JP2002038054A - Coating agent for forming titanium oxide film, method for forming titanium oxide film and photocatalyst - Google Patents
Coating agent for forming titanium oxide film, method for forming titanium oxide film and photocatalystInfo
- Publication number
- JP2002038054A JP2002038054A JP2001144543A JP2001144543A JP2002038054A JP 2002038054 A JP2002038054 A JP 2002038054A JP 2001144543 A JP2001144543 A JP 2001144543A JP 2001144543 A JP2001144543 A JP 2001144543A JP 2002038054 A JP2002038054 A JP 2002038054A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- oxide film
- forming
- titanium
- coating agent
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 196
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 239000008199 coating composition Substances 0.000 claims description 27
- 238000010304 firing Methods 0.000 claims description 23
- 239000010419 fine particle Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 238000000576 coating method Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000975 dye Substances 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 iso-isopropanol Chemical compound 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229960004592 isopropanol Drugs 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007788 liquid Substances 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
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
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- 239000003973 paint Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 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 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- 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 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000012327 Ruthenium complex Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- GRHBQAYDJPGGLF-UHFFFAOYSA-N isothiocyanic acid Chemical compound N=C=S GRHBQAYDJPGGLF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- 229910052707 ruthenium Inorganic materials 0.000 description 2
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
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- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100325793 Arabidopsis thaliana BCA2 gene Proteins 0.000 description 1
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- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒活性に優れ
た酸化チタン膜の形成用塗布剤、形成方法及び光触媒に
関する。The present invention relates to a coating agent for forming a titanium oxide film having excellent photocatalytic activity, a method for forming the same, and a photocatalyst.
【０００２】[0002]
【従来の技術】従来、酸化チタン膜を形成する方法とし
ては、（１）酸化チタンゾルを、基材に塗布後、焼成す
る方法、（２）塩化チタン又は硫酸チタンの水溶液を、
基材に塗布後、焼成する方法、（３）真空中で酸化チタ
ンをターゲットとしてスパッタリングして基材上に膜を
形成させるスパッタ法、（４）有機チタン化合物を、電
気炉中で揮発、分解して基材上に膜を形成させるＣＶＤ
法等が公知である。2. Description of the Related Art Conventionally, as a method of forming a titanium oxide film, (1) a method in which a titanium oxide sol is applied to a base material and then fired, and (2) an aqueous solution of titanium chloride or titanium sulfate is used.
(3) Sputtering method in which a film is formed on a substrate by sputtering using titanium oxide as a target in a vacuum, and (4) volatilization and decomposition of an organic titanium compound in an electric furnace. CVD to form a film on a substrate
Methods and the like are known.
【０００３】しかしながら、（１）の方法には、造膜性
に劣り、０．１μｍ以上の膜厚ではワレ、剥がれを生じ
るという欠点がある。（２）の方法には、塗布液の熱分
解物による基材への悪影響があるという欠点がある。
（３）及び（４）の方法には、減圧下でなければ良好な
膜が得られず、真空排気できる反応容器が必要であり、
又膜形成速度が遅い、という欠点がある。また、これら
のいずれの方法によっても、酸化チタンの多孔質膜を得
ることはできなかった。[0003] However, the method (1) has a drawback that the film-forming property is inferior, and cracking and peeling occur at a film thickness of 0.1 µm or more. The method (2) has a drawback that a thermal decomposition product of the coating solution has an adverse effect on the substrate.
In the methods (3) and (4), a good film cannot be obtained unless the pressure is reduced, and a reaction vessel that can be evacuated is required.
Further, there is a disadvantage that the film forming speed is low. Further, a porous film of titanium oxide could not be obtained by any of these methods.
【０００４】また、最近、（５）塩化チタン又は硫酸チ
タンの水溶液と塩基性物質から得られる水酸化チタンの
過酸化水素水溶液を、基材に塗布後、加熱又は焼成して
酸化チタン膜を形成する方法（特開平9-71418号）、
（６）テトライソプロポキシチタンをイソプロパノール
及び水と混合後加熱して得た酸化チタンの過酸化水素水
溶液に、基材を浸漬後、焼成して酸化チタン膜を形成す
る方法（特開平10-46317号）等が提案されている。Recently, a titanium oxide film is formed by applying (5) an aqueous solution of titanium chloride or titanium sulfate and an aqueous solution of hydrogen peroxide of titanium hydroxide obtained from a basic substance to a substrate, followed by heating or firing. Method (Japanese Patent Laid-Open No. 9-71418),
(6) A method of forming a titanium oxide film by immersing a base material in an aqueous solution of titanium oxide hydrogen peroxide obtained by mixing tetraisopropoxytitanium with isopropanol and water and then heating the mixture (Japanese Patent Laid-Open No. 10-46317) No.) has been proposed.
【０００５】しかしながら、（５）の方法には、水酸化
チタンの過酸化水素水溶液を得る工程が複雑で、塩基性
物質の除去が面倒である、原料に含まれるＦｅ、Ｃｕ等
の金属が混入し易く純度の高い酸化チタン膜を得ること
は難しい等の欠点がある。（６）の方法には、酸化チタ
ンの過酸化水素水溶液の調製に大量のイソプロパノール
を使用しなければならず、コストがかかるという欠点が
ある。また、これらのいずれの方法によっても、酸化チ
タンの多孔質膜を得ることはできなかった。However, in the method (5), the step of obtaining an aqueous hydrogen peroxide solution of titanium hydroxide is complicated, and removal of a basic substance is troublesome. Metals such as Fe and Cu contained in raw materials are mixed. It is difficult to obtain a highly pure titanium oxide film easily. The method (6) has a disadvantage that a large amount of isopropanol must be used for preparing an aqueous solution of titanium oxide in hydrogen peroxide, which is costly. Further, a porous film of titanium oxide could not be obtained by any of these methods.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、上記
従来技術の諸欠点が解消され、酸化チタンの多孔質膜を
容易に形成できる酸化チタン膜形成用塗布剤、酸化チタ
ン膜形成方法及び光触媒を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to easily form a titanium oxide porous film, a titanium oxide film forming method, a titanium oxide film forming method and a titanium oxide film forming method. It is to provide a photocatalyst.
【０００７】[0007]
【課題を解決するための手段】本発明は、以下の酸化チ
タン膜形成用塗布剤、酸化チタン膜形成方法及び光触媒
を提供するものである。The present invention provides the following coating agent for forming a titanium oxide film, a method for forming a titanium oxide film, and a photocatalyst.
【０００８】１．（Ａ）加水分解して水酸基になる基を
有するチタン化合物及び／又はその低縮合物を過酸化水
素水と混合して得られるペルオキソチタン酸水溶液、並
びに（Ｂ）ポリエチレングリコールを含有することを特
徴とする酸化チタン膜形成用塗布剤。[0008] 1. (A) an aqueous solution of peroxotitanic acid obtained by mixing a titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low-condensate thereof with aqueous hydrogen peroxide, and (B) a polyethylene glycol. Coating agent for forming a titanium oxide film.
【０００９】２．上記チタン化合物が、一般式 Ｔｉ（ＯＲ）4 （Ｉ） （式中、Ｒは、同一又は異なって、炭素数１〜５のアル
キル基を示す。）で表されるテトラアルコキシチタンで
ある上記項１に記載の塗布剤。[0009] 2. The above-mentioned item, wherein the titanium compound is a tetraalkoxytitanium represented by a general formula: Ti (OR) 4 (I) (wherein, R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). 2. The coating composition according to 1.
【００１０】３．上記チタン化合物の低縮合物が、一般
式 Ｔｉ（ＯＲ）4 （Ｉ） （式中、Ｒは、同一又は異なって、炭素数１〜５のアル
キル基を示す。）で表されるテトラアルコキシチタンを
お互いに縮合反応させてなる縮合度２〜３０の化合物で
ある上記項１に記載の塗布剤。[0010] 3. A low-condensation product of the titanium compound is a tetraalkoxytitanium represented by the general formula: Ti (OR) 4 (I) (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). The coating agent according to the above item 1, which is a compound having a degree of condensation of 2 to 30 obtained by subjecting the compounds to a condensation reaction with each other.
【００１１】４．加水分解して水酸基になる基を有する
チタン化合物及び／又はその低縮合物と過酸化水素水と
の混合割合が、前者１０重量部に対して後者が過酸化水
素換算で０．１〜１００重量部の範囲内である上記項１
に記載の塗布剤。4. The mixing ratio of a titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low-condensate thereof and aqueous hydrogen peroxide is such that the latter is 10 to 100 parts by weight and the latter is 0.1 to 100 parts by weight in terms of hydrogen peroxide. Item 1 which is within the range of
The coating agent according to the above.
【００１２】５．ペルオキソチタン酸水溶液（Ａ）が、
酸化チタンゾルの存在下で、加水分解して水酸基になる
基を有するチタン化合物及び／又はその低縮合物を過酸
化水素水と混合して得られたものである上記項１に記載
の塗布剤。5. The aqueous solution of peroxotitanic acid (A)
Item 2. The coating agent according to the above item 1, which is obtained by mixing a titanium compound having a group that becomes a hydroxyl group by hydrolysis in the presence of a titanium oxide sol and / or a low condensate thereof with a hydrogen peroxide solution.
【００１３】６．酸化チタンゾルが、アナターゼ型酸化
チタンの水分散液である上記項５に記載の塗布剤。6. Item 6. The coating agent according to Item 5, wherein the titanium oxide sol is an aqueous dispersion of anatase type titanium oxide.
【００１４】７．酸化チタンゾルの使用量が、加水分解
して水酸基になる基を有するチタン化合物及び／又はそ
の低縮合物１重量部に対して、固形分で０．０１〜１０
重量部である上記項５に記載の塗布剤。7. The used amount of the titanium oxide sol is 0.01 to 10 as a solid content with respect to 1 part by weight of the titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or 1 part by weight of a low condensate thereof.
Item 6. The coating agent according to Item 5, which is part by weight.
【００１５】８．ペルオキソチタン酸水溶液（Ａ）が、
加水分解して水酸基になる基を有するチタン化合物及び
／又はその低縮合物を過酸化水素水と混合して得られる
ペルオキソチタン酸水溶液を、８０℃以上の温度で加熱
処理又はオートクレーブ処理して得られる平均粒子径が
１０ｎｍ以下の酸化チタン微粒子の分散液である上記項
１に記載の塗布剤。[8] The aqueous solution of peroxotitanic acid (A)
An aqueous peroxotitanic acid solution obtained by mixing a titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low-condensate thereof with aqueous hydrogen peroxide is subjected to heat treatment or autoclave treatment at a temperature of 80 ° C. or more. Item 2. The coating agent according to the above item 1, which is a dispersion liquid of titanium oxide fine particles having an average particle diameter of 10 nm or less.
【００１６】９．ポリエチレングリコール（Ｂ）が、平
均分子量２００〜４００万のものである上記項１に記載
の塗布剤。9. Item 2. The coating agent according to item 1, wherein the polyethylene glycol (B) has an average molecular weight of 2 to 4,000,000.
【００１７】１０．ポリエチレングリコール（Ｂ）の使
用割合が、ペルオキソチタン酸水溶液（Ａ）の固形分１
００重量部に対して、０．１〜２００重量部である上記
項１に記載の塗布剤。10. The proportion of the polyethylene glycol (B) used is 1 per solid content of the aqueous solution of peroxotitanic acid (A).
Item 2. The coating agent according to the above item 1, wherein the amount is 0.1 to 200 parts by weight with respect to 00 parts by weight.
【００１８】１１．上記項１に記載の塗布剤を、基材に
塗布した後、２００℃以上の温度で焼成して酸化チタン
多孔質膜を形成することを特徴とする酸化チタン膜形成
方法。11. 2. A method for forming a titanium oxide film, comprising: applying the coating agent according to the above item 1 to a substrate, followed by firing at a temperature of 200 ° C. or higher to form a titanium oxide porous film.
【００１９】１２．酸化チタン多孔質膜が、アナターゼ
型酸化チタン多孔質膜である上記項１１に記載の酸化チ
タン膜形成方法。[12] Item 12. The method for forming a titanium oxide film according to Item 11, wherein the titanium oxide porous film is an anatase-type titanium oxide porous film.
【００２０】１３．上記項１１に記載の方法により、基
材上に酸化チタン多孔質膜が形成されてなる光触媒。13. Item 12. A photocatalyst obtained by forming a titanium oxide porous film on a substrate by the method according to Item 11.
【００２１】１４．酸化チタン多孔質膜が、アナターゼ
型酸化チタン多孔質膜である上記項１３に記載の光触
媒。14. Item 14. The photocatalyst according to Item 13, wherein the titanium oxide porous film is an anatase-type titanium oxide porous film.
【００２２】本発明者は、前記目的を達成すべく鋭意研
究を重ねた。その結果、（Ａ）加水分解して水酸基にな
る基を有するチタン化合物及び／又はその低縮合物を過
酸化水素水と混合して得られるペルオキソチタン酸水溶
液及び（Ｂ）ポリエチレングリコールを含有する塗布剤
が、貯蔵安定性に優れ、製造上の問題が無いこと、当該
塗布剤を基材に塗布後、焼成することにより、酸化チタ
ン膜を容易に形成できること、得られる酸化チタン膜は
付着性に優れた緻密な多孔質膜であること、又多孔質膜
であるため酸化チタンの光触媒活性が向上していること
等を見出した。上記本発明は、かかる新たな諸知見に基
づいて、完成されたものである。The present inventors have conducted intensive studies to achieve the above object. As a result, (A) a peroxotitanic acid aqueous solution obtained by mixing a titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low condensate thereof with a hydrogen peroxide solution, and (B) a coating containing polyethylene glycol The agent is excellent in storage stability, there is no problem in production, after applying the coating agent to the base material, by firing, the titanium oxide film can be easily formed, the obtained titanium oxide film has an adhesive property. It has been found that the film is an excellent and dense porous film, and that the photocatalytic activity of titanium oxide is improved due to the porous film. The present invention has been completed based on these new findings.
【００２３】[0023]
【発明の実施の形態】本発明の酸化チタン膜形成用塗布
剤におけるペルオキソチタン酸水溶液（Ａ）は、加水分
解して水酸基になる基を有するチタン化合物及び／又は
その低縮合物を過酸化水素水と混合して得られるもので
ある。BEST MODE FOR CARRYING OUT THE INVENTION The aqueous solution of peroxotitanic acid (A) in the coating composition for forming a titanium oxide film of the present invention is obtained by converting a titanium compound having a group which becomes a hydroxyl group by hydrolysis and / or a low condensate thereof to hydrogen peroxide. It is obtained by mixing with water.
【００２４】該チタン化合物としては、特に一般式 Ｔｉ（ＯＲ）4 （Ｉ） （式中、Ｒは、同一又は異なって、炭素数１〜５のアル
キル基を示す。）で表されるテトラアルコキシチタンが
好ましい。Ｒで示される炭素数１〜５のアルキル基とし
ては、例えば、メチル基、エチル基、ｎ−プロピル基、
ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル
基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げら
れる。The titanium compound is particularly a tetraalkoxy represented by the general formula: Ti (OR) 4 (I) (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). Titanium is preferred. Examples of the alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group,
Examples thereof include an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group.
【００２５】また、上記チタン化合物の低縮合物として
は、上記一般式（Ｉ）の化合物をお互いに縮合反応させ
てなる縮合度２〜３０のものを使用するのが好ましく、
縮合度２〜１０のものを使用することがより好ましい。As the low condensate of the titanium compound, it is preferable to use a compound having a degree of condensation of 2 to 30 obtained by subjecting the compounds of the above general formula (I) to a condensation reaction with each other.
It is more preferable to use one having a condensation degree of 2 to 10.
【００２６】加水分解して水酸基になる基を有するチタ
ン化合物及び／又はその低縮合物（以下、これらのもの
を単に「加水分解性チタン化合物」と略す）と過酸化水
素水との混合割合は、前者１０重量部に対して、後者が
過酸化水素換算で０．１〜１００重量部、特に１〜２０
重量部の範囲内が好ましい。後者が、過酸化水素換算で
０．１重量部未満になるとペルオキソチタン酸の形成が
不十分になり白濁沈殿を生じるので好ましくない。一
方、１００重量部を超えると未反応の過酸化水素が残存
し易く貯蔵中に危険な活性酸素を放出するので好ましく
ない。The mixing ratio between the titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low-condensate thereof (hereinafter, these are simply referred to as “hydrolyzable titanium compound”) and the hydrogen peroxide solution are as follows: The former is 10 parts by weight, and the latter is 0.1 to 100 parts by weight, particularly 1 to 20 parts by weight in terms of hydrogen peroxide.
It is preferably within the range of parts by weight. If the amount of the latter is less than 0.1 part by weight in terms of hydrogen peroxide, the formation of peroxotitanic acid becomes insufficient and cloudy precipitation occurs, which is not preferable. On the other hand, if it exceeds 100 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.
【００２７】過酸化水素水の過酸化水素濃度は、特に限
定されないが、３〜４０重量％の範囲内であることが取
り扱い易さの点から好ましい。The concentration of hydrogen peroxide in the aqueous hydrogen peroxide is not particularly limited, but is preferably in the range of 3 to 40% by weight from the viewpoint of easy handling.
【００２８】また、本発明の塗布剤におけるペルオキソ
チタン酸水溶液（Ａ）は、通常、加水分解性チタン化合
物を、温度１〜７０℃程度の範囲内で１０分〜２０時間
程度、過酸化水素水と撹拌下に混合することにより調製
できる。この混合の際、必要に応じて、例えば、メタノ
ール、エタノール、ｎ−プロパノール、ｉｓｏ−イソプ
ロパノール、エチレングリコールモノブチルエーテル、
プロピレングリコールモノメチルエーテル等の水可溶性
溶媒を使用することもできる。The aqueous solution of peroxotitanic acid (A) in the coating composition of the present invention is usually prepared by adding a hydrolyzable titanium compound at a temperature of about 1 to 70 ° C. for about 10 minutes to 20 hours using a hydrogen peroxide solution. Can be prepared by mixing with stirring. During this mixing, if necessary, for example, methanol, ethanol, n-propanol, iso-isopropanol, ethylene glycol monobutyl ether,
A water-soluble solvent such as propylene glycol monomethyl ether can also be used.
【００２９】ペルオキソチタン酸水溶液（Ａ）は、加水
分解性チタン化合物を過酸化水素水と混合させることに
より、加水分解性チタン化合物が水で加水分解されて水
酸基含有チタン化合物を生成し、次いでこの水酸基含有
チタン化合物に過酸化水素が直ちに配位してペルオキソ
チタン酸を形成することにより得られるものと推察され
る。このペルオキソチタン酸水溶液（Ａ）は、室温域で
安定性が高く長期の保存に耐える。The aqueous solution of peroxotitanic acid (A) is prepared by mixing a hydrolyzable titanium compound with aqueous hydrogen peroxide, whereby the hydrolyzable titanium compound is hydrolyzed with water to produce a hydroxyl-containing titanium compound. It is presumed that hydrogen peroxide is obtained by immediately coordinating hydrogen peroxide to the hydroxyl group-containing titanium compound to form peroxotitanic acid. This aqueous solution of peroxotitanic acid (A) has high stability at room temperature and withstands long-term storage.
【００３０】上記ペルオキソチタン酸水溶液（Ａ）を、
酸化チタンゾルの存在下で、加水分解性チタン化合物を
過酸化水素水と混合して調製することにより、これにポ
リエチレングリコール（Ｂ）を混合した本発明塗布剤の
貯蔵安定性、得られる酸化チタン膜の光触媒活性等を、
更に向上させることができる。その理由は、（Ａ）成分
の調製において、加水分解性チタン化合物が酸化チタン
ゾル粒子に吸着され、この吸着された加水分解性チタン
化合物が該粒子表面に生じた水酸基と縮合反応して化学
結合すると共に、該加水分解性チタン化合物自体も縮合
反応して高分子化され、次いで過酸化水素水と混合され
ることにより、得られた（Ａ）成分を用いた塗布剤が更
に安定化され、貯蔵中のゲル化や増粘が顕著に防止され
るものと推定される。The aqueous solution of peroxotitanic acid (A) is
By preparing a hydrolyzable titanium compound and aqueous hydrogen peroxide in the presence of a titanium oxide sol, the storage stability of the coating composition of the present invention in which polyethylene glycol (B) is mixed, and the obtained titanium oxide film The photocatalytic activity of
It can be further improved. The reason is that, in the preparation of the component (A), the hydrolyzable titanium compound is adsorbed on the titanium oxide sol particles, and the adsorbed hydrolyzable titanium compound undergoes a condensation reaction with a hydroxyl group generated on the particle surface to form a chemical bond. At the same time, the hydrolyzable titanium compound itself is polymerized by a condensation reaction and then mixed with aqueous hydrogen peroxide to further stabilize the obtained coating composition using the component (A), It is presumed that gelation and thickening in the inside are significantly prevented.
【００３１】尚、本発明の（Ａ）成分に代えて、酸化チ
タンゾルだけを用いる場合には、造膜性に劣り、又これ
に後からペルオキソチタン酸水溶液を加えても相溶性が
低く造膜性もそれほど向上しない。When only titanium oxide sol is used in place of the component (A) of the present invention, the film-forming property is poor, and the compatibility is low even if an aqueous solution of peroxotitanic acid is added later. Sex is not much improved.
【００３２】本発明で使用する酸化チタンゾルは、無定
型酸化チタン微粒子、アナターゼ型酸化チタン微粒子が
水に分散されたゾルである。酸化チタンゾルとしては、
アナターゼ型酸化チタンの水分散液が、光触媒活性の点
から、好ましい。酸化チタンゾルは、水以外に、必要に
応じて、例えば、アルコール系、アルコールエーテル系
等の水性有機溶剤を含有していても構わない。The titanium oxide sol used in the present invention is a sol in which amorphous titanium oxide fine particles and anatase type titanium oxide fine particles are dispersed in water. As titanium oxide sol,
An aqueous dispersion of anatase-type titanium oxide is preferred from the viewpoint of photocatalytic activity. The titanium oxide sol may contain, for example, an aqueous organic solvent such as an alcohol or an alcohol ether, if necessary, in addition to water.
【００３３】上記酸化チタンゾルとしては、従来から公
知のものを使用することができる。該酸化チタンゾルと
しては、例えば、酸化チタン凝集物を水に分散した無定
型酸化チタン微粒子や、該酸化チタン凝集物を焼成して
アナターゼ型酸化チタン微粒子としこれを水に分散した
ものを使用することができる。無定形酸化チタンの焼成
は少なくともアナターゼの結晶化温度以上の温度、通
常、２００℃以上の温度で焼成すれば、無定形酸化チタ
ンをアナターゼ型酸化チタンに変換させることができ
る。上記酸化チタン凝集物としては、例えば、（１）硫
酸チタン、硫酸チタニル等の無機チタン化合物を加水分
解して得られるもの、（２）チタンアルコキシド等の有
機チタン化合物を加水分解して得られるもの、（３）四
塩化チタン等のハロゲン化チタン溶液を加水分解又は中
和して得られるもの等を挙げることができる。As the titanium oxide sol, conventionally known sols can be used. As the titanium oxide sol, for example, an amorphous titanium oxide fine particle in which a titanium oxide aggregate is dispersed in water, or an anatase type titanium oxide fine particle obtained by firing the titanium oxide aggregate to be used in water is used. Can be. The amorphous titanium oxide can be converted into anatase type titanium oxide by firing at least at a temperature higher than the crystallization temperature of anatase, usually at a temperature higher than 200 ° C. Examples of the titanium oxide aggregates include (1) those obtained by hydrolyzing an inorganic titanium compound such as titanium sulfate and titanyl sulfate, and (2) those obtained by hydrolyzing an organic titanium compound such as titanium alkoxide. And (3) those obtained by hydrolyzing or neutralizing a titanium halide solution such as titanium tetrachloride.
【００３４】上記酸化チタンゾルの市販品としては、例
えば、「ＴＫＳ−２０１」（テイカ（株）製、商品名、
平均粒子径６ｎｍのアナターゼ型酸化チタン微粒子の水
性ゾル）、「ＴＡ−１５」（日産化学（株）製、商品
名、アナターゼ型酸化チタン微粒子の水性ゾル）、「Ｓ
ＴＳ−１１」（石原産業（株）製、商品名、アナターゼ
型酸化チタン微粒子の水性ゾル）等が挙げられる。As the commercially available titanium oxide sol, for example, “TKS-201” (trade name, manufactured by Teika Co., Ltd.)
Aqueous sol of anatase-type titanium oxide fine particles having an average particle diameter of 6 nm), "TA-15" (trade name, manufactured by Nissan Chemical Industries, Ltd., aqueous sol of anatase-type titanium oxide fine particles), "S
TS-11 "(manufactured by Ishihara Sangyo Co., Ltd., trade name, aqueous sol of anatase type titanium oxide fine particles) and the like.
【００３５】加水分解性チタン化合物と過酸化水素水を
混合する際に、存在させる酸化チタンゾルの使用量は、
通常、加水分解性チタン化合物１重量部に対して、固形
分で０．０１〜１０重量部、好ましくは０．１〜８重量
部の範囲である。酸化チタンゾルの使用量が０．０１重
量部未満になると塗布剤の貯蔵安定性、得られる酸化チ
タン膜の光触媒活性等の向上という酸化チタンゾルを添
加した効果が得られず、一方１０重量部を越えると塗布
剤の造膜性が劣るので好ましくない。When mixing the hydrolyzable titanium compound and the hydrogen peroxide solution, the amount of titanium oxide sol to be used is as follows:
Usually, the solid content is in the range of 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 1 part by weight of the hydrolyzable titanium compound. When the amount of the titanium oxide sol is less than 0.01 part by weight, the effect of adding the titanium oxide sol such as the storage stability of the coating agent and the improvement of the photocatalytic activity of the obtained titanium oxide film cannot be obtained, while the amount exceeds 10 parts by weight. This is not preferable because the film forming property of the coating agent is inferior.
【００３６】本発明におけるペルオキソチタン酸水溶液
（Ａ）は、加水分解性チタン化合物を過酸化水素水と混
合して得られるペルオキソチタン酸水溶液を、更に、８
０℃以上の温度で加熱処理又はオートクレーブ処理して
平均粒子径が１０ｎｍ以下の酸化チタン微粒子の分散液
としてから、使用することもできる。この分散液の外観
は、通常半透明状である。The aqueous solution of peroxotitanic acid (A) in the present invention is obtained by mixing an aqueous solution of peroxotitanic acid obtained by mixing a hydrolyzable titanium compound with aqueous hydrogen peroxide,
Heat treatment or autoclave treatment at a temperature of 0 ° C. or higher can be used as a dispersion of titanium oxide fine particles having an average particle diameter of 10 nm or less. The appearance of this dispersion is usually translucent.
【００３７】加熱処理又はオートクレーブ処理の温度が
８０℃未満では、十分に酸化チタンの結晶化が進まな
い。上記処理により得られる酸化チタン微粒子は、粒子
径が１０ｎｍ以下、好ましくは１ｎｍ〜６ｎｍの範囲で
ある。該粒子径が１０ｎｍより大きくなると造膜性が低
下して、膜厚１μｍ以上でワレを生じるので好ましくな
い。If the temperature of the heat treatment or the autoclave treatment is lower than 80 ° C., crystallization of titanium oxide does not proceed sufficiently. The titanium oxide fine particles obtained by the above treatment have a particle diameter of 10 nm or less, preferably in the range of 1 nm to 6 nm. When the particle diameter is larger than 10 nm, the film-forming property is deteriorated, and cracks occur at a film thickness of 1 μm or more, which is not preferable.
【００３８】本発明の塗布剤におけるポリエチレングリ
コール（Ｂ）は、基材に塗布剤を塗布後、焼成したとき
に揮発し、揮発するときに多くの細孔を生じることによ
り、形成される酸化チタン膜を多孔質化する機能を有す
る。ポリエチレングリコール（Ｂ）は、２０℃で液状乃
至固体状であり、その平均分子量が２００〜４００万で
あるのが好ましく、６００〜７万であるのがより好まし
い。ポリエチレングリコール（Ｂ）としては、例えば、
平均分子量が６００、１，０００、１，５００、２，０
００、３，０００、８，５００、２万、７万、５０万、
４００万等の各種市販品を使用できる。The polyethylene glycol (B) in the coating agent of the present invention is formed by applying a coating agent to a base material, and then volatilizing when firing and forming many pores when volatilizing. It has the function of making the membrane porous. The polyethylene glycol (B) is liquid or solid at 20 ° C., and preferably has an average molecular weight of 2 to 4,000,000, and more preferably 600 to 70,000. As the polyethylene glycol (B), for example,
Average molecular weight of 600, 1,000, 1,500, 2,0
00, 3,000, 8,500, 20,000, 70,000, 500,000,
Various commercial products such as 4,000,000 can be used.
【００３９】本発明塗布剤におけるポリエチレングリコ
ール（Ｂ）の使用割合は、ペルオキソチタン酸水溶液
（Ａ）の固形分１００重量部に対して、０．１〜２００
重量部、好ましくは１〜１００重量部の範囲である。こ
こで、ペルオキソチタン酸水溶液（Ａ）の固形分は、二
酸化チタンに換算した固形分を意味する。ポリエチレン
グリコール（Ｂ）の使用割合が０．１重量部未満では、
酸化チタン膜の多孔質化が不十分であるので好ましくな
い。また、ポリエチレングリコール（Ｂ）の使用割合が
２００重量を超える場合には、細孔の孔径がばらついて
均一な多孔質膜が得られないので好ましくない。The proportion of polyethylene glycol (B) used in the coating composition of the present invention is 0.1 to 200 parts by weight per 100 parts by weight of the solid content of the aqueous solution of peroxotitanic acid (A).
Parts by weight, preferably in the range of 1 to 100 parts by weight. Here, the solid content of the aqueous solution of peroxotitanic acid (A) means a solid content converted to titanium dioxide. When the use ratio of the polyethylene glycol (B) is less than 0.1 part by weight,
It is not preferable because the titanium oxide film is insufficiently porous. On the other hand, if the use ratio of the polyethylene glycol (B) is more than 200%, it is not preferable because the pore diameter of the pores varies and a uniform porous film cannot be obtained.
【００４０】本発明の酸化チタン膜形成用塗布剤には、
必要に応じて、各種の添加物を含有することもできる。
添加物としては、例えば、市販されている酸化チタンゾ
ル、酸化チタン粉末、顔料等を挙げることができる。The coating agent for forming a titanium oxide film of the present invention includes:
If necessary, various additives can be contained.
Examples of the additive include commercially available titanium oxide sol, titanium oxide powder, and pigment.
【００４１】本発明の酸化チタン膜形成用塗布剤は、基
材に塗布後、通常、２００℃以上の温度で焼成すること
により、酸化チタン多孔質膜を好適に形成できる。本発
明塗布剤は、酸化チタン以外の不純物が少ないため、得
られる酸化チタン膜は、酸化チタンの純度が高い。The coating agent for forming a titanium oxide film of the present invention can be suitably formed into a titanium oxide porous film by baking at a temperature of usually 200 ° C. or more after being applied to a substrate. Since the coating agent of the present invention contains few impurities other than titanium oxide, the titanium oxide film obtained has high purity of titanium oxide.
【００４２】該塗布剤を、基材に塗布する場合の塗装方
法は、特に限定されず、公知の方法によれば良い。塗装
方法としては、例えば、印刷塗装、ナイフコーター塗
装、ドクターブレード塗装、浸漬塗装、シャワー塗装、
スプレー塗装、ロール塗装、電着塗装等の各種塗装方法
を採用することができる。The method of applying the coating agent to the substrate is not particularly limited, and may be a known method. As a coating method, for example, printing coating, knife coater coating, doctor blade coating, dip coating, shower coating,
Various coating methods such as spray coating, roll coating, and electrodeposition coating can be adopted.
【００４３】本発明塗布剤を塗布すべき基材としては、
例えば、金属、陶磁器、プラスチックス、繊維、ガラ
ス、コンクリート等の焼成又は加熱処理に耐え得る素材
であればあらゆるものを使用できる。また、基材の形状
としても、板状、球状、直方体状、円筒形状等のいずれ
の形状でも良い。更に、基材として、多孔体、粉体等を
用いて、多孔体の内部処理、粉体の表面処理を行なうこ
とも可能である。多孔体としては、例えば、ハニカム構
造体、コルゲート構造体等を挙げることができる。ま
た、粉体としては、例えば、マイカ、タルク、シリカ、
硫酸バリウム、クレー等の体質顔料を挙げることができ
る。The substrate on which the coating composition of the present invention is to be applied includes:
For example, any material that can withstand firing or heat treatment, such as metal, ceramics, plastics, fiber, glass, and concrete, can be used. Further, the shape of the substrate may be any shape such as a plate shape, a spherical shape, a rectangular parallelepiped shape, and a cylindrical shape. Furthermore, using a porous body, powder, or the like as a substrate, it is also possible to perform internal treatment of the porous body and surface treatment of the powder. Examples of the porous body include a honeycomb structure, a corrugated structure, and the like. As the powder, for example, mica, talc, silica,
Extender pigments such as barium sulfate and clay.
【００４４】本発明の酸化チタン膜形成用塗布剤を、基
材上に塗布後、２００℃以上の温度で焼成することによ
り、付着性に優れた緻密で均一な酸化チタン多孔質膜を
形成できる。また、２００℃以上で焼成することによ
り、アナターゼ型酸化チタン多孔質膜となっており、光
触媒活性が大幅に向上している。９１５℃を超えると、
アナターゼ型酸化チタンがルチル型酸化チタンに転移す
るので、焼成温度の上限は９１５℃である。焼成温度
は、好ましくは、２００〜７００℃程度である。また、
焼成時間は、温度によって変動するが、通常、１０分〜
３時間程度とするのが適当である。By coating the coating material for forming a titanium oxide film of the present invention on a substrate and firing at a temperature of 200 ° C. or more, a dense and uniform titanium oxide porous film having excellent adhesion can be formed. . Further, by firing at 200 ° C. or more, a porous film of anatase type titanium oxide is obtained, and the photocatalytic activity is greatly improved. If it exceeds 915 ° C,
Since anatase-type titanium oxide transfers to rutile-type titanium oxide, the upper limit of the firing temperature is 915 ° C. The firing temperature is preferably about 200 to 700 ° C. Also,
The firing time varies depending on the temperature, but is usually from 10 minutes to
About 3 hours is appropriate.
【００４５】得られる酸化チタン多孔質膜の多孔化の度
合いを、比表面積で示すと、通常、１０〜８００ｍ2／
ｇ程度、特に５０〜５００ｍ2／ｇ程度である。When the degree of porosity of the obtained titanium oxide porous membrane is represented by a specific surface area, it is usually from 10 to 800 m 2 /
g, especially about 50 to 500 m 2 / g.
【００４６】得られる酸化チタン多孔質膜の膜厚は、
０．００１〜２０μｍ程度であるのが好ましく、０．１
〜１５μｍの範囲であるのがより好ましい。また、通
常、１回の塗布で、剥離し難い付着性に優れた厚さ１μ
ｍ以上という厚膜の均一で緻密な酸化チタン多孔質膜を
形成できる。勿論、必要に応じて、複数回塗布しても良
い。The thickness of the obtained titanium oxide porous film is
It is preferably about 0.001 to 20 μm,
More preferably, it is in the range of 15 μm. In addition, a thickness of 1 μm, which is usually excellent in adhesiveness that is difficult to peel off in one application, is used.
m and a thick, uniform and dense porous titanium oxide film. Of course, if necessary, it may be applied a plurality of times.
【００４７】また、ペルオキソチタン酸水溶液（Ａ）と
して、酸化チタンゾルの存在下で、加水分解性チタン化
合物を過酸化水素水と混合して得たものを使用すること
により、本発明塗布剤による厚膜の形成がより容易にな
る。The aqueous solution of peroxotitanic acid (A) obtained by mixing a hydrolyzable titanium compound with an aqueous hydrogen peroxide solution in the presence of a titanium oxide sol can be used to obtain a coating composition of the present invention. The formation of the film becomes easier.
【００４８】本発明の酸化チタン膜形成用塗布剤を、基
材上に塗布後、２００℃未満の温度で加熱乾燥すると非
晶質の酸化チタン膜を形成できるが、付着性が低下し、
又多孔質膜とならないので、好ましくない。When the coating composition for forming a titanium oxide film of the present invention is applied on a substrate and then heated and dried at a temperature of less than 200 ° C., an amorphous titanium oxide film can be formed, but the adhesion is reduced.
Also, it is not preferable because it does not become a porous film.
【００４９】また、本発明塗布剤において、ペルオキソ
チタン酸水溶液（Ａ）が、加水分解性チタン化合物を過
酸化水素水と混合して得られるペルオキソチタン酸水溶
液を、更に、８０℃以上の温度で加熱処理又はオートク
レーブ処理して得られる平均粒子径が１０ｎｍ以下の酸
化チタン微粒子の分散液である場合にも、同様に、２０
０℃以上の温度で焼成することにより、付着性に優れた
均一で緻密なアナターゼ型酸化チタン多孔質膜を形成で
きる。In the coating composition of the present invention, the aqueous solution of peroxotitanic acid (A) is obtained by mixing a peroxotitanic acid aqueous solution obtained by mixing a hydrolyzable titanium compound with aqueous hydrogen peroxide at a temperature of 80 ° C. or more. Similarly, when the dispersion is a dispersion of titanium oxide fine particles having an average particle diameter of 10 nm or less obtained by a heat treatment or an autoclave treatment,
By firing at a temperature of 0 ° C. or higher, a uniform and dense anatase-type titanium oxide porous film having excellent adhesion can be formed.
【００５０】成分（Ａ）として上記酸化チタン微粒子の
分散液を使用した塗布剤を、塗布し、２００℃未満の温
度で加熱乾燥をした場合は、アナターゼ型酸化チタン膜
を形成できるが、付着性が低下し、多孔質膜とはならな
いので、好ましくない。但し、加熱処理をできない材料
の塗布剤として使用することが可能である。When a coating agent using the above dispersion liquid of titanium oxide fine particles as the component (A) is applied and dried by heating at a temperature lower than 200 ° C., an anatase type titanium oxide film can be formed. Is not preferred because a porous film is not formed. However, it can be used as a coating agent for a material that cannot be heated.
【００５１】また、この場合に得られる酸化チタン膜
は、耐水性と共に含侵性を有しているので、該膜に他の
物質の溶液を含侵させ、その後焼成又は加熱乾燥させる
ことにより、酸化チタン膜の中に他の物質を担持又は分
散した複合体を形成することも可能である。他の物質と
しては、特に限定されないが、例えば、金、銀、銅及び
白金族元素（ルテニウム、ロジウム、パラジウム、オス
ミウム、イリジウム及び白金）から選ばれる金属自体、
これらの金属の酸化物、塩化物、錯体等の金属化合物を
使用できる。Since the titanium oxide film obtained in this case has water resistance and impregnation, the film is impregnated with a solution of another substance, and then fired or dried by heating. It is also possible to form a complex in which another substance is supported or dispersed in the titanium oxide film. Other substances are not particularly limited, for example, metals themselves selected from gold, silver, copper and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium and platinum),
Metal compounds such as oxides, chlorides and complexes of these metals can be used.
【００５２】本発明によって得られる酸化チタン膜は、
付着性に優れた均一な多孔質膜であり、又通常アナター
ゼ型酸化チタンであるため、酸化チタンの光触媒活性が
大幅に向上している。従って、本発明により、基材上に
酸化チタン多孔質膜が形成されてなる光触媒は、抗菌
性、親水性、耐汚染性、防曇性、ガス分解性、脱臭性、
水処理性、エネルギー変換性、脱色性等の活性に優れて
いる。The titanium oxide film obtained according to the present invention comprises:
The photocatalytic activity of titanium oxide is greatly improved because it is a uniform porous film having excellent adhesion and is usually an anatase type titanium oxide. Therefore, according to the present invention, a photocatalyst having a porous titanium oxide film formed on a substrate has antibacterial properties, hydrophilic properties, stain resistance, antifogging properties, gas decomposability, deodorizing properties,
It has excellent activities such as water treatment, energy conversion, and decolorization.
【００５３】本発明の光触媒は、例えば、大気浄化、水
質浄化、親水化処理、抗菌処理、消臭処理、防曇処理、
排水処理、エネルギー変換等の分野で好適に利用でき
る。The photocatalyst of the present invention can be used, for example, for air purification, water purification, hydrophilic treatment, antibacterial treatment, deodorizing treatment, antifogging treatment,
It can be suitably used in fields such as wastewater treatment and energy conversion.
【００５４】より具体的には、例えば、窒素酸化物等を
酸化して硝酸に変化させる場合、アセトアルデヒドを分
解処理する場合等に好適に使用できる。More specifically, it can be suitably used, for example, when oxidizing nitrogen oxide or the like to convert it into nitric acid, or when decomposing acetaldehyde.
【００５５】また、本発明の光触媒を、エネルギー変換
材料として利用する場合、酸化チタン膜表面に増感色素
を塗布することが好ましい。増感色素は可視光領域及び
／又は赤外光領域に吸収を持つものであり、種々の金属
錯体や有機色素の一種又は二種以上を用いることができ
る。増感色素としては、分子中にカルボキシル基、ヒド
ロキシアルキル基、ヒドロキシル基、スルホン基、カル
ボキシアルキル基等の官能基を有するものが半導体への
吸着が早いため、好ましい。また、分光増感の効果や耐
久性に優れているため金属錯体が好ましい。When the photocatalyst of the present invention is used as an energy conversion material, it is preferable to apply a sensitizing dye to the surface of the titanium oxide film. The sensitizing dye has absorption in the visible light region and / or the infrared light region, and one or more of various metal complexes and organic dyes can be used. As the sensitizing dye, those having a functional group such as a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfone group, and a carboxyalkyl group in the molecule are preferable because of quick adsorption to a semiconductor. Further, a metal complex is preferable because of its excellent spectral sensitizing effect and durability.
【００５６】金属錯体としては、例えば、銅フタロシア
ニン、チタニルフタロシアニンなどの金属フタロシアニ
ン、クロロフイル、ヘミン、特開平１−２２０３８０号
や特表平５−５０４０２３号に記載のルテニウム、オス
ミウム、鉄、亜鉛の錯体を用いることができる。また、
有機色素としては、例えば、メタルフリーフタロシアニ
ン、シアニン朱色素、メロシアニン系色素、キサンテン
系色素、トリフェニルメタン色素を用いることができ
る。シアニン系色素としては、具体的には、「ＮＫ１１
９４」、「ＮＫ３４２２」（商品名、いずれも日本感光
色素研究所製）が挙げられる。メロシアニン系色素とし
ては、具体的には、「ＮＫ２４２６」、「ＮＫ２５０
１」（商品名、いずれも日本感光色素研究所製〉が挙げ
られる。キサンテン系色素としては、具体的には、ウラ
ニン、エオシン、ローズベンガル、ローダミンＢ、ジブ
ロムフルオレセインが挙げられる。トリフェニルメタン
色素としては、具体的には、マラカイトグリーン、クリ
スタルバイオレットが挙げられる。Examples of the metal complex include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll and hemin, and complexes of ruthenium, osmium, iron and zinc described in JP-A-1-220380 and JP-A-5-504033. Can be used. Also,
As the organic dye, for example, metal-free phthalocyanine, cyanine red dye, merocyanine dye, xanthene dye, and triphenylmethane dye can be used. Specific examples of the cyanine dye include “NK11
94 "and" NK3422 "(trade names, both manufactured by Japan Photosensitive Dye Laboratories). Specific examples of the merocyanine dyes include “NK2426” and “NK250”.
1 "(trade names, both manufactured by Japan Photographic Dye Laboratories). Specific examples of xanthene dyes include uranine, eosin, rose bengal, rhodamine B, and dibromofluorescein. Specific examples of the dye include malachite green and crystal violet.
【００５７】また、本発明によって得られた酸化チタン
膜は、光触媒活性の性質以外に、耐熱性、防食性等にも
優れているので耐熱塗膜、防食塗膜等として利用するこ
ともできる。The titanium oxide film obtained according to the present invention is excellent in heat resistance, corrosion resistance and the like in addition to the property of photocatalytic activity, so that it can be used as a heat-resistant coating, an anti-corrosion coating and the like.
【００５８】[0058]
【実施例】次に、実施例、比較例及び試験例を挙げて、
本発明をより具体的に説明する。但し、本発明は以下の
例に限定されるものではない。各例に記載の「部」及び
「％」は、重量基準である。Next, examples, comparative examples and test examples will be described.
The present invention will be described more specifically. However, the present invention is not limited to the following examples. “Parts” and “%” described in each example are based on weight.
【００５９】各試験例における貯蔵安定性、塗膜状態、
付着性、鉛筆硬度、耐水性、水濡れ性（水接触角）及び
比表面積の試験方法は、下記の通りである。The storage stability, coating state,
Test methods for adhesion, pencil hardness, water resistance, water wettability (water contact angle) and specific surface area are as follows.
【００６０】（１）塗布剤の貯蔵安定性：塗布剤を５０
℃で１００時間貯蔵後の粘度、沈降の有無等の変化を、
貯蔵前と比較して、貯蔵安定性を調べた。(1) Storage stability of coating agent: 50 coating agents
Changes in viscosity, sedimentation, etc. after storage at 100 ° C for 100 hours,
The storage stability was examined as compared to before storage.
【００６１】（２）塗膜状態：塗膜の平滑性、透明性、
ワレ等の塗膜異常の有無を目視で観察した。異常が無い
ものを塗膜状態良好とした。(2) State of coating film: smoothness, transparency,
The presence or absence of a coating abnormality such as cracks was visually observed. A film having no abnormality was evaluated as having a good coating state.
【００６２】（３）付着性：ＪＩＳ Ｋ−５４００
８．５．２（１９９０）碁盤目テ−プ法に準じて、１ｍ
ｍ×１ｍｍのマス目を１００個作成し、その表面にテー
プを密着させ剥離した際のマス目の残った数により、付
着性を評価した。(3) Adhesion: JIS K-5400
8.5.2 (1990) 1 m
100 squares of mx 1 mm were prepared, and the adhesion was evaluated based on the number of squares remaining when the tape was adhered to the surface and peeled off.
【００６３】（４）鉛筆硬度：ＪＩＳ Ｋ−５４００
８．４．２（１９９０）に規定する鉛筆引っかき試験を
行ない、すり傷により硬度を評価した。(4) Pencil hardness: JIS K-5400
A pencil scratch test specified in 8.4.2 (1990) was performed, and the hardness was evaluated by scratches.
【００６４】（５）耐水性：２０℃の水に７日間浸漬し
た後、白化、フクレ、ハガレ等の塗膜異常の有無を目視
で観察した。異常が無いものを耐水性良好とした。(5) Water resistance: After immersion in water at 20 ° C. for 7 days, the presence or absence of a coating abnormality such as whitening, blistering and peeling was visually observed. Those having no abnormality were regarded as having good water resistance.
【００６５】（６）水濡れ性：４ＫＷ高圧水銀灯を塗膜
表面からの距離３０ｃｍで５分間照射後、水接触角を測
定して、水濡れ性を評価した。水接触角は、２０℃にて
試験塗板上に０．０３ｃｃの脱イオン水の水滴を形成
し、水滴の接触角を協和化学（株）製、コンタクタング
ルメーターＤＣＣＡ型にて測定した。(6) Water wettability: After irradiation with a 4 KW high-pressure mercury lamp at a distance of 30 cm from the coating surface for 5 minutes, the water contact angle was measured to evaluate the water wettability. The water contact angle was determined by forming a water droplet of 0.03 cc of deionized water on a test coated plate at 20 ° C., and measuring the contact angle of the water droplet with a contact angle meter DCCA manufactured by Kyowa Chemical Industry Co., Ltd.
【００６６】（７）比表面積：酸化チタン膜形成用塗布
剤を、ガラス板に、バーコーターで、焼成後の膜厚が
１．０μｍになるように塗装し、５００℃で３０分間焼
成して、酸化チタン膜を形成した。次いで、酸化チタン
膜を横０．５ｃｍ、縦２ｃｍの大きさに切断し、ガラス
板から剥離し、測定サンプルを得た。このサンプルを測
定セルに入れ、「マイクロメリティックス高速比表面積
／細孔分布測定装置２０１０」（（株）島津製作所製、
アサップ２０１０クリプトン対応型）を用いて、ＩＳＯ
９２７７に規定される定容法（ガス吸着法）により、
表面積（ｍ2）を測定した。次いで、サンプル重量
（ｇ）当たりの比表面積（ｍ2／ｇ）を算出した。この
比表面積の値により、酸化チタン膜の多孔化度が判る。(7) Specific surface area: A coating material for forming a titanium oxide film is applied on a glass plate by a bar coater so that the film thickness after firing becomes 1.0 μm, and fired at 500 ° C. for 30 minutes. Then, a titanium oxide film was formed. Next, the titanium oxide film was cut into a size of 0.5 cm in width and 2 cm in length, and separated from the glass plate to obtain a measurement sample. This sample is put into a measuring cell, and “Micromeritics high-speed specific surface area / pore distribution measuring device 2010” (manufactured by Shimadzu Corporation)
Asap 2010 Krypton compatible type)
According to the constant volume method (gas adsorption method) specified in 9277,
The surface area (m 2 ) was measured. Next, the specific surface area (m 2 / g) per sample weight (g) was calculated. The value of the specific surface area indicates the degree of porosity of the titanium oxide film.
【００６７】加水分解性チタン化合物を過酸化水素水と
混合して得られるペルオキソチタン酸水溶液（Ａ）及び
ポリエチレングリコール（Ｂ）を含有する塗布剤につい
ての例 実施例１ テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロ
パノール１０部の混合物を、３０％過酸化水素水１０部
と脱イオン水１００部の混合物中に２０℃で１時間かけ
て撹拌しながら滴下した。その後２５℃で２時間熟成し
黄色透明の少し粘性のあるペルオキソチタン酸水溶液を
得た。さらに、ポリエチレングリコール（分子量２，０
００）５部を脱イオン水１５部に溶解した溶液を添加、
撹拌して、本発明の酸化チタン膜形成用塗布剤を得た。The hydrolyzable titanium compound is combined with a hydrogen peroxide solution.
Aqueous solution of peroxotitanic acid (A) obtained by mixing and
About the coating agent containing polyethylene glycol (B)
Examples Example 1 tetra iso- propoxy mixture of 10 parts of titanium iso- propanol 10 parts, and stirred for 1 hour at 20 ° C. in a mixture of 100 parts of 30% aqueous hydrogen peroxide 10 parts of deionized water Te While dripping. Thereafter, the mixture was aged at 25 ° C. for 2 hours to obtain a yellow transparent and slightly viscous aqueous solution of peroxotitanic acid. Furthermore, polyethylene glycol (molecular weight 2,0
00) A solution prepared by dissolving 5 parts in 15 parts of deionized water was added.
By stirring, a coating material for forming a titanium oxide film of the present invention was obtained.
【００６８】実施例２ 実施例１に記載のペルオキソチタン酸水溶液に、ポリエ
チレングリコール（分子量２万）３部を脱イオン水９部
に溶解した溶液を添加、撹拌して、本発明の酸化チタン
膜形成用塗布剤を得た。Example 2 A solution prepared by dissolving 3 parts of polyethylene glycol (molecular weight: 20,000) in 9 parts of deionized water was added to the aqueous solution of peroxotitanic acid described in Example 1 and stirred to obtain a titanium oxide film of the present invention. A coating agent for forming was obtained.
【００６９】実施例３ 実施例１に記載のペルオキソチタン酸水溶液を９５℃で
６時間加熱処理し、白黄色の半透明な酸化チタン分散液
を得た。これに、ポリエチレングリコール（分子量２，
０００）５部を脱イオン水１５部に溶解した溶液を添
加、撹拌して、本発明の酸化チタン膜形成用塗布剤を得
た。Example 3 The aqueous solution of peroxotitanic acid described in Example 1 was heated at 95 ° C. for 6 hours to obtain a white-yellow translucent titanium oxide dispersion. In addition, polyethylene glycol (molecular weight 2,
000) in 15 parts of deionized water was added and stirred to obtain a coating composition for forming a titanium oxide film of the present invention.
【００７０】実施例４ 実施例１の塗布剤と実施例３の塗布剤を、１：１（重量
比）で混合し、撹拌して、本発明の酸化チタン膜形成用
塗布剤を得た。Example 4 The coating composition of Example 1 and the coating composition of Example 3 were mixed at a ratio of 1: 1 (weight ratio) and stirred to obtain a coating composition for forming a titanium oxide film of the present invention.
【００７１】実施例５ 実施例１に記載のペルオキソチタン酸水溶液に、ポリエ
チレングリコール（分子量２万）３部を脱イオン水９部
に溶解した溶液、及び光触媒用酸化チタン粉末「Ｐ２
５」（商品名、日本アエロジル社製）２部を添加し、３
ｍｍアルミナビーズを用い、ペイントシェーカーで１時
間分散して、本発明の酸化チタン膜形成用塗布剤を得
た。Example 5 A solution in which 3 parts of polyethylene glycol (molecular weight: 20,000) was dissolved in 9 parts of deionized water in the aqueous solution of peroxotitanic acid described in Example 1, and a titanium oxide powder for photocatalyst "P2
5 "(trade name, manufactured by Nippon Aerosil Co., Ltd.) and 3 parts
Using a mm-alumina bead, the mixture was dispersed with a paint shaker for 1 hour to obtain a coating agent for forming a titanium oxide film of the present invention.
【００７２】比較例１ テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロ
パノール１０部の混合物を、３０％過酸化水素水１０部
と脱イオン水１００部の混合物中に２０℃で１時間かけ
て撹拌しながら滴下した。その後２５℃で２時間熟成
し、黄色透明の少し粘性のある比較用酸化チタン膜形成
用塗布剤を得た。Comparative Example 1 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was stirred at 20 ° C. for 1 hour in a mixture of 10 parts of 30% hydrogen peroxide and 100 parts of deionized water. While dripping. Thereafter, aging was performed at 25 ° C. for 2 hours to obtain a transparent and slightly viscous coating agent for forming a comparative titanium oxide film.
【００７３】比較例２ 比較例１の酸化チタン膜形成用塗布剤に、光触媒用酸化
チタン粉末「Ｐ２５」（商品名、日本アエロジル社製）
を２部添加し、３ｍｍアルミナビーズを用い、ペイント
シェーカーで１時間分散して、比較用酸化チタン膜形成
用塗布剤を得た。Comparative Example 2 A titanium oxide powder for photocatalyst “P25” (trade name, manufactured by Nippon Aerosil Co., Ltd.) was used as the coating material for forming a titanium oxide film of Comparative Example 1.
Was added and dispersed for 1 hour with a paint shaker using 3 mm alumina beads to obtain a comparative titanium oxide film-forming coating agent.
【００７４】比較例３ 四塩化チタン６０％水溶液５ｃｃを蒸留水で５００ｃｃ
とした水溶液に、１０％アンモニア水を滴下し、水酸化
チタンを沈殿させた。沈殿を蒸留水で洗浄後、過酸化水
素水３０％溶液を１０ｃｃ加えて、攪拌し、水酸化チタ
ンを含む黄色半透明粘性液体（比較用塗布剤）７０ｃｃ
を得た。Comparative Example 3 5 cc of a 60% aqueous solution of titanium tetrachloride was added to 500 cc of distilled water.
10% ammonia water was added dropwise to the aqueous solution thus prepared to precipitate titanium hydroxide. After the precipitate was washed with distilled water, 10 cc of a 30% hydrogen peroxide solution was added thereto, followed by stirring, and 70 cc of a yellow translucent viscous liquid containing titanium hydroxide (comparative coating agent).
I got
【００７５】比較例４ 水酸化チタンを水に０．２ｍｏｌ／ｌ分散させた液体
（比較用塗布剤）を作成した。Comparative Example 4 A liquid (comparative coating agent) in which titanium hydroxide was dispersed at 0.2 mol / l in water was prepared.
【００７６】試験例１ 実施例１〜５及び比較例１〜４で得られた各酸化チタン
膜形成用塗布剤の貯蔵安定性を、前記方法により、調べ
た。Test Example 1 The storage stability of each coating agent for forming a titanium oxide film obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was examined by the above method.
【００７７】また、上記各酸化チタン膜形成用塗布剤
を、ガラス板に、バーコーターで、焼成後の膜厚が１．
０μｍになるように塗装し、５００℃で３０分間焼成し
て、各アナターゼ型酸化チタン多孔質膜を形成した。こ
の酸化チタン膜を形成した塗板を使用して、前記方法に
より、塗膜状態、付着性、鉛筆硬度、耐水性、水濡れ性
（水接触角）及び比表面積の試験を、行なった。Each of the above coating agents for forming a titanium oxide film was applied to a glass plate by a bar coater so that the film thickness after firing was 1.
It was coated so as to have a thickness of 0 μm, and baked at 500 ° C. for 30 minutes to form each anatase-type titanium oxide porous membrane. Using the coated plate on which the titanium oxide film was formed, tests of the coating film state, adhesion, pencil hardness, water resistance, water wettability (water contact angle), and specific surface area were performed by the above-described methods.
【００７８】各試験結果を、表１に示す。Table 1 shows the test results.
【００７９】[0079]
【表１】 [Table 1]
【００８０】試験例２ アセトアルデヒドガス分解試験を行った。即ち、実施例
１、比較例１及び比較例４の各酸化チタン膜形成用塗布
剤を、ガラス板に、バーコーターで、焼成後の膜厚が
１．０μｍになるように塗装し、５００℃で３０分間焼
成して、各アナターゼ型酸化チタン多孔質膜を形成し
た。４ｋＷ高圧水銀を設置した密閉試験室にアセトアル
デヒドを充満させ、次いで該水銀灯から約３０ｃｍ離れ
た場所に、上記で得た塗板を置き、室内のアセトアルデ
ヒド量（初期０．１ｇ）を測定し、１時間後、３時間後
のアセトアルデヒド減少量を測定した。試験結果を、表
２に示す。Test Example 2 An acetaldehyde gas decomposition test was performed. That is, the respective coating materials for forming a titanium oxide film of Example 1, Comparative Example 1 and Comparative Example 4 were coated on a glass plate with a bar coater so that the film thickness after firing was 1.0 μm, and then 500 ° C. For 30 minutes to form each anatase-type titanium oxide porous membrane. A sealed test chamber in which 4 kW high-pressure mercury was installed was filled with acetaldehyde, and then the coated plate obtained above was placed at a position about 30 cm away from the mercury lamp, and the amount of acetaldehyde in the room (initial 0.1 g) was measured. Then, the amount of acetaldehyde reduction after 3 hours was measured. The test results are shown in Table 2.
【００８１】[0081]
【表２】 [Table 2]
【００８２】試験例３ 耐汚染性試験を行った。即ち、実施例２、比較例１及び
比較例４の各酸化チタン膜形成用塗布剤を、ガラス板
に、バーコーターで、焼成後の膜厚が１．０μｍになる
ように塗装し、５００℃で３０分間焼成して、各アナタ
ーゼ型酸化チタン多孔質膜を形成した。得られた塗板に
３％メチレンブルー溶液を塗付し乾燥後、ブラックライ
ト１．２ｍＷ／ｃｍ2を、１０ｃｍの距離から１時間照
射した。塗膜の着色性を目視で観察して、耐汚染性を調
べた。試験結果を、表３に示す。Test Example 3 A stain resistance test was performed. That is, the respective coating materials for forming a titanium oxide film of Example 2, Comparative Example 1 and Comparative Example 4 were applied to a glass plate by a bar coater so that the film thickness after firing became 1.0 μm, and 500 ° C. For 30 minutes to form each anatase-type titanium oxide porous membrane. The obtained coated plate was coated with a 3% methylene blue solution and dried, and then irradiated with 1.2 mW / cm 2 of black light from a distance of 10 cm for 1 hour. The coloring property of the coating film was visually observed to examine the stain resistance. The test results are shown in Table 3.
【００８３】[0083]
【表３】 [Table 3]
【００８４】試験例４ エネルギー変換性の試験を行った。即ち、実施例５、比
較例２及び比較例４の各酸化チタン膜形成用塗布剤を、
フッ素ドープした酸化スズ導電ガラスに、アプリケータ
で、焼成後の膜厚が８μｍになるように塗装し、５００
℃で３０分間焼成して、各アナターゼ型酸化チタン多孔
質膜を形成した。得られた各酸化チタン膜を、Ｒｕ（Ｉ
Ｉ）（ビピリジンジカルボン酸）２（イソチオシアン
酸）２で表されるルテニウム錯体の０．１％エタノール
溶液に、２０℃で２４時間浸漬して、増感色素を吸着さ
せて、増感された酸化チタン膜電極を得た。電極と対極
用透明導電性ガラスとを重ね合わせ、その間にヨウ素−
ヨウ素イオンを酸化環元対とする電解液を入れ、これら
の側面を樹脂で封止した後、リードを取り付けて、光電
変換素子を得た。前記光電変換素子に、ソラックス社製
人工太陽灯（１００Ｗ）を用い、照射強度１００ｍＷ/
ｃｍ2における短絡電流を測定した。試験結果を、表４
に示す。Test Example 4 An energy conversion test was performed. That is, each of the coating agents for forming a titanium oxide film of Example 5, Comparative Example 2 and Comparative Example 4 was
Paint on a fluorine-doped tin oxide conductive glass with an applicator so that the film thickness after firing becomes 8 μm,
It baked at 30 degreeC for 30 minutes, and formed each anatase type titanium oxide porous membrane. Each of the obtained titanium oxide films was coated with Ru (I
I) immersed in a 0.1% ethanol solution of a ruthenium complex represented by (bipyridinedicarboxylic acid) 2 (isothiocyanic acid) 2 at 20 ° C. for 24 hours to adsorb the sensitizing dye and sensitized oxidation A titanium film electrode was obtained. The electrode and the transparent conductive glass for the counter electrode are overlapped, and iodine-
An electrolyte solution containing iodine ions as an oxidation reduction pair was charged, these side surfaces were sealed with a resin, and a lead was attached to obtain a photoelectric conversion element. An artificial solar lamp (100 W) manufactured by Solux Co., Ltd. was used for the photoelectric conversion element, and the irradiation intensity was 100 mW /
The short-circuit current in cm 2 was measured. Table 4 shows the test results.
Shown in
【００８５】[0085]
【表４】 [Table 4]
【００８６】試験例５ エネルギー変換性の試験を行った。試験例４の各酸化チ
タン多孔質膜を、エオシンＹの１％エタノール溶液に、
２０℃で２４時間浸漬して、増感色素を吸着させて、増
感された酸化チタン膜電極を得た。試験例４と同様な方
法で短絡電流を測定した。試験結果を、表５に示す。Test Example 5 An energy conversion test was performed. Each titanium oxide porous membrane of Test Example 4 was added to a 1% ethanol solution of eosin Y,
It was immersed at 20 ° C. for 24 hours to adsorb the sensitizing dye to obtain a sensitized titanium oxide film electrode. The short-circuit current was measured in the same manner as in Test Example 4. Table 5 shows the test results.
【００８７】[0087]
【表５】 [Table 5]
【００８８】酸化チタンゾルの存在下で、加水分解性チ
タン化合物を過酸化水素水と混合して得られるペルオキ
ソチタン酸水溶液（Ａ）及びポリエチレングリコール
（Ｂ）を含有する塗布剤についての例 実施例６ テトラｉｓｏ−プロポキシチタン１０部とｉｓｏ−プロ
パノール１０部の混合物を、「ＴＫＳ−２０１」（テイ
カ(株)製、酸化チタンゾル）５部（固形分）、３０％過
酸化水素水１０部及び脱イオン水１００部の混合物中に
１０℃で１時間かけて撹拌しながら滴下した。その後１
０℃で２４間熟成し黄色透明の少し粘性のあるペルオキ
ソチタン酸水溶液を得た。さらに、ポリエチレングリコ
ール（分子量２，０００）５部を脱イオン水１５部に溶
解した溶液を添加、撹拌して、本発明の酸化チタン膜形
成用塗布剤を得た。In the presence of titanium oxide sol, hydrolyzable
Peroxy compound obtained by mixing a tan compound with aqueous hydrogen peroxide
Aqueous sotitanic acid solution (A) and polyethylene glycol
Example of coating agent containing (B) Example 6 A mixture of 10 parts of tetra-iso-propoxytitanium and 10 parts of iso-propanol was mixed with 5 parts of "TKS-201" (manufactured by Teica Co., Ltd., titanium oxide sol) (solid). Min) and 10 parts of a 30% aqueous hydrogen peroxide solution and 100 parts of deionized water were added dropwise with stirring at 10 ° C. for 1 hour. Then one
Aged at 0 ° C. for 24 hours to obtain a yellow transparent, slightly viscous aqueous solution of peroxotitanic acid. Further, a solution prepared by dissolving 5 parts of polyethylene glycol (molecular weight: 2,000) in 15 parts of deionized water was added and stirred to obtain a coating composition for forming a titanium oxide film of the present invention.
【００８９】実施例７ 実施例６に記載のペルオキソチタン酸水溶液に、ポリエ
チレングリコール（分子量２万）３部を脱イオン水９部
に溶解した溶液を添加、撹拌して、本発明の酸化チタン
膜形成用塗布剤を得た。Example 7 A solution prepared by dissolving 3 parts of polyethylene glycol (molecular weight: 20,000) in 9 parts of deionized water was added to the aqueous solution of peroxotitanic acid described in Example 6, and the mixture was stirred to obtain a titanium oxide film of the present invention. A coating agent for forming was obtained.
【００９０】実施例８ 実施例６に記載のペルオキソチタン酸水溶液に、ポリエ
チレングリコール（分子量２万）３部を脱イオン水９部
に溶解した溶液、及び光触媒用酸化チタン粉末「Ｐ２
５」（商品名、日本アエロジル社製）２部を添加し、３
ｍｍアルミナビーズを用い、ペイントシェーカーで１時
間分散して、本発明の酸化チタン膜形成用塗布剤を得
た。Example 8 A solution in which 3 parts of polyethylene glycol (molecular weight: 20,000) was dissolved in 9 parts of deionized water in the aqueous solution of peroxotitanic acid described in Example 6, and titanium oxide powder for photocatalyst “P2
5 "(trade name, manufactured by Nippon Aerosil Co., Ltd.) and 3 parts
Using a mm-alumina bead, the mixture was dispersed with a paint shaker for 1 hour to obtain a coating agent for forming a titanium oxide film of the present invention.
【００９１】試験例６ 実施例６〜８で得られた各酸化チタン膜形成用塗布剤の
貯蔵安定性を、前記方法により、調べた。Test Example 6 The storage stability of each coating material for forming a titanium oxide film obtained in Examples 6 to 8 was examined by the above-mentioned method.
【００９２】また、上記各酸化チタン膜形成用塗布剤
を、ガラス板に、バーコーターで、焼成後の膜厚が１．
０μｍになるように塗装し、５００℃で３０分間焼成し
て、各アナターゼ型酸化チタン多孔質膜を形成した。こ
の酸化チタン膜を形成した塗板を使用して、前記方法に
より、塗膜状態、付着性、鉛筆硬度、耐水性、水濡れ性
（水接触角）及び比表面積の試験を行なった。Each of the above coating agents for forming a titanium oxide film was applied to a glass plate with a bar coater so that the film thickness after firing was 1.
It was coated so as to have a thickness of 0 μm and baked at 500 ° C. for 30 minutes to form each anatase-type titanium oxide porous membrane. Using the coated plate on which the titanium oxide film was formed, tests were conducted on the state of the coated film, adhesion, pencil hardness, water resistance, water wettability (water contact angle), and specific surface area by the above method.
【００９３】各試験結果を、表６に示す。Table 6 shows the results of each test.
【００９４】[0094]
【表６】 [Table 6]
【００９５】試験例７ アセトアルデヒドガス分解試験を行った。即ち、実施例
６の酸化チタン膜形成用塗布剤を、ガラス板に、バーコ
ーターで、焼成後の膜厚が１．０μｍになるように塗装
し、５００℃で３０分間焼成して、アナターゼ型酸化チ
タン多孔質膜を形成した。４ｋＷ高圧水銀を設置した密
閉試験室にアセトアルデヒドを充満させ、次いで該水銀
灯から約３０ｃｍ離れた場所に、上記で得た塗板を置
き、室内のアセトアルデヒド量（初期０．１ｇ）を測定
し、１時間後、３時間後のアセトアルデヒド減少量を測
定した。試験結果を、表７に示す。Test Example 7 An acetaldehyde gas decomposition test was performed. That is, the coating material for forming a titanium oxide film of Example 6 was applied to a glass plate with a bar coater so that the film thickness after firing would be 1.0 μm, and then fired at 500 ° C. for 30 minutes to form an anatase type A porous titanium oxide film was formed. A sealed test chamber equipped with 4 kW high-pressure mercury was filled with acetaldehyde, and then the coated plate obtained above was placed at a position about 30 cm away from the mercury lamp, and the amount of acetaldehyde in the room (initial 0.1 g) was measured. Then, the amount of acetaldehyde reduction after 3 hours was measured. The test results are shown in Table 7.
【００９６】[0096]
【表７】 [Table 7]
【００９７】試験例８ 耐汚染性試験を行った。即ち、実施例６の酸化チタン膜
形成用塗布剤を、ガラス板に、バーコーターで、焼成後
の膜厚が１．０μｍになるように塗装し、５００℃で３
０分間焼成して、アナターゼ型酸化チタン多孔質膜を形
成した。得られた塗板に３％メチレンブルー溶液を塗付
し乾燥後、ブラックライト１．２ｍＷ／ｃｍ2を、１０
ｃｍの距離から１時間照射した。塗膜の着色性を目視で
観察して、耐汚染性を調べた。試験結果を、表８に示
す。Test Example 8 A stain resistance test was performed. That is, the coating material for forming a titanium oxide film of Example 6 was applied to a glass plate with a bar coater so that the film thickness after firing was 1.0 μm.
By baking for 0 minutes, an anatase type titanium oxide porous film was formed. The resulting coated plate in a 3% methylene blue solution after coating subjected dried, the black light 1.2 mW / cm 2, 10
Irradiated from a distance of 1 cm for 1 hour. The coloring property of the coating film was visually observed to examine the stain resistance. The test results are shown in Table 8.
【００９８】[0098]
【表８】 [Table 8]
【００９９】試験例９ エネルギー変換性の試験を行った。即ち、実施例８の酸
化チタン膜形成用塗布剤を、フッ素ドープした酸化スズ
導電ガラスに、アプリケータで、焼成後の膜厚が８μｍ
になるように塗装し、５００℃で３０分間焼成して、ア
ナターゼ型酸化チタン多孔質膜を形成した。得られた酸
化チタン膜を、Ｒｕ（ＩＩ）（ビピリジンジカルボン
酸）２（イソチオシアン酸）２で表されるルテニウム錯
体の０．１％エタノール溶液に、２０℃で２４時間浸漬
して、増感色素を吸着させて、増感された酸化チタン膜
電極を得た。電極と対極用透明導電性ガラスとを重ね合
わせ、その間にヨウ素−ヨウ素イオンを酸化環元対とす
る電解液を入れ、これらの側面を樹脂で封入した後、リ
ードを取り付けて、光電変換素子を得た。前記光電変換
素子に、ソラックス社製人工太陽灯（５００Ｗ）を用
い、照射強度１００ｍＷ/ｃｍ2における短絡電流を測定
した。試験結果を、表９に示す。Test Example 9 An energy conversion test was performed. That is, the coating material for forming a titanium oxide film of Example 8 was applied to a fluorine-doped tin oxide conductive glass using an applicator to have a thickness of 8 μm after firing.
And baked at 500 ° C. for 30 minutes to form a porous anatase-type titanium oxide film. The obtained titanium oxide film is immersed in a 0.1% ethanol solution of a ruthenium complex represented by Ru (II) (bipyridinedicarboxylic acid) 2 (isothiocyanic acid) 2 at 20 ° C. for 24 hours to obtain a sensitizing dye. Was adsorbed to obtain a sensitized titanium oxide film electrode. The electrode and the transparent conductive glass for the counter electrode are overlapped with each other, and an electrolytic solution having an iodine-iodide ion as an oxidation reduction pair is put between them, and after sealing these side surfaces with a resin, a lead is attached to the photoelectric conversion element. Obtained. The short-circuit current at an irradiation intensity of 100 mW / cm 2 was measured using an artificial solar lamp (500 W) manufactured by Solux Co., Ltd. for the photoelectric conversion element. Table 9 shows the test results.
【０１００】[0100]
【表９】 [Table 9]
【０１０１】試験例１０ エネルギー変換性の試験を行った。試験例９の酸化チタ
ン多孔質膜を、エオシンＹの１％エタノール溶液に、２
０℃で２４時間浸漬して、増感色素を吸着させて、増感
された酸化チタン膜電極を得た。試験例９と同様な方法
で短絡電流を測定した。試験結果を、表１０に示す。Test Example 10 A test for energy conversion was performed. The titanium oxide porous membrane of Test Example 9 was added to a 1% ethanol solution of eosin Y for 2 hours.
It was immersed at 0 ° C. for 24 hours to adsorb the sensitizing dye to obtain a sensitized titanium oxide film electrode. The short-circuit current was measured in the same manner as in Test Example 9. The test results are shown in Table 10.
【０１０２】[0102]
【表１０】 [Table 10]
【０１０３】[0103]
【発明の効果】本発明の酸化チタン膜形成用塗布剤、酸
化チタン膜形成方法及び光触媒によれば、次のような格
別な効果が得られる。According to the coating agent for forming a titanium oxide film, the method for forming a titanium oxide film, and the photocatalyst of the present invention, the following special effects can be obtained.
【０１０４】（１）本発明塗布剤は、酸化チタン以外の
不純物が少なく、高純度の酸化チタン膜を形成できる。(1) The coating composition of the present invention has a small amount of impurities other than titanium oxide and can form a high-purity titanium oxide film.
【０１０５】（２）本発明塗布剤は、貯蔵安定性に優れ
る。(2) The coating composition of the present invention is excellent in storage stability.
【０１０６】（３）本発明塗布剤は、製造時の副生成物
の処理等が不要で、簡便に製造することができる。(3) The coating composition of the present invention can be easily produced without the need for treatment of by-products during production.
【０１０７】（４）本発明塗布剤を用いた酸化チタン膜
形成方法によれば、基材に対する付着性に優れた均一で
緻密な酸化チタン多孔質膜を容易に得られる。また、こ
の多孔質膜は、容易に１μｍ以上の厚膜にできる。(4) According to the method for forming a titanium oxide film using the coating composition of the present invention, a uniform and dense porous titanium oxide film having excellent adhesion to a substrate can be easily obtained. Further, this porous film can be easily formed into a film having a thickness of 1 μm or more.
【０１０８】（５）得られる多孔質膜は、通常、アナタ
ーゼ型酸化チタンであり、光触媒活性が大幅に向上して
いる。(5) The obtained porous membrane is usually an anatase type titanium oxide, and the photocatalytic activity is greatly improved.
【０１０９】（６）本発明塗布剤において、ペルオキソ
チタン酸水溶液（Ａ）として、酸化チタンゾルの存在下
で、加水分解性チタン化合物を過酸化水素水と混合して
調製したものを使用することにより、本発明塗布剤の貯
蔵安定性を、更に向上させることができ、又厚膜の形成
がより容易になる。(6) In the coating composition of the present invention, an aqueous solution of peroxotitanic acid (A) prepared by mixing a hydrolyzable titanium compound with hydrogen peroxide in the presence of a titanium oxide sol is used. The storage stability of the coating composition of the present invention can be further improved, and the formation of a thick film becomes easier.
【０１１０】（７）本発明形成方法により、基材上に酸
化チタン多孔質膜が形成されてなる光触媒は、酸化チタ
ンの光触媒活性が大幅に向上しているので、例えば、有
毒ガスの分解等の環境浄化、エネルギー変換等の分野に
おいて、好適に利用できる。(7) The photocatalyst in which the titanium oxide porous film is formed on the substrate by the formation method of the present invention has a greatly improved photocatalytic activity of titanium oxide. It can be suitably used in fields such as environmental purification and energy conversion.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０１Ｇ 23/04 Ｃ０１Ｇ 23/04 Ｃ Ｃ０９Ｄ 5/00 Ｃ０９Ｄ 5/00 Ｚ 171/02 171/02 (72)発明者 磯崎 理 神奈川県平塚市東八幡４丁目17番１号 関 西ペイント株式会社内 Ｆターム(参考） 4D075 BB28Z BB93Z CA02 CA13 CA18 CA33 CA34 CA37 CA38 CA39 CA45 CB21 DA06 DA11 DA15 DA20 DA23 DA25 DB01 DB12 DB13 DB14 DB20 DB31 EA06 EA07 EA12 EB01 EB37 EB47 EB52 EB56 EB57 EC02 EC07 EC08 EC53 EC54 4G047 CA02 CB06 CB08 CC03 CD02 CD07 4G069 AA03 AA08 BA04A BA04B BA14A BA14B BA48A CA01 CA05 CA10 CA11 CA17 CC33 CD10 EA07 EA11 EB15Y EC02Y EC03Y EC22X EC22Y ED02 FA03 FB23 FB30 FC07 4J038 DF011 DM022 HA216 JA23──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C01G 23/04 C01G 23/04 C C09D 5/00 C09D 5/00 Z 171/02 171/02 (72) Inventor Osamu Isozaki 4-1-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term (reference) in Kansai Paint Co., Ltd. 4D075 BB28Z BB93Z CA02 CA13 CA18 CA33 CA34 CA37 CA38 CA39 CA45 CB21 DA06 DA11 DA15 DA20 DA23 DA25 DB01 DB12 DB13 DB14 DB20 DB31 EA06 EA07 EA12 EB01 EB37 EB47 EB52 EB56 EB57 EC02 EC07 EC08 EC53 EC54 4G047 CA02 CB06 CB08 CC03 CD02 CD07 4G069 AA03 AA08 BA04A BA04B BA14A BA14B BA48A CA01 CA05 CA10 CA11 EC03 EC03 EC03 EC03 EC03 EC10 DF011 DM022 HA216 JA23
Claims (14)
ン化合物及び／又はその低縮合物を過酸化水素水と混合
して得られるペルオキソチタン酸水溶液（Ａ）、並びに
ポリエチレングリコール（Ｂ）を含有することを特徴と
する酸化チタン膜形成用塗布剤。An aqueous solution of peroxotitanic acid (A) and a polyethylene glycol (B) obtained by mixing a titanium compound having a group which becomes a hydroxyl group by hydrolysis and / or a low condensate thereof with aqueous hydrogen peroxide. A coating agent for forming a titanium oxide film, characterized by containing.
キル基を示す。）で表されるテトラアルコキシチタンで
ある請求項１に記載の塗布剤。2. The above-mentioned titanium compound is a tetraalkoxy represented by the general formula Ti (OR) 4 (I) (wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms). The coating agent according to claim 1, which is titanium.
キル基を示す。）で表されるテトラアルコキシチタンを
お互いに縮合反応させてなる縮合度２〜３０の化合物で
ある請求項１に記載の塗布剤。3. The low-condensation product of the titanium compound is represented by the general formula: Ti (OR) 4 (I), wherein R is the same or different and represents an alkyl group having 1 to 5 carbon atoms. The coating agent according to claim 1, which is a compound having a degree of condensation of 2 to 30 obtained by subjecting the tetraalkoxytitaniums to be subjected to a condensation reaction with each other.
ン化合物及び／又はその低縮合物と過酸化水素水との混
合割合が、前者１０重量部に対して後者が過酸化水素換
算で０．１〜１００重量部の範囲内である請求項１に記
載の塗布剤。4. The mixing ratio of a titanium compound having a group which becomes a hydroxyl group by hydrolysis and / or a low condensate thereof to hydrogen peroxide water is such that the latter is 10 parts by weight and the latter is 0 in terms of hydrogen peroxide. 2. The coating agent according to claim 1, wherein the amount is in the range of 1 to 100 parts by weight.
チタンゾルの存在下で、加水分解して水酸基になる基を
有するチタン化合物及び／又はその低縮合物を過酸化水
素水と混合して得られたものである請求項１に記載の塗
布剤。5. An aqueous solution of peroxotitanic acid (A) obtained by mixing a titanium compound having a group which becomes a hydroxyl group by hydrolysis in the presence of a titanium oxide sol and / or a low condensate thereof with aqueous hydrogen peroxide. The coating composition according to claim 1, wherein the coating composition is prepared.
ンの水分散液である請求項５に記載の塗布剤。6. The coating agent according to claim 5, wherein the titanium oxide sol is an aqueous dispersion of anatase type titanium oxide.
水酸基になる基を有するチタン化合物及び／又はその低
縮合物１重量部に対して、固形分で０．０１〜１０重量
部である請求項５に記載の塗布剤。7. The titanium oxide sol is used in an amount of 0.01 to 10 parts by weight in terms of solids based on 1 part by weight of a titanium compound having a group which becomes a hydroxyl group by hydrolysis and / or 1 part by weight of a low condensate thereof. The coating composition according to claim 5.
分解して水酸基になる基を有するチタン化合物及び／又
はその低縮合物を過酸化水素水と混合して得られるペル
オキソチタン酸水溶液を、８０℃以上の温度で加熱処理
又はオートクレーブ処理して得られる平均粒子径が１０
ｎｍ以下の酸化チタン微粒子の分散体である請求項１に
記載の塗布剤。8. A peroxotitanic acid aqueous solution (A) obtained by mixing a titanium compound having a group that becomes a hydroxyl group by hydrolysis and / or a low condensate thereof with a hydrogen peroxide solution, The average particle size obtained by heat treatment or autoclave treatment at a temperature of 80 ° C. or more is 10
The coating composition according to claim 1, which is a dispersion of titanium oxide fine particles having a diameter of not more than nm.
子量２００〜４００万のものである請求項１に記載の塗
布剤。9. The coating composition according to claim 1, wherein the polyethylene glycol (B) has an average molecular weight of 2 to 4,000,000.
合が、ペルオキソチタン酸水溶液（Ａ）の固形分１００
重量部に対して、０．１〜２００重量部である請求項１
に記載の塗布剤。10. The solid content of the aqueous solution of peroxotitanic acid (A) is 100 when the proportion of the polyethylene glycol (B) used is 100%.
The amount is 0.1 to 200 parts by weight with respect to parts by weight.
The coating agent according to the above.
した後、２００℃以上の温度で焼成して酸化チタン多孔
質膜を形成することを特徴とする酸化チタン膜形成方
法。11. A method for forming a titanium oxide film, comprising: applying the coating composition according to claim 1 to a substrate, followed by firing at a temperature of 200 ° C. or higher to form a titanium oxide porous film.
化チタン多孔質膜である請求項１１に記載の酸化チタン
膜形成方法。12. The method for forming a titanium oxide film according to claim 11, wherein the titanium oxide porous film is an anatase-type titanium oxide porous film.
に酸化チタン多孔質膜が形成されてなる光触媒。13. A photocatalyst comprising a titanium oxide porous film formed on a substrate by the method according to claim 11.
化チタン多孔質膜である請求項１３に記載の光触媒。14. The photocatalyst according to claim 13, wherein the titanium oxide porous film is an anatase type titanium oxide porous film.
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| JP2000143225 | 2000-05-16 | ||
| JP2001144543A JP2002038054A (en) | 2000-05-16 | 2001-05-15 | Coating agent for forming titanium oxide film, method for forming titanium oxide film and photocatalyst |
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