JPH11262670A - Photocatalyst coating liquid and coating base material - Google Patents
Photocatalyst coating liquid and coating base materialInfo
- Publication number
- JPH11262670A JPH11262670A JP10065721A JP6572198A JPH11262670A JP H11262670 A JPH11262670 A JP H11262670A JP 10065721 A JP10065721 A JP 10065721A JP 6572198 A JP6572198 A JP 6572198A JP H11262670 A JPH11262670 A JP H11262670A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- film
- coating liquid
- photocatalyst coating
- weight
- 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
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000007788 liquid Substances 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 70
- 239000010419 fine particle Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 26
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000010304 firing Methods 0.000 claims abstract description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 55
- 239000013078 crystal Substances 0.000 claims description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- 229910003437 indium oxide Inorganic materials 0.000 claims description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 17
- 239000010408 film Substances 0.000 description 90
- 229910010413 TiO 2 Inorganic materials 0.000 description 27
- 239000010936 titanium Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 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 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- -1 ReO 3 Inorganic materials 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒膜形成用の
光触媒コーティング液およびそれを用いて形成された光
触媒膜を有するコーティング基材に関する。The present invention relates to a photocatalyst coating solution for forming a photocatalyst film and a coating substrate having a photocatalyst film formed using the same.
【０００２】[0002]
【従来の技術】ＴｉＯ2 （酸化チタンまたはチタニア）
は、紫外線を吸収して特異な化学反応を誘起する光触媒
としての活性を示す。このＴｉＯ2 にはアナターゼ型、
ブルッカイト型、ルチル型等の結晶型があり、製造条件
および使用条件等を考慮して効果的に使用しなければな
らない。 2. Description of the Related Art TiO 2 (titanium oxide or titania)
Shows an activity as a photocatalyst that absorbs ultraviolet rays to induce a specific chemical reaction. This TiO 2 has an anatase type,
There are crystal types such as brookite type and rutile type, and they must be used effectively in consideration of production conditions and use conditions.
【０００３】一般に、ＴｉＯ2 の光触媒活性については
アナターゼ型が優れている。しかし、緻密な光触媒膜を
形成させるには、 800℃を超える温度で焼成する必要が
あるため、結晶型が焼成過程でアナターゼ型からルチル
型に相変化する。このため、このような製造工程がある
場合には、ルチル型ＴｉＯ2 の光触媒活性を利用するこ
とになる。In general, the photocatalytic activity of TiO 2 is superior to the anatase type. However, in order to form a dense photocatalyst film, it is necessary to perform calcination at a temperature exceeding 800 ° C., so that the crystal form changes from an anatase type to a rutile type in the calcination process. Therefore, if such a manufacturing process is present, the photocatalytic activity of rutile-type TiO 2 is used.
【０００４】チタニアゾルのみからなるコーティング液
を用いて得られる光触媒膜は、実用上十分な膜強度を得
るためには、より高い温度で焼成する必要があるが、焼
成温度を高めることにより、光触媒活性が高いアナター
ゼ型の結晶相が得られにくくなる。また、低温で焼成し
た場合には、非晶質相とわずかなアナターゼ相とになる
ため、光触媒活性は十分ではない。これらの理由で、光
触媒活性と膜強度の両立が困難であった。A photocatalyst film obtained by using a coating solution consisting only of titania sol needs to be fired at a higher temperature in order to obtain sufficient film strength for practical use. Makes it difficult to obtain an anatase-type crystal phase. Further, when calcined at a low temperature, an amorphous phase and a slight anatase phase are formed, so that the photocatalytic activity is not sufficient. For these reasons, it has been difficult to achieve both photocatalytic activity and film strength.
【０００５】この他に、チタニアゾルにシリカゾルを加
えたコーティング液を用いて得られる光触媒膜では、よ
り低温の焼成温度で実用上充分な膜強度を得ることがで
きるものの、シリカ（ＳｉＯ2 ）の添加により膜の結晶
性が一段と低下し、また膜中のＴｉＯ2 分率も低下する
ため、光触媒活性は急激に低下する。[0005] In addition, a photocatalytic film obtained by using a coating solution obtained by adding silica sol to titania sol can obtain practically sufficient film strength at a lower firing temperature, but it does not contain silica (SiO 2 ). As a result, the crystallinity of the film further decreases, and the TiO 2 fraction in the film also decreases, so that the photocatalytic activity sharply decreases.
【０００６】また、基材表面にルチル型ＴｉＯ2 と、結
晶径 0.01 μｍ未満のＳｎＯ2 （酸化錫）との混合物か
らなる薄膜を形成し、ルチル型ＴｉＯ2 以外に結晶径
0.01μｍ未満のＳｎＯ2 を存在させ、光触媒膜の光触媒
活性を向上させたものがある（特開平 8-224481 号）。
しかし、光触媒活性を向上できるとしても、これはルチ
ル型に対するものであり、アナターゼ型の場合における
よりもはるかに低くく、光触媒活性効果が十分でない。Further, a thin film made of a mixture of rutile-type TiO 2 and SnO 2 (tin oxide) having a crystal diameter of less than 0.01 μm is formed on the surface of the substrate, and a crystal diameter other than the rutile-type TiO 2 is formed.
There is one in which SnO 2 of less than 0.01 μm is present to improve the photocatalytic activity of the photocatalytic film (Japanese Patent Laid-Open No. 8-224481).
However, even if the photocatalytic activity can be improved, this is for the rutile type, much lower than in the case of the anatase type, and the photocatalytic activity effect is not sufficient.
【０００７】〔問題点〕このような従来のコーティング
液を用いて得られる光触媒膜においては、チタニアゾル
にシリカゾルを加えたコーティング液を用いて得られる
光触媒膜では、シリカの添加により膜の結晶性が一段と
低下するとともに膜中のＴｉＯ2 分率も低下し、光触媒
活性は低下する。[Problems] In a photocatalyst film obtained by using such a conventional coating solution, in a photocatalyst film obtained by using a coating solution obtained by adding silica sol to titania sol, the crystallinity of the film is reduced by the addition of silica. As it further decreases, the TiO 2 fraction in the film also decreases, and the photocatalytic activity decreases.
【０００８】特に、ルチル型ＴｉＯ2 以外にＳｎＯ2 を
存在させたものでは、ルチル型としては光触媒活性を向
上させることができるとしても、アナターゼ型の場合に
おける光触媒活性よりもはるかに低くく、光触媒活性が
十分でない。また、チタニアゾルのみからなるコーティ
ング液を用いて得られる光触媒膜は、光触媒活性と膜強
度の両立が困難である。等々、光触媒活性と膜強度とが
共に優れた光触媒膜を形成することが困難であるという
問題点があった。In particular, in the case where SnO 2 is present in addition to the rutile type TiO 2 , even if the photocatalytic activity of the rutile type can be improved, the photocatalytic activity is much lower than that of the anatase type. Not enough activity. Further, it is difficult to achieve both photocatalytic activity and film strength of a photocatalyst film obtained using a coating solution composed of only titania sol. For example, there is a problem that it is difficult to form a photocatalyst film having both excellent photocatalytic activity and film strength.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、従来の技術
における問題点を解消するためのものであり、そのため
の課題は、光触媒活性と膜強度とが共に優れた光触媒膜
を形成することのできる光触媒コーティング液、およ
び、それを用いて形成された光触媒膜を有するコーティ
ング基材を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the problems in the prior art, and an object of the present invention is to form a photocatalytic film having excellent photocatalytic activity and film strength. An object of the present invention is to provide a photocatalyst coating solution that can be formed and a coating substrate having a photocatalyst film formed using the same.
【００１０】[0010]
【課題を解決するための手段】本発明における請求項１
に係る光触媒コーティング液は、Ｔｉアルコキシドの加
水分解物および平均粒径 100ｎｍ以下の電子伝導性酸化
物微粒子を含有させたことを特徴とするものである。Means for Solving the Problems Claim 1 of the present invention
The photocatalyst coating liquid according to the above is characterized by containing a hydrolyzate of Ti alkoxide and electron-conductive oxide fine particles having an average particle diameter of 100 nm or less.
【００１１】請求項２に係る光触媒コーティング液は、
前記電子伝導性酸化物微粒子が分散粒子径 100ｎｍ以下
に分散されていることを特徴とする。The photocatalyst coating liquid according to claim 2 is
The electron conductive oxide fine particles are dispersed in a dispersion particle diameter of 100 nm or less.
【００１２】請求項３に係る光触媒コーティング液は、
前記Ｔｉアルコキシドの加水分解物および前記電子伝導
性酸化物微粒子を、それぞれ、前記光触媒コーティング
液の固形分中、酸化物重量換算で、 80 〜 99.99 重量
％、0.01〜 20 重量％含有することを特徴とする。The photocatalyst coating solution according to claim 3 is:
The hydrolyzate of the Ti alkoxide and the electron conductive oxide fine particles are contained in the solid content of the photocatalyst coating solution in an amount of 80 to 99.99% by weight and 0.01 to 20% by weight, respectively, in terms of oxide weight. And
【００１３】請求項４に係る光触媒コーティング液は、
平均粒径 100ｎｍ以下のアナターゼ型ＴｉＯ2 微粒子を
0.1〜 20 重量％添加したことを特徴とする。The photocatalyst coating liquid according to claim 4 is
Anatase TiO 2 fine particles with an average particle size of 100 nm or less
It is characterized by adding 0.1 to 20% by weight.
【００１４】請求項５に係る光触媒コーティング液は、
Ｓｉアルコキシドの加水分解物を0.1 〜 20 重量％添加
したことを特徴とする。[0014] The photocatalyst coating liquid according to claim 5 comprises:
It is characterized by adding 0.1 to 20% by weight of a hydrolyzate of Si alkoxide.
【００１５】請求項６に係る光触媒コーティング液は、
前記電子伝導性酸化物微粒子がアンチモンドープ酸化
錫、錫ドープ酸化インジウム、ＲｅＯ3 ，ＲｕＯ2 ，Ｉ
ｒＯ2，ＯｓＯ2 ，ＶＯ2 のうち少なくとも１種以上を
含む電子伝導性酸化物であることを特徴とする。[0015] The photocatalyst coating liquid according to claim 6 comprises:
The electron conductive oxide fine particles are composed of antimony-doped tin oxide, tin-doped indium oxide, ReO 3 , RuO 2 , I
It is an electron conductive oxide containing at least one of rO 2 , OsO 2 , and VO 2 .
【００１６】請求項７に係るコーティング基材は、請求
項１〜６のいずれかに記載の光触媒コーティング液を用
いて、耐熱性基板上に塗布、焼成させて形成した光触媒
膜を有することを特徴とするものである。According to a seventh aspect of the present invention, there is provided a coating base material having a photocatalyst film formed by applying and baking a heat-resistant substrate using the photocatalyst coating solution according to any one of the first to sixth aspects. It is assumed that.
【００１７】請求項８に係るコーティング基材は、前記
光触媒膜が、主としてアナターゼ結晶相からなることを
特徴とする。According to an eighth aspect of the present invention, in the coating substrate, the photocatalytic film mainly comprises an anatase crystal phase.
【００１８】請求項９に係るコーティング基材は、前記
光触媒膜と耐熱性基材との間に、ＳｉＯ2 アンダーコー
ト層を有することを特徴とする。According to a ninth aspect of the present invention, there is provided a coating substrate having an SiO 2 undercoat layer between the photocatalytic film and the heat-resistant substrate.
【００１９】[0019]
【発明の実施の形態】以下、本発明の実施の形態を具体
的に説明する。ただし、この実施の形態は、本発明の趣
旨をより良く理解させるため具体的に説明するもので、
特に指定のない限り、発明内容を限定させるものではな
い。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. However, this embodiment is specifically described for better understanding of the gist of the present invention.
It does not limit the invention unless otherwise specified.
【００２０】チタニウムテトライソプロポキシド等のチ
タニウムアルコキシド（これを本明細書中Ｔｉアルコキ
シドと言う）に水と触媒を加えた加水分解液に、平均粒
子径100ｎｍ以下の電子伝導性酸化物微粒子を加えてコ
ーティング液を作製し、このコーティング液を基材に塗
布し、焼成することにより、ＴｉＯ2 の周囲に微小電極
を生成せしめ、紫外線の照射によって生じた電子をトラ
ップして、電子正孔対の再結合を抑制し、光触媒活性が
高められた光触媒膜を得ることができる。この際、前記
電子伝導性酸化物微粒子は、高い解砕力が与えられて分
散粒子径が 100ｎｍ以下まで分散されているのが好まし
い。以下、この場合に基づいて詳述する。To a hydrolyzate obtained by adding water and a catalyst to a titanium alkoxide such as titanium tetraisopropoxide (hereinafter referred to as Ti alkoxide), electron conductive oxide fine particles having an average particle diameter of 100 nm or less are added. A coating liquid is prepared by applying the coating liquid to a base material, and by baking, a microelectrode is generated around TiO 2 , electrons generated by irradiation with ultraviolet rays are trapped, and electron-hole pairs are formed. Recombination can be suppressed, and a photocatalytic film having enhanced photocatalytic activity can be obtained. At this time, it is preferable that the electron conductive oxide fine particles are given a high crushing power and dispersed to a dispersed particle diameter of 100 nm or less. Hereinafter, a detailed description will be given based on this case.
【００２１】光触媒膜の製造には、例えばポリオキシエ
チレンアルキルリン酸エステル、ポリエステル酸塩等の
界面活性剤を添加したアルコール等の有機溶媒中に、平
均粒径 100ｎｍ以下の電子伝導性酸化物微粒子を加え、
ボールミル、サンドミル等の粉砕機械を用いて高い解砕
力を与えることにより、電子伝導性酸化物微粒子を分散
粒子径が 100ｎｍ以下にまで高分散させた分散液と、Ｔ
ｉアルコキシドを含むアルコール溶液に水（必要に応じ
て酸またはアルカリ触媒を添加）を加えて加水分解させ
た溶液（以下チタニアゾルと言う）を混合した液に、必
要に応じて分散粒子径が 100ｎｍ以下にまで分散させた
アナターゼ型ＴｉＯ2 微粒子分散液（以下アナターゼ型
ＴｉＯ2 分散液と言う）、および／またはアルコール中
にオルトケイ酸テトラメチルまたはオルトケイ酸テトラ
エチルを加えて酸またはアルカリ触媒を含む水を添加す
ることにより得られた溶液（以下シリカゾルと言う）を
加えたコーティング液を用いる。For the production of the photocatalytic film, for example, electron-conductive oxide fine particles having an average particle size of 100 nm or less are dissolved in an organic solvent such as alcohol to which a surfactant such as polyoxyethylene alkyl phosphate or polyester salt is added. And add
By applying a high crushing force using a crushing machine such as a ball mill or a sand mill, a dispersion liquid in which electron conductive oxide fine particles are highly dispersed to a dispersed particle diameter of 100 nm or less, and T
A solution obtained by adding water (an acid or an alkali catalyst is added as necessary) to an alcohol solution containing i-alkoxide and hydrolyzing the solution (hereinafter referred to as titania sol) is mixed with a solution having a dispersed particle diameter of 100 nm or less as necessary. adding water containing anatase TiO 2 fine particle dispersion (hereinafter anatase say TiO 2 dispersion), and / or an acid or alkali catalyst added tetramethyl orthosilicate or tetraethyl orthosilicate in alcohol dispersed until the A coating solution to which a solution (hereinafter, referred to as silica sol) obtained by the above-mentioned process is added is used.
【００２２】作製されるコーティング液における配合量
（全て酸化物換算，単位は重量％）は、以下のように配
合する。 80 ≦ チタニアゾル ＜ 100 0 ＜ 電子伝導性酸化物 ≦ 20 0 ≦ アナターゼ型ＴｉＯ2 分散液 ≦ 20 0 ≦ シリカゾル ≦ 20The amount of the coating solution to be prepared (all in terms of oxide, unit is% by weight) is as follows. 80 ≦ titania sol <100 0 <electron conductive oxide ≦ 200 0 ≦ anatase type TiO 2 dispersion ≦ 200 0 ≦ silica sol ≦ 20
【００２３】このコーティング液を基材にコーティング
して、温度 150℃以上 800℃未満で焼成することによ
り、高い光触媒活性、高い透明性および高い膜強度を有
する光触媒膜を得る。The coating solution is coated on a substrate and fired at a temperature of 150 ° C. or more and less than 800 ° C. to obtain a photocatalytic film having high photocatalytic activity, high transparency and high film strength.
【００２４】ここで用いられるＴｉアルコキシドとして
は、チタニウムテトラブトキシド、チタニウムテトライ
ソプロポキシド等が好ましく用いられる。また、電子伝
導性酸化物としては、酸化錫、アンチモンドープ酸化ス
ズ（ＡＴＯ）、酸化インジウム、スズドープ酸化インジ
ウム（ＩＴＯ）、ＲｅＯ3 、ＲｕＯ2 、ＩｒＯ2 、Ｏｓ
Ｏ2 、ＶＯ2 等を例示することができるが、これに限ら
ず、ＴｉＯ2 の周囲に微小電極を生成せしめ、紫外線の
照射によって生じた電子をトラップすることにより、電
子正孔対の再結合を抑制できる物質であれば、何でも良
い。As the Ti alkoxide used here, titanium tetrabutoxide, titanium tetraisopropoxide and the like are preferably used. Examples of the electron conductive oxide include tin oxide, antimony-doped tin oxide (ATO), indium oxide, tin-doped indium oxide (ITO), ReO 3 , RuO 2 , IrO 2 , and Os.
O 2 , VO 2, etc. can be exemplified. However, the present invention is not limited to this. By generating microelectrodes around TiO 2 and trapping electrons generated by irradiation with ultraviolet rays, recombination of electron-hole pairs is achieved. Any substance can be used as long as it is a substance capable of suppressing the odor.
【００２５】コーティング液は、電極形成材として加え
る電子伝導性酸化物微粒子の量が全体の 20 重量％を超
えると、膜の強度低下が大きく、実用上十分ではなくな
ってしまう。また、電子伝導性酸化物微粒子を分散粒子
径で 100ｎｍ以下にまで高分散させておかないと、膜の
透明性が得られないばかりか、膜中の凝集粒子が膜の強
度を大幅に低下させてしまう。If the amount of the electron conductive oxide fine particles added as an electrode forming material exceeds 20% by weight of the coating liquid, the strength of the film is greatly reduced, and the coating liquid is not practically sufficient. In addition, unless the electron conductive oxide fine particles are highly dispersed to a dispersion particle diameter of 100 nm or less, not only the transparency of the film is not obtained, but also the aggregated particles in the film significantly reduce the strength of the film. Would.
【００２６】一方、コーティング液は、膜強度をより高
めるために、シリカ加水分解物を加える場合でも、その
量が全体の 20 重量％を超えると、たとえ電子伝導性酸
化物微粒子を加えていたとしても、結晶性の低下への影
響が大きく、膜中のＴｉＯ2分率も低下するため、光触
媒活性がほとんど発現しなくなる。On the other hand, even if a silica hydrolyzate is added in order to further increase the film strength, if the amount of the coating liquid exceeds 20% by weight of the coating liquid, it is assumed that the electron conductive oxide fine particles are added. However, the effect on the reduction in crystallinity is large, and the TiO 2 fraction in the film is also reduced, so that the photocatalytic activity hardly appears.
【００２７】このため、チタニアゾルと電子伝導性酸化
物分散液とを少なくとも含有させて作製したコーティン
グ液を塗布し、焼成することにより、光触媒活性と膜強
度とを両立させた光触媒膜が得られるようになるから、
コーティング液にはＴｉアルコキシドの加水分解物およ
び平均粒径 100ｎｍ以下の電子伝導性酸化物微粒子を含
有させる必要がある。For this reason, a coating solution prepared by containing at least a titania sol and an electron-conductive oxide dispersion is applied and fired to obtain a photocatalytic film having both photocatalytic activity and film strength. Because
The coating liquid must contain a hydrolyzate of Ti alkoxide and electron conductive oxide fine particles having an average particle diameter of 100 nm or less.
【００２８】このうち、チタニウムテトラブトキシド、
チタニウムテトライソプロポキシド等のＴｉアルコキシ
ドの加水分解物を用いることにより、光触媒膜の膜強度
が向上し、また、焼成により一部がアナターゼ型ＴｉＯ
2 となるため、光触媒膜の光触媒活性効果が発現する。Among them, titanium tetrabutoxide,
By using a hydrolyzate of Ti alkoxide such as titanium tetraisopropoxide, the film strength of the photocatalyst film is improved, and part of the photocatalyst film is anatase type TiO.
As a result, the photocatalytic activity of the photocatalytic film is exhibited.
【００２９】コーティング液の固形分中、酸化物重量換
算の重量％として、Ｔｉアルコキシドが80重量％未満で
は膜強度が不十分となり、99.99 重量％を超える場合は
電子伝導性酸化物の配合量が少なくなり、光触媒膜の高
い光触媒活性効果を得ることができない。When the content of Ti alkoxide is less than 80% by weight in terms of the weight of oxide in the solid content of the coating solution, the film strength becomes insufficient, and when it exceeds 99.99% by weight, the amount of the electron conductive oxide is reduced. Therefore, a high photocatalytic activity effect of the photocatalytic film cannot be obtained.
【００３０】また、電子伝導性酸化物微粒子は酸化錫、
アンチモンドープ酸化錫、酸化インジウム、錫ドープ酸
化インジウム、ＲｅＯ3 ，ＲｕＯ2 ，ＩｒＯ2 ，ＯｓＯ
2 ，ＶＯ2 のうち少なくとも１種以上を含む電子伝導性
酸化物を用いることができ、平均粒子径 100ｎｍ以下の
電子伝導性酸化物微粒子を用いることにより、光触媒膜
が高い光触媒活性効果および透明性を備えたものとな
る。The electron conductive oxide fine particles are tin oxide,
Antimony-doped tin oxide, indium oxide, tin-doped indium oxide, ReO 3 , RuO 2 , IrO 2 , OsO
An electron conductive oxide containing at least one of VO 2 and VO 2 can be used. By using electron conductive oxide fine particles having an average particle diameter of 100 nm or less, a photocatalytic film has a high photocatalytic activity and transparency. Will be provided.
【００３１】平均粒径 100ｎｍを超える電子伝導性酸化
物微粒子を用いた場合には、光触媒膜の透明性が不十分
になり、また、光触媒膜中の凝集粒子が膜強度の低下の
原因となる。光触媒コーティング液の固形分中、酸化物
重量換算の重量％で、 0.01 重量％未満では光触媒膜の
高い光触媒活性効果が得られず、 20 重量％を超える場
合では、Ｔｉアルコキシシドの配合量が少なくなり、光
触媒膜の膜強度が不十分となる。When electron conductive oxide fine particles having an average particle diameter of more than 100 nm are used, the transparency of the photocatalyst film becomes insufficient, and the aggregated particles in the photocatalyst film cause a decrease in the film strength. . In the solid content of the photocatalyst coating solution, in terms of weight% in terms of oxide weight, if it is less than 0.01% by weight, a high photocatalytic activity effect of the photocatalyst film cannot be obtained. The film strength of the photocatalyst film becomes insufficient.
【００３２】平均粒径 100ｎｍ以下のアナターゼ型Ｔｉ
Ｏ2 微粒子を添加することが好ましい。この平均粒径 1
00ｎｍ以下のアナターゼ型ＴｉＯ2 微粒子を用いること
により、光触媒膜中のＴｉＯ2 のうちアナターゼ型結晶
の比率が増加するため、高い光触媒活性効果が得られ
る。Anatase type Ti having an average particle size of 100 nm or less
It is preferable to add O 2 fine particles. This average particle size 1
By using anatase-type TiO 2 fine particles having a diameter of 00 nm or less, the ratio of anatase-type crystals in TiO 2 in the photocatalytic film increases, so that a high photocatalytic activity effect can be obtained.
【００３３】平均粒径 100ｎｍを超えるアナターゼ型Ｔ
ｉＯ2 微粒子を用いた場合には、比表面積が小さいため
光触媒膜の光触媒活性効果が低下し、また光触媒膜の透
明性も低下する。アナターゼ型ＴｉＯ2 微粒子の配合量
が光触媒コーティング液の固形分中、酸化物重量換算の
重量％で、0.1 重量％未満では光触媒膜の光触媒活性効
果の向上が現れず、 20 重量％を超える場合では膜強度
が低下する。Anatase type T having an average particle size exceeding 100 nm
When iO 2 fine particles are used, the photocatalytic activity of the photocatalytic film is reduced due to the small specific surface area, and the transparency of the photocatalytic film is also reduced. When the blending amount of the anatase type TiO 2 fine particles is the weight percentage in terms of oxide weight in the solid content of the photocatalyst coating liquid, if it is less than 0.1% by weight, the improvement of the photocatalytic activity effect of the photocatalyst film does not appear. The film strength decreases.
【００３４】膜強度の向上の点でＳｉアルコキシドの加
水分解物を添加することが好ましい。光触媒コーティン
グ液の固形分中、酸化物重量換算の重量％で、0.1 重量
％未満ではＳｉアルコキシドの添加による膜強度の向上
の効果が現れず、 20 重量％を超える場合はＴｉアルコ
キシドの加水分解物および電子伝導性酸化物の配合量が
少なくなり光触媒膜の光触媒活性効果が低下する。It is preferable to add a hydrolyzate of Si alkoxide from the viewpoint of improving the film strength. In the solid content of the photocatalyst coating liquid, in terms of weight% in terms of oxide weight, if less than 0.1% by weight, the effect of improving the film strength by adding Si alkoxide does not appear. If it exceeds 20% by weight, hydrolyzate of Ti alkoxide In addition, the compounding amount of the electron conductive oxide decreases, and the photocatalytic activity effect of the photocatalytic film decreases.
【００３５】光触媒膜のＴｉＯ2 は、ルチル型結晶では
光触媒活性効果が十分でないため、主としてアナターゼ
型結晶からなることが好ましい。It is preferable that the TiO 2 of the photocatalyst film is mainly composed of an anatase type crystal because the photocatalytic activity effect is not sufficient with a rutile type crystal.
【００３６】焼成温度は、Ｔｉアルコキシドの加水分解
物の結晶成長の点で、実用的に充分な温度範囲である15
0 〜700 ℃が好ましい。The firing temperature is a temperature range which is practically sufficient in terms of crystal growth of the hydrolyzate of Ti alkoxide.
0-700 ° C is preferred.
【００３７】基材については、焼成温度範囲において使
用可能な材料ならば使用することができる。例えば、15
0 ℃以上の温度に耐え得るプラスチックも使用できる
が、特に、ガラス、陶器、磁器、金属またはステンレス
鋼を含む合金、ファインセラミックスなどの耐熱性基材
の使用が好ましい。As the base material, any material that can be used within the firing temperature range can be used. For example, 15
Although a plastic that can withstand a temperature of 0 ° C. or more can be used, it is particularly preferable to use a heat-resistant base material such as glass, pottery, porcelain, metal or an alloy including stainless steel, and fine ceramics.
【００３８】光触媒を基材との間に、基材と光触媒膜の
密着性の向上、さらにガラス等のアルカリ成分を含む基
材の場合にはアルカリバリアとしての効果を有するＳｉ
Ｏ2アンダーコート層を設けることが好ましい。[0038] Between the photocatalyst and the substrate, Si has an effect of improving the adhesion between the substrate and the photocatalyst film, and further has an effect as an alkali barrier in the case of a substrate containing an alkali component such as glass.
It is preferable to provide an O 2 undercoat layer.
【００３９】光触媒コーティング液中に含有させるアナ
ターゼ型ＴｉＯ2 微粒子は、アナターゼ型ＴｉＯ2 微粒
子を核として表面にシリカなどの多孔質セラミックスを
被覆した複合光触媒微粒子であっても良い。The anatase-type TiO 2 fine particles to be contained in the photocatalyst coating liquid may be composite photocatalyst fine particles having anatase-type TiO 2 fine particles as nuclei and coated on the surface with a porous ceramic such as silica.
【００４０】[0040]
【実施例】〔実施例１〕 平均粒径 20 ｎｍのＡＴＯ粒子 40 部 リン酸エステル系界面活性剤 2 部 エタノール 58 部 を 1ｍｍ径ガラスビーズ 100部とともにボールミルで一
昼夜混合分散し、ＡＴＯのエタノール分散液（ａ１）を
得た。一方、チタニウムテトライソプロポキシドのエタ
ノール溶液に当量の水と少量のＨＣｌを加えチタニア加
水分解液（ｔ１）を作成した。これらを、焼成後の酸化
物重量比で、 ［ｔ１中のＴｉアルコキシド含有量（ＴｉＯ2 換算）］
／［ａ１中のＡＴＯ含有量］ ＝ 95 ／ 5 、焼成後の酸化チタン重量濃度で 5％となるように混合
し、光触媒コーティング液（ｃ１）を得た。さらに、こ
のコーティング液を、予め、ＳｉＯ2 によるＮａバリア
層を設けたガラス上にスピンコート法で塗工し、 500℃
で 30 分間焼成して、光触媒膜付きガラス（ｇ１）を得
た。[Example 1] [Example 1] 40 parts of ATO particles having an average particle diameter of 20 nm 40 parts of a phosphate ester surfactant 2 parts 58 parts of ethanol were mixed and dispersed with 100 parts of 1 mm-diameter glass beads all day and night by a ball mill to disperse ATO in ethanol. A liquid (a1) was obtained. On the other hand, an equivalent amount of water and a small amount of HCl were added to an ethanol solution of titanium tetraisopropoxide to prepare a titania hydrolyzate (t1). These were determined by the oxide weight ratio after firing, [Ti alkoxide content in t1 (TiO 2 conversion)]
/ [ATO content in a1] = 95/5, and mixed such that the weight concentration of titanium oxide after calcination was 5% to obtain a photocatalyst coating liquid (c1). Further, this coating solution was applied onto glass in advance provided with a Na barrier layer of SiO 2 by spin coating,
For 30 minutes to obtain glass (g1) with a photocatalytic film.
【００４１】〔実施例２〕テトラエチルオルトケイ酸の
エタノール溶液に当量の水と少量のＨＣｌを加え作成し
たシリカ加水分解液（ｓ２）と、前記ｔ１及びａ１を用
いて酸化物重量比で、 ［ｔ１中のＴｉアルコキシド含有量（ＴｉＯ2 換算）］
／［ａ１中のＡＴＯ含有量］／［ｓ２中のＳｉアルコキ
シド含有量（ＳｉＯ2 換算）］＝ 90 ／ 5／ 5 、焼成後の酸化チタン重量濃度で 5％となるように混合
し、光触媒コーティング液（ｃ２）を得た。さらにこの
コーティング液を、予め、ＳｉＯ2 によるＮａバリア層
を設けたガラス上にスピンコート法で塗工し、温度 500
℃にて 30 分間焼成して、光触媒膜付きガラス（ｇ２）
を得た。Example 2 A silica hydrolyzate (s2) prepared by adding an equivalent amount of water and a small amount of HCl to an ethanol solution of tetraethylorthosilicic acid, and the above-mentioned t1 and a1 were used to determine the oxide weight ratio, Ti alkoxide content in TiO 2 conversion]
/ [ATO content in a1] / [Si alkoxide content in s2 (in terms of SiO 2 )] = 90/5/5, mixed at 5% by weight of titanium oxide after calcination, and photocatalytic coating A liquid (c2) was obtained. Further, this coating solution was applied in advance by spin coating on glass on which a Na barrier layer of SiO 2 was provided.
Baked at ℃ for 30 minutes, glass with photocatalytic film (g2)
I got
【００４２】〔比較例１〕実施例１に記載のチタニア加
水分解液（ｔ１）にエタノールを加えたコーティング液
（Ｃ１）を用いて、実施例１記載の光触媒膜と同様に、
光触媒膜付きガラス（Ｇ１）を得た。[Comparative Example 1] A coating solution (C1) obtained by adding ethanol to the titania hydrolyzate (t1) described in Example 1 was used in the same manner as in the photocatalyst film described in Example 1.
A glass with a photocatalytic film (G1) was obtained.
【００４３】〔比較例２〕実施例１に記載のチタニア加
水分解液（ｔ１）と実施例２に記載のシリカ加水分解液
（ｓ２）を用いて酸化物重量比で、 ［ｔ１中のＴｉアルコキシド含有量（ＴｉＯ2 換算）］
／［ｓ２中のＳｉアルコキシド含有量（ＳｉＯ2 換
算）］ ＝ 95 ／ 5 、焼成後の酸化チタン重量濃度で 5％となるように混合
し、光触媒コーティング液（Ｃ２）を得た。さらに同様
に、光触媒膜付きガラス（Ｇ２）を得た。Comparative Example 2 Using the titania hydrolyzate (t1) described in Example 1 and the silica hydrolyzate (s2) described in Example 2, the weight ratio of the oxides was as follows: [Ti alkoxide in t1] Content (TiO 2 equivalent)]
/ [Si alkoxide content in s2 (in terms of SiO 2 )] = 95/5, and mixed such that the weight concentration of titanium oxide after calcination was 5% to obtain a photocatalyst coating liquid (C2). Furthermore, similarly, glass (G2) with a photocatalytic film was obtained.
【００４４】〔膜の透明性および強度〕得られた光触媒
膜の鉛筆硬度を表１に、ヘイズ値を表２に示す。これら
の結果より、ＳｉＯ2 の添加で膜強度はより増大する。
高分散状態で添加されたＡＴＯ微粒子は膜強度、透明性
ともに大きな影響を与えない。[Transparency and Strength of Film] The pencil hardness of the obtained photocatalyst film is shown in Table 1, and the haze value is shown in Table 2. From these results, the film strength is further increased by the addition of SiO 2 .
ATO fine particles added in a highly dispersed state do not significantly affect both film strength and transparency.
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】〔光触媒活性〕光触媒膜を赤色有機色素で
着色し、 1.5ｍＷ・ｃｍ-2の紫外線を当てたときの色素
の分解活性（吸収極大波長の吸光度変化）を図１に示
す。微小電極形成材としてＡＴＯ微粒子を加えた膜の方
が明らかに高活性である。[Photocatalytic Activity] The photocatalytic film is colored with a red organic dye, and the decomposition activity (change in absorbance at the maximum absorption wavelength) of the dye when exposed to ultraviolet light of 1.5 mW · cm −2 is shown in FIG. A film to which ATO fine particles are added as a microelectrode-forming material is clearly higher in activity.
【００４８】[0048]
【発明の効果】以上のように本発明では、請求項１に係
る光触媒コーティング液では、Ｔｉアルコキシドの加水
分解物および平均粒径 100ｎｍ以下の電子伝導性酸化物
微粒子を含有させたことにより、この光触媒コーティン
グ液を用いることによって従来技術で得られたものより
も高い光触媒活性を有し、高い透明性、および高い膜強
度を有する光触媒膜を得ることができる。As described above, according to the present invention, the photocatalyst coating liquid according to claim 1 contains a hydrolyzate of Ti alkoxide and electron conductive oxide fine particles having an average particle diameter of 100 nm or less. By using a photocatalyst coating liquid, a photocatalytic film having higher photocatalytic activity, higher transparency, and higher film strength than that obtained by the conventional technique can be obtained.
【００４９】請求項２に係る光触媒コーティング液で
は、前記電子伝導性酸化物微粒子が分散粒子径 100ｎｍ
以下まで分散されているから、更に高い光触媒活性、透
明性および膜強度を有する光触媒膜を得ることができ
る。In the photocatalyst coating liquid according to claim 2, the electron conductive oxide fine particles have a dispersed particle diameter of 100 nm.
Since it is dispersed to the following, a photocatalytic film having higher photocatalytic activity, transparency and film strength can be obtained.
【００５０】請求項３に係る光触媒コーティング液で
は、前記Ｔｉアルコキシドの加水分解物および前記電子
伝導性酸化物微粒子を、それぞれ、前記光触媒コーティ
ング液の固形分中、酸化物重量換算で、 80 〜 99.99
重量％、0.01〜 20 重量％含有することにより、高い光
触媒活性を維持するとともに高い膜強度を有する光触媒
膜と得ることができる。In the photocatalyst coating liquid according to the third aspect, the hydrolyzate of the Ti alkoxide and the electron conductive oxide fine particles are each contained in the solid content of the photocatalyst coating liquid in an amount of 80 to 99.99 in terms of oxide weight.
When the content is 0.01% to 20% by weight, a photocatalytic film having high photocatalytic activity and high film strength can be obtained.
【００５１】請求項４に係る光触媒コーティング液で
は、平均粒径 100ｎｍ以下のアナターゼ型ＴｉＯ2 微粒
子を 0.1〜 20 重量％添加したことにより、光触媒膜の
形成時にアナターゼ型の結晶成長を促進して、得られる
光触媒膜のＴｉＯ2 をアナターゼ型結晶の割合を増加さ
せて光触媒活性を高めることができる。In the photocatalyst coating liquid according to claim 4, by adding 0.1 to 20% by weight of anatase type TiO 2 fine particles having an average particle diameter of 100 nm or less, the growth of the anatase type crystal during the formation of the photocatalytic film is promoted. Photocatalytic activity can be enhanced by increasing the proportion of anatase type crystals in TiO 2 of the obtained photocatalytic film.
【００５２】請求項５に係る光触媒コーティング液で
は、Ｓｉアルコキシドの加水分解物を0.1〜 20 重量％
添加したことにより、得られる光触媒膜の膜強度を高
め、光触媒活性と膜強度との両立を容易に実現させるこ
とができる。In the photocatalyst coating liquid according to claim 5, the hydrolyzate of the Si alkoxide is contained in an amount of 0.1 to 20% by weight.
By the addition, the film strength of the obtained photocatalyst film can be increased, and compatibility between the photocatalytic activity and the film strength can be easily realized.
【００５３】請求項６に係る光触媒コーティング液で
は、前記電子伝導性酸化物微粒子がアンチモンドープ酸
化錫、錫ドープ酸化インジウム、ＲｅＯ3 ，ＲｕＯ2 ，
ＩｒＯ 2 ，ＯｓＯ2 ，ＶＯ2 のうち少なくとも１種以上
を含む電子伝導性酸化物であることにより、得られる光
触媒膜が、紫外線の照射によって生じた電子をトラップ
して電子正孔対の再結合を抑制して光触媒活性を高める
ことができる。The photocatalyst coating liquid according to claim 6
Means that the electron conductive oxide fine particles are antimony-doped acid
Tin oxide, tin-doped indium oxide, ReOThree, RuOTwo,
IrO Two, OsOTwo, VOTwoAt least one of
Light obtained by being an electron conductive oxide containing
Catalytic film traps electrons generated by UV irradiation
To increase photocatalytic activity by suppressing recombination of electron-hole pairs
be able to.
【００５４】請求項７に係る光触媒コーティング基材で
は、前記光触媒コーティング液を用いて、耐熱性基板上
に塗布、焼成させて形成した光触媒膜を有することによ
り、高い光触媒活性、高い透明性、および高い膜強度を
同時に実現できる。The photocatalyst-coated substrate according to claim 7 has a photocatalyst film formed by coating and baking on a heat-resistant substrate using the photocatalyst coating liquid, thereby achieving high photocatalytic activity, high transparency, and High film strength can be realized at the same time.
【００５５】請求項８に係る光触媒コーティング基材で
は、前記光触媒膜が、主としてアナターゼ結晶相からな
ることにより、高い光触媒活性を得ることができる。In the photocatalyst-coated substrate according to the eighth aspect, since the photocatalyst film mainly comprises an anatase crystal phase, high photocatalytic activity can be obtained.
【００５６】請求項９に係る光触媒コーティング基材で
は、前記光触媒膜と耐熱性基材との間に、ＳｉＯ2 アン
ダーコート層を有することにより、基材と光触媒膜との
間のアルカリバリアを形成して耐久性を向上させること
ができ、光触媒膜の密着性を向上させることができる。The photocatalyst-coated substrate according to the ninth aspect has an SiO 2 undercoat layer between the photocatalyst film and the heat-resistant substrate to form an alkali barrier between the substrate and the photocatalyst film. As a result, the durability can be improved, and the adhesion of the photocatalyst film can be improved.
【図１】本発明の実施例における光触媒膜付きガラスの
色素分解活性を示すグラフである。FIG. 1 is a graph showing the dye decomposition activity of glass with a photocatalytic film in an example of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｄ 1/00 Ｃ０９Ｄ 1/00 5/00 5/00 Ｚ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C09D 1/00 C09D 1/00 5/00 5/00 Z
Claims (9)
粒径 100ｎｍ以下の電子伝導性酸化物微粒子を含有させ
たことを特徴とする光触媒コーティング液。1. A photocatalyst coating solution containing a hydrolyzate of Ti alkoxide and electron-conductive oxide fine particles having an average particle size of 100 nm or less.
100ｎｍ以下に分散されていることを特徴とする請求項
１記載の光触媒コーティング液。2. The method according to claim 1, wherein the electron-conductive oxide fine particles have a dispersed particle size.
The photocatalyst coating solution according to claim 1, wherein the photocatalyst coating solution is dispersed at a wavelength of 100 nm or less.
前記電子伝導性酸化物微粒子を、それぞれ、前記光触媒
コーティング液の固形分中、酸化物重量換算で、 80 〜
99.99重量％、0.01〜 20 重量％含有することを特徴と
する請求項１記載の光触媒コーティング液。3. The hydrolyzate of the Ti alkoxide and the electron-conductive oxide fine particles are each contained in the solid content of the photocatalyst coating solution in an amount of 80 to 80 in terms of oxide weight.
2. The photocatalyst coating liquid according to claim 1, wherein the content is 99.99% by weight and 0.01 to 20% by weight.
Ｏ2 微粒子を 0.1〜 20 重量％添加したことを特徴とす
る請求項１記載の光触媒コーティング液。4. Anatase type Ti having an average particle size of 100 nm or less.
2. The photocatalyst coating liquid according to claim 1, wherein 0.1 to 20% by weight of O2 fine particles is added.
0 重量％添加したことを特徴とする請求項１記載の光触
媒コーティング液。5. The hydrolyzate of Si alkoxide is used in an amount of 0.1 to 2
The photocatalyst coating liquid according to claim 1, wherein 0% by weight is added.
ドープ酸化錫、錫ドープ酸化インジウム、ＲｅＯ3 ，Ｒ
ｕＯ2 ，ＩｒＯ2 ，ＯｓＯ2 ，ＶＯ2 のうち少なくとも
１種以上を含む電子伝導性酸化物であることを特徴とす
る請求項１記載の光触媒コーティング液。6. An electron conductive oxide fine particle comprising antimony-doped tin oxide, tin-doped indium oxide, ReO 3 , R
uO 2, IrO 2, OsO 2 , the photocatalytic coating liquid according to claim 1, wherein the one of the VO 2 is an electron conductive oxide containing at least one.
ーティング液を用いて、耐熱性基板上に塗布、焼成させ
て形成した光触媒膜を有することを特徴とするコーティ
ング基材。7. A coating substrate comprising a photocatalyst film formed by applying and firing the photocatalyst coating solution according to claim 1 on a heat-resistant substrate.
相からなることを特徴とする請求項７記載のコーティン
グ基材。8. The coating substrate according to claim 7, wherein said photocatalytic film mainly comprises an anatase crystal phase.
Ｏ2 アンダーコート層を有することを特徴とする請求項
７記載のコーティング基材。9. A method according to claim 9, wherein said photocatalytic film and said heat-resistant base material are provided with Si.
Coated substrate according to claim 7, characterized in that it has an O 2 undercoat layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10065721A JPH11262670A (en) | 1998-03-16 | 1998-03-16 | Photocatalyst coating liquid and coating base material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10065721A JPH11262670A (en) | 1998-03-16 | 1998-03-16 | Photocatalyst coating liquid and coating base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11262670A true JPH11262670A (en) | 1999-09-28 |
Family
ID=13295178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10065721A Pending JPH11262670A (en) | 1998-03-16 | 1998-03-16 | Photocatalyst coating liquid and coating base material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11262670A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096154A (en) * | 1999-09-29 | 2001-04-10 | Yamada Sangyo Kk | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method |
-
1998
- 1998-03-16 JP JP10065721A patent/JPH11262670A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001096154A (en) * | 1999-09-29 | 2001-04-10 | Yamada Sangyo Kk | Vanadium oxide/titania hybrid photocatalyst and its manufacturing method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5897958A (en) | Modified titanium oxide sol, photocatalyst composition and photocatalyst composition-forming agent | |
| CN1097477C (en) | Titanium oxide photocatalyst structure and method of manufacturing the same | |
| JP4803180B2 (en) | Titanium oxide photocatalyst, its production method and use | |
| JP5784481B2 (en) | Coating composition and use thereof | |
| JP4698981B2 (en) | Fibrous titanium oxide particles, method for producing the same, and uses of the particles | |
| CN102382490A (en) | Preparation method and use of hydrophilic automatically-cleaning coating with photocatalytic activity | |
| CN104085165B (en) | A kind of preparation method of photocatalyst of titanium dioxide coating | |
| JP3755852B2 (en) | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film | |
| JP3818811B2 (en) | Photocatalytic filter for air purification | |
| JP2000289134A (en) | Article having hydrophilic surface and production thereof | |
| JPH07155598A (en) | Photocatalyst coating film and its formation | |
| CN1194922C (en) | Nano self-cleaning super hydrophilic glass product production method | |
| JPH10167727A (en) | Modified titanium oxide sol, photocatalyst composition and its forming agent | |
| CN104911672A (en) | Micro-arc oxidation solution for WO3-doped TiO2 photocatalysis film and applications | |
| JPH11262670A (en) | Photocatalyst coating liquid and coating base material | |
| JP2010040172A (en) | Manufacturing method of photoelectric cell | |
| JPH11262669A (en) | Photocatalyst coating liquid and coating base material | |
| JP3885248B2 (en) | Photocatalyst composition | |
| CN101044419A (en) | Anti-fog device and outside mirror | |
| JP3317668B2 (en) | Photocatalyst film forming ink and photocatalyst film forming method | |
| JP3537110B2 (en) | Coating composition for forming transparent film having photocatalytic activity and substrate with transparent film | |
| JP4343335B2 (en) | Titanium oxide coating film forming composition for photocatalyst and process for producing the same | |
| JPH09227158A (en) | Non-fogging film-forming base material, non-fogging film using the same and its production | |
| JPH072522A (en) | Production of titanium oxide film | |
| KR100442919B1 (en) | Preparation method for photocatalyst sol having high transparency photoactivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040615 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061128 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070126 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20070417 |