JPH11262669A - Photocatalyst coating liquid and coating base material - Google Patents
Photocatalyst coating liquid and coating base materialInfo
- Publication number
- JPH11262669A JPH11262669A JP10065720A JP6572098A JPH11262669A JP H11262669 A JPH11262669 A JP H11262669A JP 10065720 A JP10065720 A JP 10065720A JP 6572098 A JP6572098 A JP 6572098A JP H11262669 A JPH11262669 A JP H11262669A
- Authority
- JP
- Japan
- Prior art keywords
- film
- photocatalyst
- coating liquid
- anatase
- photocatalytic
- 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
- 239000011248 coating agent Substances 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 57
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 230000001699 photocatalysis Effects 0.000 claims abstract description 65
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 48
- 239000013078 crystal Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 16
- 238000010304 firing Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 description 17
- 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 11
- 239000011521 glass Substances 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- -1 titanium alkoxide Chemical class 0.000 description 6
- 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 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000004528 spin coating Methods 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
- 230000004913 activation Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction 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
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Chemical class 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Surface Treatment Of Glass (AREA)
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及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。BACKGROUND OF THE INVENTION 1. Field of the Invention 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、光触媒活性についてはアナターゼ
型ＴｉＯ2 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。Generally, anatase type TiO 2 is excellent in photocatalytic activity. 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】〔問題点〕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
があるから、光触媒活性が高いアナターゼ型の結晶相が
得られにくい。一方、低温で焼成した場合、非晶質相と
わずかなアナターゼ相とからなるため、光触媒活性は十
分ではない。このように、チタニアゾルのみからなるコ
ーティング液を用いた場合には、光触媒活性と膜強度の
両立が困難であった。[Problem] A photocatalytic film obtained by using a coating solution consisting of titania sol alone has a high photocatalytic activity because it must be fired at a higher temperature in order to obtain sufficient film strength in practical use. It is difficult to obtain an anatase type crystal phase. On the other hand, when calcined at a low temperature, the photocatalytic activity is not sufficient because it is composed of an amorphous phase and a slight anatase phase. As described above, when the coating liquid composed of only the titania sol is used, it is difficult to achieve both photocatalytic activity and film strength.
【０００５】これに対して、チタニアゾルにシリカゾル
を加えたコーティング液よりなる膜は、より低温で膜強
度を得ることができるものの、シリカの添加により膜の
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。On the other hand, a film composed of a coating solution obtained by adding silica sol to titania sol can obtain film strength at a lower temperature, but the crystallinity of the film is further reduced by the addition of silica, Since the TiO 2 fraction also decreases, the photocatalytic activity sharply decreases.
【０００６】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、チタニアゾルのみでは光
触媒活性効果と膜強度の両方に優れた膜を得ることが困
難であり、またチタニアゾルにシリカゾルを加えた場合
では、膜の結晶性が一段と低下し、光触媒活性は急激に
低下するため光触媒活性効果と膜強度の両方に優れた膜
を得ることが困難であるという問題点があった。In a photocatalytic film obtained by using such a conventional coating solution, it is difficult to obtain a film excellent in both photocatalytic activity and film strength by using titania sol alone, and silica sol is added to titania sol. In this case, there is a problem that the crystallinity of the film is further reduced and the photocatalytic activity is rapidly reduced, so that it is difficult to obtain a film excellent in both the photocatalytic activity effect and the film strength.
【０００７】[0007]
【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、その問題
点解消ため具体的に設定する課題は、光触媒活性と膜強
度とに優れた効果を有する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 the problems to be set specifically for solving the problems are excellent in photocatalytic activity and film strength. An object of the present invention is to provide a photocatalyst coating liquid capable of forming a photocatalyst film having an effect, and a coating substrate having a photocatalyst film formed using the same.
【０００８】[0008]
【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以下のアナターゼ型Ｔ
ｉＯ2 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
Is a hydrolyzate of Ti alkoxide and an anatase type T having an average particle size of 100 nm or less.
It is characterized by containing iO 2 fine particles.
【０００９】請求項２に係る光触媒コーティング液は、
前記アナターゼ型ＴｉＯ2 微粒子が分散粒子径 100ｎｍ
以下まで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 anatase TiO 2 fine particles have a dispersed particle diameter of 100 nm.
It is characterized by being dispersed to the following.
【００１０】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アナター
ゼ型ＴｉＯ2 微粒子を、前記光触媒コーティング液の固
形分中の酸化物重量換算で、それぞれ 80 重量％以上 9
9.9 重量％以下、0.1 重量％以上 20 重量％以下の範囲
で含有することを特徴とする。[0010] The photocatalyst coating liquid according to claim 3 is:
The hydrolyzate of the Ti alkoxide and the anatase-type TiO 2 fine particles are each 80% by weight or more in terms of oxide weight in the solid content of the photocatalytic coating solution.
It is characterized by containing 9.9% by weight or less, 0.1% by weight or more and 20% by weight or less.
【００１１】請求項４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重量％以上 20 重
量％以下の範囲で含有することを特徴とする。[0011] The photocatalyst coating liquid according to claim 4 comprises:
It is characterized by containing a hydrolyzate of Si alkoxide in a range of 0.1% by weight or more and 20% by weight or less.
【００１２】請求項５に係るコーティング基材は、請求
項１〜４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 fifth aspect of the present invention, there is provided a coating substrate 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 fourth aspects. It is assumed that.
【００１３】請求項６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 a sixth aspect of the present invention, in the coating substrate, the photocatalyst film mainly comprises an anatase crystal phase.
【００１４】請求項７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 seventh aspect of the present invention, there is provided a coating substrate comprising an SiO 2 undercoat layer between the photocatalytic film and the heat-resistant substrate.
【００１５】[0015]
【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、発明内容を限定するものではな
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.
The contents of the invention are not limited unless otherwise specified.
【００１６】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に水と触媒を加えた加水分解液
に、平均分散粒子径が 100ｎｍ以下のアナターゼ型Ｔｉ
Ｏ2 微粒子を結晶成長の核として加え、必要に応じてテ
トラエトキシシラン等の加水分解液を加えたコーティン
グ液を作製する。この際、前記アナターゼ型ＴｉＯ2 微
粒子は、高い解砕力が与えられて分散粒子径 100ｎｍ以
下まで分散されていることが好ましい。以下、この場合
に基づいて、詳述する。An anatase type Ti having an average dispersed particle diameter of 100 nm or less is added to a hydrolyzate obtained by adding water and a catalyst to a titanium alkoxide such as titanium tetraisopropoxide.
O 2 fine particles are added as nuclei for crystal growth, and a coating solution to which a hydrolyzing solution such as tetraethoxysilane is added as necessary is prepared. At this time, it is preferable that the anatase-type TiO 2 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.
【００１７】このコーティング液を用いて、基材上に成
膜・焼成することにより、結晶性が高く且つアナターゼ
型の結晶型の比率の高いＴｉＯ2 膜を得ることができ、
高い透明性と高い膜強度を有しながら、従来にない高い
光触媒活性を有する光触媒膜を得ることができる。By using this coating solution to form a film on a substrate and firing it, it is possible to obtain a TiO 2 film having high crystallinity and a high ratio of the anatase type crystal,
It is possible to obtain a photocatalyst film having high photocatalytic activity, which has never been seen before, while having high transparency and high film strength.
【００１８】光触媒膜の製造には、例えばアルコール等
の有機溶媒中に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、アナ
ターゼ型の結晶形を有し平均粒子径が 100ｎｍ以下のＴ
ｉＯ2 微粒子を加え、ボールミル、サンドミル等を用い
て高い解砕力を与えることにより、アナターゼ型ＴｉＯ
2 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、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チタニウムアルコキシドを
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）とを混合した液に、必要に応じてアル
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、酸またはアルカリ触媒を含む水
を添加して得られた溶液（以下シリカゾルと言う）を加
えた下記配合量となるコーティング液を用いる。In the production of the photocatalytic film, for example, a surfactant such as polyoxyethylene alkyl phosphate ester or polyester salt is added to an organic solvent such as alcohol to form an anatase type crystal having an average particle diameter of T below 100nm
By adding TiO 2 fine particles and giving high crushing power using a ball mill, a sand mill or the like, anatase type TiO 2 is obtained.
(2 ) Water (adding an acid or alkali catalyst as necessary) to a dispersion in which fine particles are highly dispersed to a particle diameter of 100 nm or less and an alcohol solution containing titanium alkoxide such as titanium tetrabutoxide and titanium tetraisopropoxide. Is added to a solution obtained by adding a hydrolyzed solution (hereinafter referred to as titania sol) to a solution obtained by adding tetramethyl orthosilicate or tetraethyl orthosilicate to an alcohol, if necessary, and adding water containing an acid or an alkali catalyst. A coating solution having the following blending amount to which the obtained solution (hereinafter referred to as silica sol) is added is used.
【００１９】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，重量％）は以下のように配合する。 80 ％ ≦ チタニアゾル ＜ 100％ 0 ％ ＜ アナターゼ型ＴｉＯ2 分散液 ≦ 20 ％ 0 ％ ≦ シリカゾル ≦ 20 ％The amount of the coating solution to be prepared (all in terms of oxide, weight%) is as follows. 80% ≦ titania sol <100% 0% <anatase TiO 2 dispersion ≦ 20% 0% ≦ silica sol ≦ 20%
【００２０】このコーティング液を基材にコーティング
して、 200℃以上の温度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
膜を有するコーティング基材を得る。This coating solution is coated on a substrate and baked at a temperature of 200 ° C. or higher to obtain a coated substrate having a photocatalytic film having high photocatalytic activity, high transparency and high film strength.
【００２１】この際、結晶成長の核として加えるアナタ
ーゼ型ＴｉＯ2 微粒子の量が全体の20 ％を超えると、
膜の強度低下が大きく、実用上は強度不足となる。ま
た、結晶成長の核として加えるアナターゼ型ＴｉＯ2 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。At this time, if the amount of the anatase type TiO 2 fine particles added as a nucleus for crystal growth exceeds 20% of the whole,
The strength of the film is greatly reduced, and the strength is insufficient in practical use. Unless the anatase-type TiO 2 fine particles to be added as crystal nuclei 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 may have a strength of the film. Is greatly reduced.
【００２２】一方、膜強度をより高めるためにシリカ加
水分解液を加える場合でも、その量が全体の 20 ％を超
えると、たとえアナターゼ型ＴｉＯ2 微粒子を加えてい
たとしても、結晶性の低下を抑えることができず、膜中
のＴｉＯ2 分率も低下して、光触媒活性がほとんど発現
しなくなる。On the other hand, even when a silica hydrolyzate is added to further increase the film strength, if the amount exceeds 20% of the total amount, the crystallinity is reduced even if anatase type TiO 2 fine particles are added. It cannot be suppressed, the TiO 2 fraction in the film also decreases, and the photocatalytic activity hardly appears.
【００２３】このため、ルチル型ＴｉＯ2 微粒子または
非晶質のＴｉＯ2 微粒子を用いた場合では光触媒膜の光
触媒活性効果が十分でなく、平均粒径 100ｎｍ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
膜が高い光触媒活性効果を有するようになるから、コー
ティング液には平均粒径 100ｎｍ以下のアナターゼ型Ｔ
ｉＯ2 微粒子を含有させる必要がある。For this reason, when rutile-type TiO 2 fine particles or amorphous TiO 2 fine particles are used, the photocatalytic activity of the photocatalytic film is not sufficient, and by using anatase-type TiO 2 fine particles having an average particle diameter of 100 nm or less. Since the photocatalytic film has a high photocatalytic activity, the coating solution contains an anatase type T having an average particle size of 100 nm or less.
It is necessary to contain iO 2 fine particles.
【００２４】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十分でなく、また光触
媒膜の透明性も不十分なものとなる。そして、光触媒コ
ーティング液の固形分中、アナターゼ型ＴｉＯ2 微粒子
が酸化物重量換算で 0.1重量％未満では、光触媒膜の光
触媒活性効果が不十分となり、 20 重量％を超える場合
では膜強度が不十分となる。Anatase type T having an average particle size exceeding 100 nm
When the iO 2 fine particles are used, the specific surface area is small, so that the photocatalytic activity of the photocatalytic film is not sufficient, and the transparency of the photocatalytic film is also insufficient. When the amount of anatase TiO 2 fine particles in the solid content of the photocatalyst coating solution is less than 0.1% by weight in terms of oxide weight, the photocatalytic activity effect of the photocatalyst film becomes insufficient, and when it exceeds 20% by weight, the film strength becomes insufficient. Becomes
【００２５】また、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ＴｉＯ2 となるため、光
触媒膜の光触媒活性効果の向上に寄与するから、Ｔｉア
ルコキシドの加水分解物を含有させる必要がある。そし
て、光触媒コーティング液の固形分中Ｔｉアルコキシド
の加水分解物が、酸化物重量換算で、80重量％未満では
膜強度が不十分となり、99.9重量％超過の場合はアナタ
ーゼ型ＴｉＯ2 微粒子の配合量が少なくなり、光触媒膜
の光触媒活性効果が不十分となる。Further, the film strength of the photocatalyst film is improved.
Since a part becomes anatase-type TiO 2 by calcination, which contributes to improvement of the photocatalytic activity effect of the photocatalytic film, it is necessary to contain a hydrolyzate of Ti alkoxide. If the hydrolyzate of Ti alkoxide in the solid content of the photocatalyst coating solution is less than 80% by weight in terms of oxide weight, the film strength becomes insufficient, and if it exceeds 99.9% by weight, the blending amount of anatase type TiO 2 fine particles And the photocatalytic activity effect of the photocatalytic film becomes insufficient.
【００２６】また、膜強度向上の点からは、Ｓｉアルコ
キシドの加水分解物を含有することが好ましい。そし
て、光触媒コーティング液の固形分中、Ｓｉアルコキシ
ドの加水分解物が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、また、 20 重量％を超える場合にはア
ナターゼ型ＴｉＯ2 微粒子およびＴｉアルコキシドの加
水分解物の配合が少なくなり、光触媒膜の光触媒活性効
果が不十分となる。From the viewpoint of improving the film strength, it is preferable to contain a hydrolyzate of Si alkoxide. Then, in the solid content of the photocatalyst coating liquid, the hydrolyzate of the Si alkoxide is 0.1% by weight in terms of the weight of the oxide.
If it is less than 20 wt%, the effect of improving the film strength by the addition of Si alkoxide will not be exhibited, and if it exceeds 20 wt%, the blending of the anatase type TiO 2 fine particles and the hydrolyzate of Ti alkoxide will decrease, and The activation effect becomes insufficient.
【００２７】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。光触媒膜形成時に、平
均粒径 100ｎｍ以下のアナターゼ型ＴｉＯ2 微粒子を核
として、Ｔｉアルコキシドの加水分解物がアナターゼ型
ＴｉＯ2 結晶として成長する。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、150 〜700 ℃が
好ましい。The TiO 2 of the photocatalytic film is preferably mainly composed of an anatase type crystal since rutile type crystal does not have a sufficient photocatalytic activity. At the time of forming the photocatalytic film, a hydrolyzate of Ti alkoxide grows as anatase TiO 2 crystal with anatase TiO 2 fine particles having an average particle diameter of 100 nm or less as nuclei. The firing temperature is preferably from 150 to 700 ° C. from the viewpoint of crystal growth of the hydrolyzate of Ti alkoxide.
【００２８】また、基材については、前記焼成温度範囲
で使用できる基材ならば使用することができる。このた
め、150 ℃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、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 substrate, any substrate can be used as long as it can be used within the above-mentioned firing temperature range. For this reason, plastics that can withstand temperatures of 150 ° C. or higher can be used, but it is particularly preferable to use heat-resistant base materials such as glass, ceramics, porcelain, metal, and fine ceramics.
【００２９】基材と光触媒膜の密着性の向上、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
しての効果等を有するＳｉＯ2 アンダーコート層を、光
触媒膜と基材との間に設けることが好ましい。An SiO 2 undercoat layer having an effect of improving the adhesion between the base material and the photocatalyst film and, in the case of a base material containing an alkali component such as glass, has an effect as an alkali barrier, is provided between the photocatalyst film and the base material. Is preferably provided.
【００３０】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粉末であっても良い。The anatase-type TiO 2 fine particles to be contained in the photocatalyst coating liquid may be a composite photocatalyst powder having anatase-type TiO 2 fine particles as a nucleus and a surface coated with a porous ceramic such as silica.
【００３１】[0031]
【実施例】 〔実施例１〕 平均粒子径 7ｎｍのアナターゼ型ＴｉＯ2 微粒子 30 部 リン酸エステル系界面活性剤 2 部 エタノール 68 部 を、 1ｍｍ径のガラスビーズ 100部とともにボールミル
で一昼夜混合分散し、アナターゼ型ＴｉＯ2 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）を作製し
た。これらを、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ＴｉＯ2 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
て、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 分焼成して、光触媒膜付きガラス（ｇ１）を得
た。[Example 1] 30 parts of anatase-type TiO 2 fine particles having an average particle diameter of 7 nm 30 parts of a phosphate ester surfactant 2 parts 68 parts of ethanol were mixed and dispersed with a 100 mm 1-mm diameter glass bead in a ball mill for 24 hours. An ethanol dispersion liquid (a1) of anatase TiO 2 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 are expressed as oxide weight ratios: [Ti alkoxide content in t1 (TiO 2 conversion) /
[TiO 2 content in a1] = 95/5 The mixture was mixed so 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.
【００３２】〔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を加えて
作製したシリカ加水分解液（ｓ２）と、前記ｔ１及びａ
１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ＴｉＯ2 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、 500℃で
30 分焼成して、光触媒膜付きガラス（ｇ２）を得た。Example 2 A hydrolyzed silica solution (s2) prepared by adding an equivalent amount of water and a small amount of HCl to an ethanol solution of tetraethylorthosilicic acid,
1 and the oxide weight ratio: [Ti alkoxide content in t1 (TiO 2 conversion) /
[TiO 2 content in a1] / [Si alkoxide content of s2 (SiO 2 conversion)] = 90/5/5 were mixed at 5% titanium oxide concentration by weight after firing, the photocatalytic coating liquid (C2) was obtained. Further, this coating solution is applied in advance by spin coating on glass on which a Na barrier layer of SiO 2 has been provided.
By firing for 30 minutes, a glass with a photocatalytic film (g2) was obtained.
【００３３】〔比較例１〕実施例１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 Glass with a photocatalytic film (T1) was prepared by using the coating solution (C1) obtained by adding ethanol to the titania hydrolyzate (t1) described in Example 1 in the same manner as the photocatalytic film described in Example 1. G1) was obtained.
【００３４】〔比較例２〕実施例１記載のチタニア加水
分解液（ｔ１）と、実施例２記載のシリカ加水分解液
（ｓ２）とを用いて、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）／
［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 oxide weight ratio after calcination was calculated as follows: [t1 Ti alkoxide content of (TiO 2 equivalent) /
[Content of Si alkoxide in s2 (in terms of SiO 2 )]
= 95/5 Titanium oxide after calcination was mixed to a weight concentration of 5% to obtain a photocatalyst coating liquid (C2). Furthermore, similarly, glass (G2) with a photocatalytic film was obtained.
【００３５】〔結晶相の同定〕得られた光触媒膜のＸ線
回折図形を図１〜２に示す。図１の実施例１（ｇ１）と
比較例１（Ｇ１）との比較から、結晶成長の核としてア
ナターゼ型ＴｉＯ2 微粒子を加えることで、ルチル型結
晶相の生成が抑えられ、より光触媒活性の高いアナター
ゼ型結晶相の成長が促されていることが分かる。また実
施例２（ｇ２）と比較例２（Ｇ２）との比較から、膜強
度を得るためにＳｉＯ2 を加えても、結晶成長の核とし
てアナターゼ型ＴｉＯ2 微粒子を加えることで、結晶性
の低下を抑えられることが分かる。[Identification of Crystal Phase] FIGS. 1 and 2 show X-ray diffraction patterns of the obtained photocatalytic film. From the comparison between Example 1 (g1) in FIG. 1 and Comparative Example 1 (G1), by adding anatase-type TiO 2 fine particles as nuclei for crystal growth, generation of a rutile-type crystal phase was suppressed, and photocatalytic activity was improved. It can be seen that the growth of a high anatase type crystal phase is promoted. Further, from the comparison between Example 2 (g2) and Comparative Example 2 (G2), even if SiO 2 is added to obtain a film strength, the crystallinity can be improved by adding anatase-type TiO 2 fine particles as nuclei for crystal growth. It can be seen that the decrease can be suppressed.
【００３６】〔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。ＳｉＯ
2 の添加で膜強度はより増大する。高分散状態で添加さ
れたアナターゼ型ＴｉＯ2 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. SiO
Addition of 2 further increases the film strength. Anatase-type TiO 2 fine particles added in a highly dispersed state do not significantly affect film strength and transparency.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】〔光触媒活性〕光触媒膜を赤色有機色素で
着色し、1.5 ｍＷ・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３に示
す。結晶成長の核としてアナターゼ型ＴｉＯ2 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 dye decomposition activity (change in absorbance at the absorption maximum wavelength) when 1.5 mW · cm −2 ultraviolet light is applied is shown in FIG. The film to which anatase-type TiO 2 fine particles are added as nuclei for crystal growth is clearly higher in activity.
【００４０】〔作用効果〕以上のようにチタニウムアル
コキシドに水と触媒を加えた加水分解液に高い解砕力を
与えることにより、分散粒子径を 100ｎｍ以下にまで高
分散させたアナターゼ型ＴｉＯ2 微粒子を結晶成長の核
として加え、必要に応じてテトラエトキシシラン等の加
水分解液を加えたコーティング液を作成し、これを用い
て、基材上に成膜・焼成することにより、ルチル型結晶
相の生成が抑えられ、より光触媒活性の高いアナターゼ
型結晶相の成長が促され、かつＳｉＯ2 を加えても結晶
性の低下を抑えることができる。その結果、高い透明性
と高い膜強度を有しながら、従来にない、高い光触媒活
性を有する光触媒膜を得ることができる。[Function and Effect] As described above, the hydrolyzate obtained by adding water and a catalyst to a titanium alkoxide is given a high crushing power, whereby anatase-type TiO 2 fine particles having a highly dispersed particle diameter of 100 nm or less are crystallized. A coating solution is prepared by adding a hydrolysis solution such as tetraethoxysilane, etc., as necessary, as a growth nucleus, and by using this, a film is formed and fired on a substrate, thereby generating a rutile-type crystal phase. Is suppressed, the growth of an anatase type crystal phase having a higher photocatalytic activity is promoted, and a decrease in crystallinity can be suppressed even when SiO 2 is added. As a result, it is possible to obtain a photocatalytic film having high photocatalytic activity, which has never been seen before, while having high transparency and high film strength.
【００４１】[0041]
【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以下のアナターゼ型Ｔｉ
Ｏ2 微粒子を含有させたことにより、光触媒活性と膜強
度とに優れた効果を有する光触媒膜を形成することがで
きる。As described above, according to the present invention, in the photocatalyst coating liquid according to claim 1, a hydrolyzate of Ti alkoxide and an anatase type Ti having an average particle diameter of 100 nm or less are used.
By including the O 2 fine particles, a photocatalytic film having excellent effects in photocatalytic activity and film strength can be formed.
【００４２】請求項２に係る光触媒コーティング液で
は、前記アナターゼ型ＴｉＯ2 微粒子が分散粒子径 100
ｎｍ以下まで分散されているから、光触媒活性と膜強度
とが更に優れた光触媒膜を形成することができる。In the photocatalyst coating liquid according to claim 2, the anatase TiO 2 fine particles have a dispersed particle diameter of 100%.
Since the particles are dispersed to the order of nm or less, a photocatalytic film having more excellent photocatalytic activity and film strength can be formed.
【００４３】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アナ
ターゼ型ＴｉＯ2 微粒子を、前記光触媒コーティング液
の固形分中の酸化物重量換算で、それぞれ 80 重量％以
上 99.9 重量％以下、0.1 重量％以上 20 重量％以下の
範囲で含有することにより、アナターゼ型ＴｉＯ2 の結
晶成長を効果的に促進し、膜中のアナターゼ型ＴｉＯ2
分率を高めることができ、光触媒活性を向上させること
ができる。In the photocatalyst coating solution according to the third aspect, the hydrolyzate of the Ti alkoxide and the anatase type TiO 2 fine particles are each 80% by weight or more and 99.9% or more in terms of the oxide weight in the solid content of the photocatalyst coating solution. When the content is in the range of not more than 0.1% by weight and not more than 20% by weight, the crystal growth of anatase type TiO 2 is effectively promoted, and the anatase type TiO 2
The fraction can be increased, and the photocatalytic activity can be improved.
【００４４】請求項４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重量％以上 20
重量％以下の範囲で含有することにより、形成された
膜の強度を効果的に向上させることができる。In the photocatalyst coating liquid according to the fourth aspect, the hydrolyzate of the Si alkoxide is 0.1% by weight or more.
When the content is not more than the weight%, the strength of the formed film can be effectively improved.
【００４５】請求項５に係る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、
アナターゼ型の結晶の比率が高いＴｉＯ2 膜を形成で
き、高い透明性と高い膜強度とを両立させることができ
るとともに高い光触媒活性を付与することができる。The coating substrate according to claim 5 has a photocatalyst film formed by applying and baking a heat-resistant substrate using the photocatalyst coating solution.
A TiO 2 film having a high ratio of anatase-type crystals can be formed, and both high transparency and high film strength can be achieved, and high photocatalytic activity can be imparted.
【００４６】請求項６に係る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層からなること
により、光触媒膜の光触媒活性効果を向上させることが
できる。In the coating substrate according to the sixth aspect, since the photocatalytic film mainly comprises an anatase crystal layer, the photocatalytic activity of the photocatalytic film can be improved.
【００４７】請求項７に係るコーティング基材では、前
記光触媒膜と耐熱性基材と間に、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密着性を
向上させることができるとともにアルカリバリアができ
る。In the coating substrate according to the seventh aspect, by having an SiO 2 undercoat layer between the photocatalytic film and the heat-resistant substrate, the adhesion between the substrate and the photocatalytic film can be improved. Along with that, an alkali barrier can be formed.
【図１】本発明による光触媒膜のＸ線回析結果を示すグ
ラフであり、（Ａ）は実施例１の場合、（Ｂ）は比較例
１の場合を示す。FIG. 1 is a graph showing the results of X-ray diffraction of a photocatalytic film according to the present invention, wherein (A) shows the case of Example 1 and (B) shows the case of Comparative Example 1.
【図２】本発明による光触媒膜のＸ線回析結果を示すグ
ラフであり、（Ａ）は実施例２の場合、（Ｂ）は比較例
２の場合を示す。FIG. 2 is a graph showing the results of X-ray diffraction of a photocatalyst film according to the present invention, wherein (A) shows the case of Example 2 and (B) shows the case of Comparative Example 2.
【図３】本発明によ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. 3 is a graph showing the pigment decomposition activity of the glass with a photocatalytic film according to the present invention.
Claims (7)
粒径 100ｎｍ以下のアナターゼ型ＴｉＯ2 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 liquid containing a hydrolyzate of Ti alkoxide and anatase TiO 2 fine particles having an average particle diameter of 100 nm or less.
子径 100ｎｍ以下まで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 photocatalyst coating liquid according to claim 1, wherein said anatase type TiO 2 fine particles are dispersed to a dispersed particle diameter of 100 nm or less.
前記アナターゼ型ＴｉＯ2 微粒子を、前記光触媒コーテ
ィング液の固形分中の酸化物重量換算で、それぞれ 80
重量％以上 99.9 重量％以下、0.1 重量％以上 20 重量
％以下の範囲で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 anatase-type TiO 2 fine particles are each converted into 80 wt.
2. The photocatalyst coating liquid according to claim 1, wherein the photocatalyst coating liquid is contained in a range of not less than 0.1% by weight and not more than 20% by weight.
％以上 20 重量％以下の範囲で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。4. The photocatalyst coating liquid according to claim 1, comprising a hydrolyzate of the Si alkoxide in a range of 0.1% by weight to 20% by weight.
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。5. A coating substrate comprising a photocatalyst film formed by applying and baking a photocatalytic coating solution on a heat-resistant substrate using the photocatalyst coating solution according to claim 1.
相からなることを特徴とする請求項５記載のコーティン
グ基材。6. The coating substrate according to claim 5, wherein said photocatalytic film mainly comprises an anatase crystal phase.
2 アンダーコート層を有することを特徴とする請求項５
記載のコーティング基材。7. A method according to claim 1, further comprising the step of:
6. An undercoat layer having two layers.
A coated substrate as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10065720A JPH11262669A (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 |
|---|---|---|---|
| JP10065720A JPH11262669A (en) | 1998-03-16 | 1998-03-16 | Photocatalyst coating liquid and coating base material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11262669A true JPH11262669A (en) | 1999-09-28 |
Family
ID=13295148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10065720A Pending JPH11262669A (en) | 1998-03-16 | 1998-03-16 | Photocatalyst coating liquid and coating base material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11262669A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018579A1 (en) * | 2002-08-21 | 2004-03-04 | Jsr Corporation | Coating composition |
| WO2004096935A1 (en) * | 2003-04-30 | 2004-11-11 | Ube Nitto Kasei Co., Ltd. | Photocatalyst coating liquid, photocatalyst film and photocatalyst member |
| JP2005528312A (en) * | 2002-04-17 | 2005-09-22 | サン−ゴバン グラス フランス | Substrate with self-cleaning coating |
| JP2007044657A (en) * | 2005-08-11 | 2007-02-22 | Mie Prefecture | Manufacturing method of titania paste, manufacturing method of titania porous layer, and photocatalyst layer |
| US7588196B2 (en) | 2004-02-20 | 2009-09-15 | Toyota Jidosha Kabushiki Kaisha | Cartridge-type coating machine and cartridge thereof |
-
1998
- 1998-03-16 JP JP10065720A patent/JPH11262669A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005528312A (en) * | 2002-04-17 | 2005-09-22 | サン−ゴバン グラス フランス | Substrate with self-cleaning coating |
| JP4739677B2 (en) * | 2002-04-17 | 2011-08-03 | サン−ゴバン グラス フランス | Method for manufacturing a substrate having a self-cleaning coating |
| WO2004018579A1 (en) * | 2002-08-21 | 2004-03-04 | Jsr Corporation | Coating composition |
| CN100376646C (en) * | 2002-08-21 | 2008-03-26 | 捷时雅株式会社 | Coating composition |
| WO2004096935A1 (en) * | 2003-04-30 | 2004-11-11 | Ube Nitto Kasei Co., Ltd. | Photocatalyst coating liquid, photocatalyst film and photocatalyst member |
| JPWO2004096935A1 (en) * | 2003-04-30 | 2006-07-13 | 宇部日東化成株式会社 | Photocatalyst coating liquid, photocatalyst film and photocatalyst member |
| CN100381527C (en) * | 2003-04-30 | 2008-04-16 | 宇部日东化成株式会社 | Photocatalyst coating liquid, photocatalyst film and photocatalyst member |
| US7588196B2 (en) | 2004-02-20 | 2009-09-15 | Toyota Jidosha Kabushiki Kaisha | Cartridge-type coating machine and cartridge thereof |
| JP2007044657A (en) * | 2005-08-11 | 2007-02-22 | Mie Prefecture | Manufacturing method of titania paste, manufacturing method of titania porous layer, and photocatalyst layer |
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