dip coating, spray coating, bar coating, roll coating and the like. After the application, it may be forcibly dried as required by oven heating, warm air or the like.
【００３５】上述のような方法で支持体にゾルを塗布し
た後、支持体とともに加熱、焼成し、支持体の表面に酸
化チタン膜を固定する。After the sol is applied to the support by the method as described above, the sol is heated and baked together with the support to fix the titanium oxide film on the surface of the support.
【００３６】焼成温度は、酸化チタン粒子が十分に結晶
化を起こす温度で、さらにゾルに含まれる有機化合物が
速やかに分解、揮発する温度とするのがよい。具体的に
は４００℃以上、１０００℃以下が好ましい。４００℃
未満では分解、揮発すべき溶媒、ポリビニルピロリドン
等の有機物が酸化チタン膜内に残留しやすい。そのため
に、光触媒活性が不十分になりやすく、外観的にも透明
で均一な膜質の酸化チタン膜を得にくい。一方、焼成温
度が１０００℃を超えると、酸化チタンの粒成長が著し
く、酸化チタンの比表面積が低下するので、十分に高い
光触媒活性が得られない。焼成温度のより好ましい範囲
は、５００℃以上、８００℃以下である。The firing temperature is preferably a temperature at which the titanium oxide particles sufficiently crystallize, and a temperature at which the organic compound contained in the sol is quickly decomposed and volatilized. Specifically, the temperature is preferably from 400 ° C. to 1000 ° C. 400 ° C
If it is less than 3, the solvent to be decomposed and volatilized, and organic substances such as polyvinylpyrrolidone tend to remain in the titanium oxide film. Therefore, the photocatalytic activity tends to be insufficient, and it is difficult to obtain a titanium oxide film having a transparent and uniform film quality in appearance. On the other hand, when the firing temperature exceeds 1000 ° C., the grain growth of titanium oxide is remarkable, and the specific surface area of titanium oxide decreases, so that a sufficiently high photocatalytic activity cannot be obtained. A more preferable range of the firing temperature is 500 ° C. or more and 800 ° C. or less.
【００３７】焼成温度が上記の範囲の場合には、酸化チ
タンの結晶構造は光触媒として有効なアナターゼ型とな
り、結晶粒も微細なため、光触媒活性に優れた機能性部
材が得られる。When the calcination temperature is in the above range, the crystal structure of titanium oxide is an anatase type effective as a photocatalyst and the crystal grains are fine, so that a functional member having excellent photocatalytic activity can be obtained.
【００３８】酸化チタン膜の膜厚は、２０ｎｍから２μ
ｍ程度が好ましい。膜厚が２０ｎｍ未満の場合には、十
分な光触媒活性が得られないことがある。膜厚が２μｍ
を超えると光透過性が低下し、膜の機械的強度が低下す
る傾向がある。ただし、本発明のゾルの場合には、スピ
ンコーティング、ディップコーティング等厚膜が形成し
にくい塗布法でも、１回の操作で十分な光触媒活性を持
つ膜厚の酸化チタン膜が得られる。The thickness of the titanium oxide film is from 20 nm to 2 μm.
m is preferable. When the film thickness is less than 20 nm, sufficient photocatalytic activity may not be obtained. 2 μm thick
If the ratio exceeds the above range, the light transmittance tends to decrease, and the mechanical strength of the film tends to decrease. However, in the case of the sol of the present invention, a titanium oxide film having a sufficient photocatalytic activity can be obtained by a single operation even with a coating method such as spin coating and dip coating in which a thick film is difficult to form.
【００３９】焼成温度までの加熱速度は、２０℃／分以
下が好ましい。急速に加熱すると、光触媒性能の上では
ほとんど問題にはならないが、有機物の分解、揮発が同
時に、かつ急激に起きるため、酸化チタン膜に光沢むら
やクラックが発生することがある。The heating rate up to the firing temperature is preferably 20 ° C./min or less. When heated rapidly, there is almost no problem in terms of photocatalytic performance, but the decomposition and volatilization of organic substances occur simultaneously and rapidly, which may cause uneven gloss and cracks in the titanium oxide film.
【００４０】（ｃ）多機能部材の使用方法 上記の方法で得られる光触媒作用を有する多機能部材
は、太陽光や蛍光灯、ブラックライト、水銀灯、キセノ
ン灯等からの光によって、光触媒作用を発現する。この
触媒作用によって、様々な有害物質、付着物質などの分
解、除去、無害化に優れた効果を発揮する。本発明の方
法で得られる多機能部材のおもな用途としては、空気中
または水中に含まれる有害物質および汚染物質の分解、
除去がある。その対象となる物質は、空気中に含まれる
ＮＯＸ、ＳＯＸ、フロン、アルデヒド類、アミン類、メ
ルカプタン類、アルコール類、ＢＴＸ、フェノール類等
の有機化合物、アンモニア、硫化水素など、水中に含ま
れるトリハロメタン、トリクロロエチレン、フロン等の
有機ハロゲン化合物、除草剤、殺菌剤、殺虫剤等の種々
の農薬、蛋白質やアミノ酸等の種々の生物学的酸素要求
物質、界面活性材、アルデヒド類、アミン類、メルカプ
タン類、アルコール類、ＢＴＸ、フェノール類等の有機
化合物、シアン化合物、硫黄化合物等の無機化合物、種
々の重金属イオン等、さらには細菌、放線菌、菌類、藻
類等の微生物などである。さらに、本発明の多機能部材
の具体的用途としては、大腸菌、ブドウ球菌、緑濃菌、
カビ等の様々な菌類に対する抗菌、アルデヒド、メルカ
プタン、アンモニア、硫化水素等の臭気の防止、油、タ
バコのヤニ、指紋、雨垂れ、泥などへの防汚等があげら
れる。(C) Method of Using Multifunctional Member The multifunctional member having a photocatalytic action obtained by the above method exhibits a photocatalytic action by sunlight, fluorescent light, black light, mercury lamp, xenon lamp or the like. I do. By this catalytic action, an excellent effect of decomposing, removing, and detoxifying various harmful substances and attached substances is exhibited. The main uses of the multifunctional member obtained by the method of the present invention include decomposition of harmful substances and pollutants contained in air or water,
There is removal. The target substances are NOX, SOX, Freon, aldehydes, amines, mercaptans, alcohols, organic compounds such as BTX and phenols contained in air, trihalomethane contained in water such as ammonia and hydrogen sulfide. , Organic halogen compounds such as trichloroethylene and chlorofluorocarbon, various pesticides such as herbicides, fungicides, insecticides, various biological oxygen demanding substances such as proteins and amino acids, surfactants, aldehydes, amines, and mercaptans Organic compounds such as alcohols, BTX, and phenols; inorganic compounds such as cyanide compounds and sulfur compounds; various heavy metal ions; and microorganisms such as bacteria, actinomycetes, fungi, and algae. Furthermore, specific uses of the multifunctional member of the present invention include Escherichia coli, Staphylococcus, Pseudomonas,
Antibacterial against various fungi such as mold, prevention of odors such as aldehyde, mercaptan, ammonia, and hydrogen sulfide, and antifouling to oil, tobacco tar, fingerprint, rain dripping, mud, and the like.
【００４１】[0041]
（実施例１）酸化チタン光触媒用ゾルを調製し、ゾル中
に存在する化合物を調査した。(Example 1) A sol for a titanium oxide photocatalyst was prepared, and compounds present in the sol were investigated.
【００４２】ゾルは次の方法で調製した。試験ａおよび
試験ｂ（いずれも本発明例）では、チタン−ｎ−ブトキ
シド６８ｇ（０．２ｍｏｌ）を脱水エタノール（９８ｍ
ｌ）に加えた混合液を３０分間室温で撹拌した後、氷浴
を用いて冷却した。その後、エタノール（９８ｍｌ）、
水（２．６ｍｌ）、硝酸（１ｍｌ）の混合液をゆっくり
と滴下、１時間撹拌した後、氷浴を除いて室温に戻し、
１２時間撹拌を続けた。さらに、この反応液１００ｍｌ
に、試験ａの場合は分子量約４万、試験ｂの場合は分子
量約１２０万のポリビニルピロリドンを１０ｇ加え、室
温下で１時間撹拌した。この操作により、黄色に着色し
た酸化チタン光触媒用ゾルが得られた。The sol was prepared by the following method. In Test a and Test b (both examples of the present invention), 68 g (0.2 mol) of titanium-n-butoxide was added to dehydrated ethanol (98 m
After the mixture added in l) was stirred at room temperature for 30 minutes, it was cooled using an ice bath. Then, ethanol (98ml),
A mixture of water (2.6 ml) and nitric acid (1 ml) was slowly added dropwise, and after stirring for 1 hour, the ice bath was removed and the temperature was returned to room temperature.
Stirring was continued for 12 hours. Furthermore, 100 ml of this reaction solution
Then, 10 g of polyvinylpyrrolidone having a molecular weight of about 40,000 for test a and about 1.2 million for test b was added, and stirred at room temperature for 1 hour. By this operation, a titanium oxide photocatalyst sol colored yellow was obtained.
【００４３】また、比較例（試験ｃ）として、ポリビニ
ルピロリドンを用いないこと以外は、上記試験ａおよび
ｂと同じ条件で酸化チタン光触媒用ゾルを調製した。そ
の結果、透明な酸化チタンゾルが得られた。As a comparative example (test c), a sol for a titanium oxide photocatalyst was prepared under the same conditions as in the tests a and b except that polyvinylpyrrolidone was not used. As a result, a transparent titanium oxide sol was obtained.
【００４４】これらの酸化チタンゾルを自記分光光度計
によって分析し、それぞれの液の吸収スペクトルを測定
した。図１にその結果を示す。These titanium oxide sols were analyzed by a self-recording spectrophotometer, and the absorption spectra of each liquid were measured. FIG. 1 shows the results.
【００４５】試験ａおよびｂの吸収スペクトル（それぞ
れａ、ｂ）は、試験ｃ（比較例）の吸収スペクトル
（ｃ）に比べて長波長側にシフトしている。また、試験
ａと試験ｂの吸収量と試験ｃの吸収量の差を求めること
によって得られる差スペクトル（曲線ｄおよび曲線ｅ）
は、ポリビニルピロリドンの吸収スペクトル（ｆ、ｇ）
に比べると波形がまったく異なっており、３６０ｎｍ付
近にピークが認められる。このスペクトルは、チタン−
ｎ−ブトキシドとポリビニルピロリドンとから生じた有
機チタン錯体に由来するものであることを示している。The absorption spectra of tests a and b (a and b, respectively) are shifted to longer wavelengths than the absorption spectrum (c) of test c (comparative example). Further, a difference spectrum (curve d and curve e) obtained by obtaining a difference between the absorption amounts of the test a and the test b and the absorption amount of the test c.
Is the absorption spectrum of polyvinylpyrrolidone (f, g)
The waveform is completely different from that of the above, and a peak is observed around 360 nm. This spectrum is similar to titanium-
This indicates that the compound is derived from an organic titanium complex generated from n-butoxide and polyvinylpyrrolidone.
【００４６】この結果から、本発明例の酸化チタン光触
媒用ゾルには、配合原料であるチタン化合物、ポリビニ
ルピロリドンおよびこれらの反応によって生成した有機
チタン錯体が存在することが確認された。From the results, it was confirmed that the titanium oxide photocatalyst sol according to the present invention contained a titanium compound, polyvinylpyrrolidone as a compounding raw material, and an organic titanium complex formed by the reaction thereof.
【００４７】（実施例２）酸化チタン光触媒用ゾルを支
持体に被覆し、触媒としての性能を調査した。Example 2 A sol for a titanium oxide photocatalyst was coated on a support, and the performance as a catalyst was investigated.
【００４８】支持体としては、石英板、陶器製の白色タ
イルおよびステンレス鋼板（ＪＩＳＳＵＳ３０４）の３
種類を用いた。支持体の大きさは、縦横４０ｍｍ、厚さ
は、石英板およびステンレス鋼板は１ｍｍ、タイルは５
ｍｍである。As the support, quartz plate, ceramic white tile and stainless steel plate (JISSUS304) were used.
The type was used. The size of the support is 40 mm in length and width, the thickness is 1 mm for quartz and stainless steel plates, and 5 for tiles.
mm.
【００４９】これらの支持体の表面に、酸化チタン光触
媒用ゾルをディップコーティング法（引き上げ速度：１
００ｍｍ／分。ただし、試験Ｎｏ．３は１０ｍｍ／分）
によって塗布した。次に、１００℃で３０分間乾燥した
後、電熱炉を用いて１０℃／分の昇温速度で加熱し、最
終温度５５０℃または７００℃で３０分間焼成した。こ
の処理によって、酸化チタンが薄膜状に固定された試験
材が得られた。On the surface of these supports, a sol for a titanium oxide photocatalyst was applied by a dip coating method (pulling speed: 1).
00 mm / min. However, the test No. 3 is 10 mm / min)
Was applied. Next, after drying at 100 ° C. for 30 minutes, it was heated at a heating rate of 10 ° C./min using an electric furnace and baked at a final temperature of 550 ° C. or 700 ° C. for 30 minutes. By this treatment, a test material having titanium oxide fixed in a thin film was obtained.
【００５０】実施例２における試験Ｎｏ．１〜１１の試
験材の製造条件を表１にまとめて示す。なお、ゾルの調
製法は、基本的には実施例１の場合と同様とした。ただ
し、試験によっては酸化チタン生成用のチタン化合物、
ポリビニルピロリドンの分子量およびその他の添加剤を
変えているので、それらの条件については、表１に併記
した。Test No. 2 in Example 2 Table 1 summarizes the manufacturing conditions of the test materials 1 to 11. The method of preparing the sol was basically the same as in Example 1. However, depending on the test, a titanium compound for producing titanium oxide,
Since the molecular weight of polyvinylpyrrolidone and other additives were changed, those conditions are also shown in Table 1.
【００５１】なお、試験Ｎｏ．７、９および１０につい
ては、ゾルの調製の際にアセチルアセトンを用いたため
に、次の方法で調製を行った。The test No. 7, 9, and 10 were prepared by the following method because acetylacetone was used in preparing the sol.
【００５２】チタンイソプロポキシド５６．８ｇ（０．
２ｍｏｌ）と、硝酸亜鉛４．５４ｇ（０．０２４ｍｏ
ｌ）（試験Ｎｏ．７）またはハフニウムエトキシド８．
６ｇ（０．０２４ｍｏｌ）（試験Ｎｏ．９）またはアル
ミニムイソプロポキシド４．９ｇ（０．０２４ｍｏｌ）
（試験Ｎｏ．１０）、アセチルアセトン３０ｇを脱水エ
タノール（１９６ｍｌ）に加えた液を２時間環流した。
冷却後、この反応液１００ｍｌに分子量約４万のポリビ
ニルピロリドンを１０ｇ加え、室温下で１時間撹拌する
ことにより、黄色に着色した酸化チタン光触媒用ゾルを
得た。56.8 g of titanium isopropoxide (0.
2 mol) and 4.54 g of zinc nitrate (0.024 mol)
1) (Test No. 7) or hafnium ethoxide
6 g (0.024 mol) (Test No. 9) or 4.9 g (0.024 mol) of aluminum isopropoxide
(Test No. 10), a solution obtained by adding 30 g of acetylacetone to dehydrated ethanol (196 ml) was refluxed for 2 hours.
After cooling, 10 g of polyvinylpyrrolidone having a molecular weight of about 40,000 was added to 100 ml of the reaction solution, and the mixture was stirred at room temperature for 1 hour to obtain a titanium oxide photocatalyst sol colored yellow.
【００５３】[0053]
【表１】 [Table 1]
【００５４】試験Ｎｏ．１（本発明例）および試験Ｎ
ｏ．３（比較例）については、Ｘ線回折法によって、支
持体に形成された酸化チタン膜の結晶構造および結晶粒
径を調査した。Test No. 1 (Example of the present invention) and Test N
o. Regarding Comparative Example 3 (Comparative Example), the crystal structure and the crystal grain size of the titanium oxide film formed on the support were examined by X-ray diffraction.
【００５５】その結果、結晶構造はいずれもアナタース
型であったが、Scherrerの式から求めた酸化チタンの結
晶粒径は、試験Ｎｏ．１の場合は約１５ｎｍ、試験Ｎ
ｏ．３の場合は約２１ｎｍであり、本発明例の方が微細
であることが確認された。As a result, the crystal structures were all anatase type, but the crystal grain size of titanium oxide determined from Scherrer's equation was the same as in Test No. 1. Approximately 15 nm for 1 and test N
o. In the case of No. 3, it was about 21 nm, and it was confirmed that the example of the present invention was finer.
【００５６】次に、光触媒としての性能を調査するため
に、各試験材について、強い毒性と臭気をもつアセトア
ルデヒドの分解試験を行った。分解試験方法は次のとお
りである。Next, in order to investigate the performance as a photocatalyst, a decomposition test of acetaldehyde having strong toxicity and odor was performed on each test material. The decomposition test method is as follows.
【００５７】石英性反応セル（容量１００ｃｍ3 ）に試
験材を入れ、閉鎖循環ラインに接続した（合計内容積８
７０ｃｍ3 ）。次に、空気で希釈したアセトアルデヒド
（約２５０ｐｐｍ）を系内に導入し、循環させながら２
５０Ｗ超高圧水銀灯から減光フィルターおよびＵＶフィ
ルターを通して光照射を行った。この時、試験材表面の
紫外線強度（波長：３６６ｎｍ）は１５ｍＷ／ｃｍ2で
あった。光照射を行いながらラインに接続したガスクロ
マトグラフを用いて、アセトアルデヒドの濃度を経時的
に定量した。The test material was placed in a quartz reaction cell (capacity 100 cm 3 ) and connected to a closed circulation line (total internal volume 8
70 cm 3 ). Next, acetaldehyde (about 250 ppm) diluted with air is introduced into the system, and circulated for 2 hours.
Light irradiation was performed from a 50 W ultra-high pressure mercury lamp through a neutral density filter and a UV filter. At this time, the ultraviolet intensity (wavelength: 366 nm) on the surface of the test material was 15 mW / cm 2 . The concentration of acetaldehyde was determined over time using a gas chromatograph connected to a line while performing light irradiation.
【００５８】図２に、試験Ｎｏ．１および３について、
光照射時間とアセトアルデヒドの濃度の関係を調査した
結果を示した。比較例の試験Ｎｏ．３に比べて、本発明
例の試験Ｎｏ．１の場合には、アセトアルデヒドが短時
間に減少した。FIG. For 1 and 3,
The results of investigating the relationship between the light irradiation time and the concentration of acetaldehyde were shown. Test No. of the comparative example. In comparison with Test No. 3, Test No. In case 1, acetaldehyde was reduced in a short time.
【００５９】表１に、各試験で求められたアセトアルデ
ヒドの分解速度定数を示した。ポリビニルピロリドンを
含まないゾルによって製造した多機能部材を用いた比較
例の試験Ｎｏ．３については、分解速度定数が０．０２
５であった。それに対して、その他の本発明例について
は、０．０３６〜０．１３８で比較例に比べて明らかに
高い値であった。また、分解速度定数に対する支持体の
材質の影響も認められなかった。Table 1 shows the decomposition rate constants of acetaldehyde determined in each test. Test No. of a comparative example using a multifunctional member manufactured with a sol containing no polyvinylpyrrolidone. For No. 3, the decomposition rate constant was 0.02
It was 5. On the other hand, the values of 0.036 to 0.138 of the other examples of the present invention were clearly higher than those of the comparative examples. In addition, the effect of the material of the support on the decomposition rate constant was not recognized.
【００６０】また、ジルコニウム、亜鉛、珪素、ハフニ
ウム、アルミニウム、ほう素のそれぞれ化合物を含む試
験Ｎｏ．６〜１１についても、高い分解速度定数が得ら
れた。In addition, Test No. 1 containing each compound of zirconium, zinc, silicon, hafnium, aluminum and boron. For 6 to 11, high decomposition rate constants were obtained.
【００６１】以上の結果から、本発明の酸化チタン光触
媒用ゾルを支持体に付着させ、焼成して薄膜状の酸化チ
タンを固定した部材は、空気中の有害物質の分解および
防臭に優れた効果を発揮する機能部材として使用できる
ことが明らかになった。From the above results, it can be seen that the member having the titanium oxide photocatalyst sol of the present invention adhered to a support and calcined to fix the titanium oxide in the form of a thin film has an excellent effect of decomposing harmful substances in air and deodorizing. It has been found that it can be used as a functional member that exhibits
【００６２】（実施例３）本発明の製造方法で得られる
多機能部材を用いて、地下水を汚染して問題となってい
るテトラクロロエチレンの分解試験を行った。(Example 3) Using the multifunctional member obtained by the production method of the present invention, a decomposition test of tetrachloroethylene, which is a problem by contaminating groundwater, was performed.
【００６３】焼成温度を７００℃としたこと以外は、実
施例２における試験Ｎｏ．１と同じ条件で、酸化チタン
を薄膜状に固定した石英基板（試験材）を作製した。濃
度３０ｐｐｍのテトラクロロエチレンの水溶液４０ｍｌ
を石英製反応セルに入れ、その中に試験材を浸漬し酸素
を２０分間バブリングした後、２５０Ｗの超高圧水銀ラ
ンプの光をＵＶフィルターを通して照射した。４時間後
反応液に含まれるテトラクロロエチレンの量をガスクロ
マトグラフを用いて定量した。Except that the firing temperature was set to 700 ° C., the test No. Under the same conditions as in 1, a quartz substrate (test material) on which titanium oxide was fixed in a thin film shape was produced. 40 ml of an aqueous solution of tetrachloroethylene having a concentration of 30 ppm
Was placed in a quartz reaction cell, the test material was immersed therein, oxygen was bubbled for 20 minutes, and then the light of a 250 W ultra-high pressure mercury lamp was irradiated through a UV filter. Four hours later, the amount of tetrachloroethylene contained in the reaction solution was quantified using a gas chromatograph.
【００６４】その結果、テトラクロロエチレンの量は２
ｐｐｍに減少していた。この結果から、本発明のゾルを
支持体に塗布し、焼成して得られる多機能部材は、水中
の汚染物質の分解、無害化にも有効であることが確認さ
れた。As a result, the amount of tetrachloroethylene was 2
ppm. From these results, it was confirmed that the multifunctional member obtained by applying the sol of the present invention to a support and firing it was also effective in decomposing and detoxifying contaminants in water.
【００６５】（実施例４）本発明の製造方法で得られる
多機能部材の抗菌効果を確認した。大腸菌（Escherichi
a coli W3110株）に対する抗菌性を、次の方法で調査し
た。Example 4 The antibacterial effect of the multifunctional member obtained by the manufacturing method of the present invention was confirmed. Escherichia coli (Escherichi
a. coli strain W3110) was examined by the following method.
【００６６】多機能部材としては、実施例２における試
験Ｎｏ．１で調製した試験材を用いた。その表面を予め
７０％エタノールで殺菌した後、大腸菌を２．５×１０
5 個／ｍｌ含む生理食塩水０．２ｍｌ（大腸菌数：５×
１０4 個）を、０．０２５ｍｌづつ８滴に分けて試験材
の表面に滴下した。次いで、相対湿度９５％の条件下で
２５０Ｗ超高圧水銀灯から、減光フィルター、ＵＶフィ
ルターを通じて３０分間光照射を行った（紫外線強度１
ｍＷ／ｃｍ2 ）。その後、試験材の表面の菌液を生理食
塩水９．８ｍｌで洗い流し、回収した液を標準寒天培地
に希釈沫塗し、３５℃で４８時間培養後、生育したコロ
ニーを計数することによって生菌数を測定した。その結
果、生存している大腸菌は１．５×１０3 個に減少して
いた。また、比較例として、酸化チタンがコーティング
されていない石英板および上記の実施例２における試験
Ｎｏ．１で調製した試験材の表面に、それぞれ大腸菌を
２．５×１０5 個／ｍｌ含む生理食塩水を滴下した後、
前者には３０分間光照射し、後者は３０分間暗所に置い
た場合の試験を行った。上記の場合と同様な方法で生存
している生菌数を測定した結果、それぞれ４．３×１０
4 個、４．６×１０4 個であった。As the multifunctional member, the test No. The test material prepared in 1 was used. After sterilizing the surface with 70% ethanol in advance, E. coli was
0.2 ml of physiological saline containing 5 cells / ml (the number of E. coli: 5 ×
10 4 ) were dropped on the surface of the test material in 8 drops of 0.025 ml each. Subsequently, light was irradiated from a 250 W ultra-high pressure mercury lamp through a neutral density filter and a UV filter for 30 minutes under the condition of a relative humidity of 95% (UV intensity 1).
mW / cm 2 ). Thereafter, the bacterial solution on the surface of the test material was washed away with 9.8 ml of physiological saline, and the collected solution was diluted and spread on a standard agar medium, cultured at 35 ° C. for 48 hours, and the grown colonies were counted by counting the grown colonies. The number was measured. As a result, the number of surviving Escherichia coli was reduced to 1.5 × 10 3 . As a comparative example, a quartz plate not coated with titanium oxide and the test No. 2 in Example 2 described above were used. A physiological saline solution containing 2.5 × 10 5 Escherichia coli / ml was dropped on the surface of the test material prepared in Step 1, respectively.
The former was irradiated with light for 30 minutes, and the latter was tested in a dark place for 30 minutes. As a result of measuring the number of viable cells surviving in the same manner as described above, 4.3 × 10
The number was 4 , 4.6 × 10 4 .
【００６７】これらの結果から、本発明のゾルを用いて
製造された多機能部材は、優れた抗菌性を備えているこ
とが明らかになった。From these results, it was clarified that the multifunctional member produced using the sol of the present invention had excellent antibacterial properties.
【００６８】（実施例５）本発明の製造方法で得られる
多機能部材の防汚効果を確認した。１例として、多機能
部材である試験材の表面に付着させたタバコのヤニを除
去する効果を調査した。Example 5 The antifouling effect of the multifunctional member obtained by the production method of the present invention was confirmed. As an example, the effect of removing the tar of tobacco adhered to the surface of the test material, which is a multifunctional member, was investigated.
【００６９】実施例２における試験Ｎｏ．４で作製した
試験材の表面にタバコ１本分のヤニを強制的に付着させ
た後、２５０Ｗ超高圧水銀灯から、減光フィルター、Ｕ
Ｖフィルターを通して光照射を行った（紫外線強度５ｍ
Ｗ／ｃｍ2 ）。ヤニの減少は、色差計を用いて、黄色の
目安となるｂ値の変化で評価した。Test No. 2 in Example 2 After forcibly adhering one cigarette tar to the surface of the test material prepared in step 4, the light was filtered from a 250 W ultra-high pressure mercury lamp,
Light irradiation was performed through a V filter (ultraviolet intensity 5 m
W / cm 2 ). The decrease in tan was evaluated using a color difference meter based on a change in the b-value as a measure of yellow.
【００７０】その結果、ｂ値は光照射前の１６．２か
ら、２時間の光照射でほぼ０となり、視覚的にも支持体
として用いたタイルの色（白色）に蘇っていた。As a result, the b value became 16. from 16.2 before the light irradiation, to almost 0 after 2 hours of light irradiation, and the color (white) of the tile used as the support was visually revived.
【００７１】一方、酸化チタン膜が固定化されていない
タイルを用いて、同様に試験を行ったところ、ｂ値は１
３．４から、２時間の光照射では８．２に減少したにす
ぎなかった。視覚的にも、ヤニがかなり残っていると認
められた。On the other hand, when the same test was performed using a tile on which the titanium oxide film was not fixed, the b value was 1
From 3.4, light irradiation for 2 hours only reduced to 8.2. Visually, it was recognized that a considerable amount of tar was left.
【００７２】これらの結果から、本発明のゾルを用いて
製造された多機能部材は、たばこのヤニを効果的に除去
する性能、すなわち防汚性を備えていることが確認され
た。From these results, it was confirmed that the multifunctional member manufactured by using the sol of the present invention had a performance of effectively removing tobacco tar, that is, an antifouling property.
【００７３】[0073]
【発明の効果】本発明の酸化チタン光触媒用ゾルを支持
体に塗布し焼成して得られる酸化チタン膜は、優れた光
触媒作用を持っている。また、本発明の酸化チタンゾル
の原料は、比較的安価であり、このゾルを用いる多機能
部材の製造にも特別な設備や操作を必要としないので、
製造コストが比較的安い。The titanium oxide film obtained by applying the titanium oxide photocatalyst sol of the present invention to a support and firing it has an excellent photocatalytic action. In addition, the raw material of the titanium oxide sol of the present invention is relatively inexpensive, and does not require any special equipment or operation for producing a multifunctional member using this sol.
Manufacturing cost is relatively low.
【００７４】このように本発明のゾルを用いて製造され
る本発明の多機能部材は、大気中、水中などに存在する
有害物質、汚染物質などを効果的に分解、除去する作用
を持っており、防臭効果も大きい。また、抗菌作用、防
汚作用にも優れているので、広い分野で利用することが
できる。As described above, the multifunctional member of the present invention manufactured using the sol of the present invention has an action of effectively decomposing and removing harmful substances and contaminants existing in the air, water and the like. It has a great deodorant effect. Also, since it has excellent antibacterial and antifouling effects, it can be used in a wide range of fields.
【図１】実施例１において、本発明例のゾル、比較例の
ゾルおよびポリビニルピロリドンの光吸収スペクトルを
自記分光光度計により測定した結果を示す図である。FIG. 1 is a diagram showing the results of measuring the optical absorption spectra of a sol of the present invention, a sol of a comparative example, and polyvinylpyrrolidone in Example 1, using a self-recording spectrophotometer.
【図２】実施例２において、石英の支持体に固定した酸
化チタン膜により、アセトアルデヒドの光分解を行った
際のアセトアルデヒドの経時変化を測定した結果を示す
図である。FIG. 2 is a view showing a result of measuring a temporal change of acetaldehyde when photodecomposition of acetaldehyde was performed using a titanium oxide film fixed to a quartz support in Example 2.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ０１Ｊ 37/02 ３０１ Ｂ０１Ｊ 37/02 ３０１Ｃ Ｃ０２Ｆ 1/30 Ｃ０２Ｆ 1/30 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI B01J 37/02 301 B01J 37/02 301C C02F 1/30 C02F 1/30
Claims (5)
むことを特徴とする酸化チタン光触媒用ゾル。1. A sol for a titanium oxide photocatalyst comprising polyvinylpyrrolidone and a titanium compound.
学反応によって形成された有機チタン錯体を含むことを
特徴とする請求項１に記載の酸化チタン光触媒用ゾル。2. The sol for a titanium oxide photocatalyst according to claim 1, comprising an organic titanium complex formed by a chemical reaction between polyvinylpyrrolidone and a titanium compound.
合物、ハフニウム化合物、アルミニウム化合物およびほ
う素化合物のうちの少なくとも１種を含むことを特徴と
する請求項１または請求項２に記載の酸化チタン光触媒
用ゾル。3. The titanium oxide photocatalyst according to claim 1, which contains at least one of a zirconium compound, a zinc compound, a silicon compound, a hafnium compound, an aluminum compound and a boron compound. Sol.
でのいずれかに記載の酸化チタン光触媒用ゾルを付着さ
せた後焼成することにより、支持体の表面に酸化チタン
膜を形成させることを特徴とする光触媒作用を持つ多機
能部材の製造方法。4. A titanium oxide film is formed on the surface of a support by baking after adhering the sol for a titanium oxide photocatalyst according to any one of claims 1 to 3 on the surface of the support. A method for producing a multifunctional member having a photocatalytic action.
機能部材により、光照射下で大気中または水中の物質を
処理することを特徴とする多機能部材の使用方法。5. A method for using a multifunctional member, wherein a substance in the air or water is treated under light irradiation by the multifunctional member obtained by the method according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15075697A JP3550947B2 (en) | 1997-06-09 | 1997-06-09 | Method for producing and using photocatalytic multifunctional member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15075697A JP3550947B2 (en) | 1997-06-09 | 1997-06-09 | Method for producing and using photocatalytic multifunctional member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10337478A true JPH10337478A (en) | 1998-12-22 |
| JP3550947B2 JP3550947B2 (en) | 2004-08-04 |
Family
ID=15503737
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15075697A Expired - Fee Related JP3550947B2 (en) | 1997-06-09 | 1997-06-09 | Method for producing and using photocatalytic multifunctional member |
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029108A1 (en) * | 1998-11-12 | 2000-05-25 | Abb Lummus Global Inc. | Attrition resistant thin film catalyst and method of preparation |
| WO2000030747A1 (en) * | 1998-11-20 | 2000-06-02 | Asahi Kasei Kabushiki Kaisha | Modified photocatalyst sol |
| JP2002060651A (en) * | 2000-08-23 | 2002-02-26 | Hitachi Chem Co Ltd | Metal oxide aqueous sol composition, method for forming membrane by using the same and member |
| KR100840899B1 (en) * | 2006-08-11 | 2008-06-24 | 오쿠야마 키쿠오 | Manufacturing methods of photo-catalytic titanium oxide with addition of polymer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664996B (en) * | 2016-03-09 | 2018-08-31 | 中国科学院地球环境研究所 | A kind of g-C3N4/TiO2The preparation method and applications of heterojunction photocatalysis film |
-
1997
- 1997-06-09 JP JP15075697A patent/JP3550947B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000029108A1 (en) * | 1998-11-12 | 2000-05-25 | Abb Lummus Global Inc. | Attrition resistant thin film catalyst and method of preparation |
| WO2000030747A1 (en) * | 1998-11-20 | 2000-06-02 | Asahi Kasei Kabushiki Kaisha | Modified photocatalyst sol |
| US7030058B1 (en) | 1998-11-20 | 2006-04-18 | Asahi Kasei Kabushiki Kaisha | Modified photocatalyst sol |
| JP2002060651A (en) * | 2000-08-23 | 2002-02-26 | Hitachi Chem Co Ltd | Metal oxide aqueous sol composition, method for forming membrane by using the same and member |
| KR100840899B1 (en) * | 2006-08-11 | 2008-06-24 | 오쿠야마 키쿠오 | Manufacturing methods of photo-catalytic titanium oxide with addition of polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3550947B2 (en) | 2004-08-04 |
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