JP2000072575A - Photocatalytic tile and its production - Google Patents
Photocatalytic tile and its productionInfo
- Publication number
- JP2000072575A JP2000072575A JP11074053A JP7405399A JP2000072575A JP 2000072575 A JP2000072575 A JP 2000072575A JP 11074053 A JP11074053 A JP 11074053A JP 7405399 A JP7405399 A JP 7405399A JP 2000072575 A JP2000072575 A JP 2000072575A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalytic
- tile
- film
- tio
- vapor
- 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
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 38
- 238000007740 vapor deposition Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract description 4
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000001771 vacuum deposition Methods 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 18
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000003980 solgel method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- -1 WO 3 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00439—Physico-chemical properties of the materials not provided for elsewhere in C04B2111/00
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は光触媒タイル及びそ
の製造方法に係り、特に、タイル表面に厚膜の光触媒機
能を有する被膜（以下「光触媒性被膜」と称す場合があ
る。）を形成することで光触媒効果を高めると共に、干
渉による虹彩現象を防止した光触媒タイルと、このよう
な光触媒タイルを化学的蒸着法（ＣＶＤ）により製造す
る方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalytic tile and a method for manufacturing the same, and more particularly, to forming a thick film having a photocatalytic function (hereinafter sometimes referred to as "photocatalytic film") on the tile surface. The present invention relates to a photocatalytic tile in which the photocatalytic effect is enhanced and the iris phenomenon due to interference is prevented, and a method for manufacturing such a photocatalytic tile by chemical vapor deposition (CVD).
【０００２】[0002]
【従来の技術】従来、鏡やレンズ、板ガラス等の透明基
材の表面を高度に親水化することにより、基材の曇りや
水滴形成を防止することを目的として、或いは、建材や
機械装置或いは各種物品の表面を高度に親水化すること
により、表面の汚れを防止し、表面の自己浄化（セルフ
クリーニング）機能を付与すると共に、汚れを落とし易
くして清掃を容易にするために、基材表面に光触媒性チ
タニア（ＴｉＯ2）等の光触媒性被膜を形成することが
行われている（特開平９−２４１０３８号公報、国際公
開ＷＯ９６／２９３７５、特開昭６１−８３１０６号公
報）。光触媒性チタニア等の光触媒機能を有する物質
は、光励起による親水化効果で基材表面を高度に親水化
し、水滴の形成を防止して、光の散乱による曇りを防止
する。また、親油性成分を多く含む汚れが付着し難くな
ると共に、表面の自己浄化及び作用が得られ、付着した
汚れも落ち易くなる。また、光触媒効果でＮＯｘやＳＯ
ｘ或いは有機物の分解が促進されることによっても上記
効果が高められる。2. Description of the Related Art Conventionally, the surface of a transparent substrate such as a mirror, a lens, a plate glass or the like is highly hydrophilized so as to prevent clouding or water droplet formation on the substrate, or to provide a building material, a mechanical device or To make the surface of various articles highly hydrophilic to prevent surface dirt and to provide a surface self-cleaning (self-cleaning) function, and to make it easy to remove dirt and facilitate cleaning, photocatalytic titania on the surface to form a photocatalytic coating of (TiO 2) or the like has been performed (JP-a-9-241038 and JP International Publication WO96 / twenty-nine thousand three hundred and seventy-five, JP 61-83106 JP). A substance having a photocatalytic function, such as photocatalytic titania, makes the surface of a substrate highly hydrophilic by a hydrophilizing effect by photoexcitation, prevents formation of water droplets, and prevents clouding due to light scattering. In addition, dirt containing a large amount of lipophilic component is less likely to adhere, self-cleaning and action of the surface is obtained, and the adhered dirt becomes easier to remove. In addition, NOx and SO
The above effect is also enhanced by promoting the decomposition of x or organic substances.
【０００３】従来においてはＴｉＯ2等の光触媒性被膜
は、１００〜８００ｎｍ（特開平９−２４１０３８号公
報）或いは、約０．２μｍ以下（国際公開ＷＯ９６／２
９３７５）といった薄膜に形成されている。このような
光触媒機能を有する膜の形成方法として、特開平９−２
４１０３８号公報及び国際公開ＷＯ９６／２９３７５に
は、ＴｉＯ2粒子を含む懸濁液の塗布、焼成によるゾル
ゲル法が記載されている。Conventionally, a photocatalytic film such as TiO 2 has a thickness of 100 to 800 nm (Japanese Patent Laid-Open No. 9-241038) or about 0.2 μm or less (International Publication WO96 / 2).
9375). As a method of forming such a film having a photocatalytic function, Japanese Patent Application Laid-Open No.
No. 41038 and International Publication WO 96/29375 describe a sol-gel method by applying and firing a suspension containing TiO 2 particles.
【０００４】特開昭６１−８３１０６号公報には被膜形
成法としてＣＶＤが記載されているが、その成膜条件や
被膜厚みについては特に考慮されていない。なお、従
来、タイル表面にＣＶＤによりＴｉＯ2被膜を形成する
場合、一般的には、図１に示す如く、タイル搬送ベルト
１上にタイル２を載せ、加熱ゾーン３に搬送して加熱し
た後、ＴｉＣｌ4（四塩化チタン）蒸気発生炉５で発生
させたＴｉＣｌ4蒸気が導入される蒸着室４に搬送し、
蒸着室４内で下記式の加水分解反応で生じたＴｉＯ2を
タイル表面に蒸着させ、その後、冷却ゾーン６で冷却す
ることにより成膜が行われる。Japanese Patent Application Laid-Open No. 61-83106 describes CVD as a method for forming a film, but does not particularly consider the film forming conditions and the film thickness. Conventionally, when a TiO 2 film is formed on a tile surface by CVD, generally, as shown in FIG. 1, the tile 2 is placed on a tile transport belt 1 and transported to a heating zone 3 for heating. The TiCl 4 (titanium tetrachloride) is transported to the vapor deposition chamber 4 into which the TiCl 4 vapor generated in the vapor generating furnace 5 is introduced.
In the vapor deposition chamber 4, TiO 2 generated by a hydrolysis reaction of the following formula is vapor-deposited on the tile surface, and then cooled in the cooling zone 6 to form a film.
【０００５】 ＴｉＣｌ4＋２Ｈ2Ｏ→ＴｉＯ2＋４ＨＣｌ このようなＣＶＤによるＴｉＯ2被膜の形成に当り、従
来では加熱ゾーンの温度は３００〜５００℃、ＴｉＣｌ
4蒸気発生炉の温度は３５℃程度とされ、０．０８μｍ
程度の厚さのＴｉＯ2被膜が形成されている。TiCl 4 + 2H 2 O → TiO 2 + 4HCl In forming a TiO 2 film by CVD, conventionally, the temperature of the heating zone is 300 to 500 ° C.
(4) The temperature of the steam generating furnace is set to about 35 ° C and 0.08 μm
A TiO 2 film having a thickness of about 30 nm is formed.
【０００６】[0006]
【発明が解決しようとする課題】光触媒性被膜を８００
ｎｍ（＝０．８μｍ）以下の厚さに形成する従来の技術
では、光の干渉による虹彩現像を生じ易く、意匠上の問
題があった。また、膜厚が薄いと、それだけ、光触媒効
果も劣るものとなる。SUMMARY OF THE INVENTION A photocatalytic coating of 800
In the conventional technique for forming a layer having a thickness of nm (= 0.8 μm) or less, iris development is likely to occur due to light interference, and there is a problem in design. Further, the thinner the film thickness, the lower the photocatalytic effect.
【０００７】また、従来のゾルゲル法による成膜では均
一な膜を形成することが困難である。ＣＶＤ法によれば
均一な膜を形成することができるが、従来のＣＶＤ条件
では被膜の厚膜化を図ることが難しい。Further, it is difficult to form a uniform film by the conventional sol-gel method. Although a uniform film can be formed by the CVD method, it is difficult to increase the thickness of the film under the conventional CVD conditions.
【０００８】本発明は上記従来の問題を解決し、タイル
表面に厚膜の光触媒性被膜を形成することで光触媒効果
を高めると共に、光の干渉による虹彩現象を防止した光
触媒タイル、及びこのような光触媒タイルをＣＶＤ法に
より製造する方法を提供することを目的とする。The present invention solves the above-mentioned conventional problems, and enhances the photocatalytic effect by forming a thick photocatalytic film on the tile surface, and prevents the iris phenomenon due to light interference. An object of the present invention is to provide a method for manufacturing a photocatalytic tile by a CVD method.
【０００９】[0009]
【課題を解決するための手段】本発明の光触媒タイル
は、表面に光触媒機能を有する被膜を形成してなる光触
媒タイルにおいて、該被膜の厚みが０．８μｍよりも大
きいことを特徴とする。The photocatalytic tile of the present invention is characterized in that a photocatalytic tile having a surface having a photocatalytic function formed on the surface has a thickness of more than 0.8 μm.
【００１０】光触媒性被膜の厚みが０．８μｍより大き
い厚膜であれば、膜厚が可視光の波長よりも厚いため、
干渉による虹彩現象が防止される。また、光触媒性被膜
が厚いことから、光触媒効果も向上し、良好な汚染防止
等の効果が得られる。If the thickness of the photocatalytic film is larger than 0.8 μm, the thickness is larger than the wavelength of visible light.
The iris phenomenon due to interference is prevented. In addition, since the photocatalytic film is thick, the photocatalytic effect is also improved, and good effects such as prevention of contamination can be obtained.
【００１１】この被膜は、ピンホール等の未被覆部分が
ないようにタイル全面に均一に形成されるのが好まし
い。The coating is preferably formed uniformly on the entire surface of the tile so that there is no uncovered portion such as a pinhole.
【００１２】本発明の一態様では、被膜は実質的にＴｉ
Ｏ2のみにて構成される。In one aspect of the invention, the coating is substantially Ti
It is composed of O 2 only.
【００１３】このような本発明の光触媒タイルは、タイ
ルを加熱ゾーンで加熱した後、ＴｉＣｌ4蒸気発生炉で
発生させたＴｉＣｌ4蒸気が導入される蒸着室にて、該
ＴｉＣｌ4蒸気の加水分解で生じたＴｉＯ2を該タイル表
面に蒸着させることにより、タイル表面に厚みが０．８
μｍよりも大きいＴｉＯ2被膜を形成することを特徴と
する本発明の光触媒タイルの製造方法により容易に製造
することができる。[0013] Photocatalytic tiles of the present invention as described above, after heating the tile at the heating zone, at TiCl 4 vapor deposition chamber TiCl 4 steam generated in the steam generator furnace is introduced, of the TiCl 4 vapor hydrolysis By depositing TiO 2 generated in the above on the tile surface, a thickness of 0.8
It can be easily manufactured by the method for manufacturing a photocatalytic tile according to the present invention, which is characterized by forming a TiO 2 coating larger than μm.
【００１４】このような方法において、加熱ゾーンにお
いてタイルを３００〜８００℃に加熱しておくことによ
り、付着強度の高い被膜を形成することができる。ま
た、加熱ゾーンの温度を５００〜７００℃とすると共
に、ＴｉＣｌ4蒸気発生炉の温度を４５℃以上とするこ
とにより、膜厚の大きな光触媒性被膜を１回の成膜操作
により形成することができる。In such a method, by heating the tile to 300 to 800 ° C. in the heating zone, a film having high adhesive strength can be formed. Further, by setting the temperature of the heating zone to 500 to 700 ° C. and the temperature of the TiCl 4 steam generating furnace to 45 ° C. or higher, a photocatalytic film having a large film thickness can be formed by one film forming operation. it can.
【００１５】蒸着により形成されたＴｉＯ2被膜を５０
０〜９００℃で焼成（結晶化アニール）することによ
り、被膜中のＴｉＯ2結晶相を更に増加させ、光触媒性
能をより一層高めることができる。The TiO 2 film formed by vapor deposition is
By baking (crystallization annealing) at 0 to 900 ° C., the TiO 2 crystal phase in the coating can be further increased, and the photocatalytic performance can be further enhanced.
【００１６】[0016]
【発明の実施の形態】以下に本発明の実施の形態を詳細
に説明する。Embodiments of the present invention will be described below in detail.
【００１７】本発明において、タイル表面に形成する光
触媒性被膜の光触媒機能を有する物質としては、ＴｉＯ
2の他、ＺｒＯ2、ＺｎＯ、ＳｎＯ2、ＷＯ3、Ｂｉ2Ｏ3、
ＳｒＴｉＯ3、Ｆｅ2Ｏ3、Ｖ2Ｏ5等の金属酸化物が挙げ
られる。これらの金属酸化物は１種を単独で用いても良
く、また２種以上を併用しても良い。In the present invention, the substance having a photocatalytic function of the photocatalytic film formed on the tile surface is TiO.
2 , ZrO 2 , ZnO, SnO 2 , WO 3 , Bi 2 O 3 ,
Metal oxides such as SrTiO 3 , Fe 2 O 3 , and V 2 O 5 are mentioned. One of these metal oxides may be used alone, or two or more thereof may be used in combination.
【００１８】本発明の一態様では、被膜はＴｉＯ2のみ
にて構成される。このＴｉＯ2のみからなる被膜は光触
媒機能がきわめて高い。In one embodiment of the present invention, the coating is composed of TiO 2 only. The coating composed of only TiO 2 has a very high photocatalytic function.
【００１９】本発明においては、このような光触媒性被
膜を０．８μｍより厚い被膜に形成する。光触媒性被膜
の厚みが０．８μｍ以下では干渉による虹彩の問題があ
り、また、十分な光触媒効果を得ることができない。こ
の光触媒性被膜が過度に厚いと被膜形成コストが高騰す
るため、光触媒性被膜の厚みは０．８μｍより大きく２
μｍ以下、特に０．８〜１．２μｍとするのが好まし
い。In the present invention, such a photocatalytic film is formed into a film thicker than 0.8 μm. If the thickness of the photocatalytic film is 0.8 μm or less, there is a problem of iris due to interference, and a sufficient photocatalytic effect cannot be obtained. If the thickness of the photocatalytic film is excessively large, the cost of forming the film increases.
It is preferably at most μm, particularly preferably 0.8 to 1.2 μm.
【００２０】このような光触媒性被膜は、ゾルゲル法に
より形成することも可能であるが、前述の如く、ゾルゲ
ル法では形成される光触媒性被膜中のＴｉＯ2等の光触
媒性物質の分布が不均一となり、均一性状の高特性光触
媒性被膜を形成することができないことから、好ましく
はＣＶＤにより形成する。Such a photocatalytic film can be formed by the sol-gel method. However, as described above, the distribution of the photocatalytic substance such as TiO 2 in the photocatalytic film formed by the sol-gel method is uneven. Since a uniform high-performance photocatalytic film cannot be formed, the film is preferably formed by CVD.
【００２１】以下に、ＴｉＯ2光触媒性被膜をＣＶＤに
より形成して光触媒タイルを製造する本発明の光触媒タ
イルの製造方法について説明する。The method for producing a photocatalytic tile of the present invention for producing a photocatalytic tile by forming a TiO 2 photocatalytic film by CVD will be described below.
【００２２】本発明では、下記のような好適なＣＶＤ条
件を採用すること以外は、図１に示す従来法と同様にし
てＣＶＤ−ＴｉＯ2被膜を形成することができる。In the present invention, a CVD-TiO 2 film can be formed in the same manner as in the conventional method shown in FIG. 1 except that the following suitable CVD conditions are employed.
【００２３】 加熱ゾーン３の温度 加熱ゾーン３の温度を３００〜８００℃とすることによ
り、被膜の付着強度を高めることができる。とりわけ、
本発明では、０．８μｍより厚い厚膜のＴｉＯ2被膜を
形成するために、この加熱ゾーン３の温度を５００〜７
００℃とするのが好ましい。このように、タイル２の予
熱温度を高めることにより、厚膜のＴｉＯ2被膜を１回
の成膜操作にて形成することが可能となる。Temperature of Heating Zone 3 By setting the temperature of the heating zone 3 to 300 to 800 ° C., the adhesion strength of the coating can be increased. Above all,
In the present invention, in order to form a thick TiO 2 film having a thickness of more than 0.8 μm, the temperature of the heating zone 3 is set to 500-7.
It is preferably set to 00 ° C. As described above, by increasing the preheating temperature of the tile 2, it is possible to form a thick TiO 2 film by a single film forming operation.
【００２４】 ＴｉＣｌ4蒸気発生炉５の温度 従来法では、ＴｉＣｌ4蒸気発生炉５の温度は３５℃程
度とされているが、本発明では、０．８μｍより厚い厚
膜のＴｉＯ2被膜を形成するために、このＴｉＣｌ4蒸気
発生炉５の温度は４５℃以上、特に５０〜７０℃とする
のが好ましい。このように、ＴｉＣｌ4蒸気発生炉５の
温度を高めることにより、大量のＴｉＣｌ4蒸気を発生
させて膜厚の厚いＴｉＯ2被膜を形成することができ
る。なお、蒸着室４では、雰囲気中の湿気により加水分
解が進行するが、この蒸着室の湿度が低く、加水分解の
ための水分が不足する場合には、蒸着室内に水を入れた
容器を入れておき、水蒸気を発生させるようにすれば良
い。また、蒸着室に大気を供給したり、この大気に水蒸
気を添加しても良い。Temperature of TiCl 4 Steam Generator 5 In the conventional method, the temperature of the TiCl 4 steam generator 5 is about 35 ° C. In the present invention, a thick TiO 2 film thicker than 0.8 μm is formed. For this purpose, the temperature of the TiCl 4 steam generating furnace 5 is preferably 45 ° C. or more, particularly preferably 50 to 70 ° C. As described above, by increasing the temperature of the TiCl 4 vapor generating furnace 5, a large amount of TiCl 4 vapor can be generated to form a thick TiO 2 film. In the vapor deposition chamber 4, hydrolysis proceeds due to moisture in the atmosphere. However, when the humidity of the vapor deposition chamber is low and the amount of water for hydrolysis is insufficient, a container containing water is placed in the vapor deposition chamber. In advance, it is sufficient to generate steam. Further, the atmosphere may be supplied to the evaporation chamber, or water vapor may be added to the atmosphere.
【００２５】形成されるＴｉＯ2蒸着膜の膜厚は、蒸着
室４の滞留時間を調節したり、ＴｉＣｌ4蒸気発生炉５
の温度を調節してＴｉＣｌ4蒸着量を増減することによ
り容易に調節することができる。The thickness of the TiO 2 vapor deposition film to be formed can be adjusted by adjusting the residence time in the vapor deposition chamber 4 or by using a TiCl 4 vapor generation furnace 5.
The temperature can be easily adjusted by increasing or decreasing the amount of TiCl 4 deposited.
【００２６】なお、その他のＣＶＤ条件は次のような条
件を採用するのが好ましい。It is preferable to employ the following conditions as other CVD conditions.
【００２７】 加熱ゾーンの滞留時間 ： １５〜３０分 蒸着室の雰囲気 ： 大気（必要に応じ加湿） 蒸着室の雰囲気圧力 ： 大気圧 蒸着室の温度 ： １５０〜２５０℃ 冷却ゾーンの冷却速度 ： ３０〜４０℃／分 このようなＣＶＤ法によりＴｉＯ2蒸着膜を形成した後
は、形成されたＴｉＯ2蒸着膜を５００〜９００℃で焼
成して結晶化アニール処理するのが好ましい。このよう
な結晶化アニール処理を行うことにより、ＴｉＯ2結晶
相を更に増加させてＴｉＯ2光触媒性被膜の光触媒性能
を高めることができる。Residence time in heating zone: 15 to 30 minutes Atmosphere in vapor deposition chamber: air (humidified as necessary) Atmospheric pressure in vapor deposition chamber: atmospheric pressure Temperature in vapor deposition chamber: 150 to 250 ° C. Cooling rate in cooling zone: 30 to 40 ° C./min After forming the TiO 2 deposited film by such a CVD method, it is preferable to bake the formed TiO 2 deposited film at 500 to 900 ° C. and to perform a crystallization annealing treatment. By performing such crystallization annealing treatment, the photocatalytic performance of the TiO 2 photocatalytic film can be enhanced by further increasing the TiO 2 crystal phase.
【００２８】なお、ＣＶＤ法によるＴｉＯ2蒸着膜の形
成に当り、ＴｉＣｌ4と共に、ＳｉＣｌ4（四塩化珪素）
やＳｎＣｌ４（四塩化錫）等の他の蒸着原料を併用する
ことにより、ＴｉＯ2−ＳｉＯ2又はＴｉＯ2−ＳｎＯ2等
の複合光触媒性被膜を形成することができる。In forming a TiO 2 deposited film by the CVD method, SiCl 4 (silicon tetrachloride) is used together with TiCl 4.
A composite photocatalytic film such as TiO 2 —SiO 2 or TiO 2 —SnO 2 can be formed by using other vapor-deposition materials such as SnCl 4 (tin tetrachloride) and the like.
【００２９】[0029]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明する。The present invention will be described more specifically below with reference to examples and comparative examples.
【００３０】実施例１〜３図１に示すＣＶＤ法により、
下記ＣＶＤ条件でタイル表面にＴｉＯ2蒸着膜を形成
し、形成されたＴｉＯ2蒸着膜を６００℃で１時間焼成
して結晶化アニール処理することにより、表１に示す厚
さのＴｉＯ2光触媒性被膜を形成した。なお、蒸着室滞
留時間は、実施例１では４０秒、実施例２では６０秒、
実施例３では８０秒とした。Examples 1 to 3 By the CVD method shown in FIG.
A TiO 2 deposited film is formed on the tile surface under the following CVD conditions, and the formed TiO 2 deposited film is baked at 600 ° C. for 1 hour and subjected to a crystallization annealing treatment to obtain a TiO 2 photocatalytic film having a thickness shown in Table 1. A coating was formed. The residence time in the vapor deposition chamber was 40 seconds in Example 1, 60 seconds in Example 2,
In Example 3, it was set to 80 seconds.
【００３１】 加熱ゾーンの温度 ： ６５０℃ 加熱ゾーン３の滞留時間 ： ２０分 蒸着室４の雰囲気 ： 大気 蒸着室４の雰囲気圧力 ： 大気圧 蒸着室４の温度 ： ２００℃ ＴｉＣｌ4蒸気発生炉５の温度： ６５℃ 冷却ゾーン６の冷却速度 ： ３０℃／秒 得られた光触媒タイルについて、目視により干渉による
虹彩現象の有無を調べ、下記基準で評価し、結果を表１
に示した。なお、平均１μｍ厚のＴｉＯ2被膜は約０．
３ｍｇ／ｃｍ2の付着量に相当する。Temperature of heating zone: 650 ° C. Residence time of heating zone 3: 20 minutes Atmosphere of vapor deposition chamber 4: atmosphere Atmospheric pressure of vapor deposition chamber 4: atmospheric pressure Temperature of vapor deposition chamber 4: 200 ° C. TiCl 4 vapor generation furnace 5 Temperature: 65 ° C. Cooling rate of cooling zone 6: 30 ° C./sec The obtained photocatalytic tile was visually inspected for the presence or absence of iris phenomenon due to interference, and evaluated according to the following criteria.
It was shown to. The average thickness of the TiO 2 film of 1 μm is about 0.1 μm.
This corresponds to an attached amount of 3 mg / cm 2 .
【００３２】＜評価基準＞ ○：干渉による虹彩現象なし △：干渉による虹彩現象若干あり ×：干渉による虹彩現象あり また、この光触媒タイルについて、メチレンブルーを付
着させ、このメチレンブルーの分解量を測定することに
より光触媒効果を調べ、結果を表１に示した。<Evaluation Criteria> ○: No iris phenomenon due to interference Δ: Some iris phenomenon due to interference ×: There is iris phenomenon due to interference Further, methylene blue is adhered to this photocatalytic tile, and the decomposition amount of this methylene blue is measured. The photocatalytic effect was examined by using the following formula.
【００３３】このメチレンブルーの付着及び分解反応条
件は次の通りである。The conditions for the adhesion and decomposition of methylene blue are as follows.
【００３４】＜メチレンブルー分解試験方法＞タイルに
２×２ｃｍの開口部を持つマスクを置き、０．０１％濃
度のメチレンブルー・エタノール溶液を５マイクロリッ
トル滴下し、乾燥させる。乾燥後、タイルを照明室に入
れ、光を照射する。光源はＢＬＢランプを用い、光の照
射量は、試験片表面で２．０ｍＷ／ｃｍ2のＵＶ強度と
する。タイル表面のメチレンブルー残存量を、分光光度
計を用い青色光の反射率として経時的に計測し、初期量
の１／２となるまでの時間をメチレンブルー半減期とし
て求めた。<Methylene Blue Decomposition Test Method> A mask having an opening of 2 × 2 cm is placed on a tile, and 5 microliters of a 0.01% strength methylene blue / ethanol solution is dropped and dried. After drying, the tiles are placed in a lighting room and irradiated with light. A BLB lamp is used as a light source, and a light irradiation amount is 2.0 mW / cm 2 UV intensity on the surface of the test piece. The remaining amount of methylene blue on the tile surface was measured over time using a spectrophotometer as the reflectance of blue light, and the time until the amount became 1/2 of the initial amount was determined as the methylene blue half-life.
【００３５】さらに、この光触媒タイルについて、表面
の被膜の付着強度も次の方法により評価した。Further, the adhesion strength of the film on the surface of this photocatalytic tile was evaluated by the following method.
【００３６】＜被膜付着強度試験法＞ＪＩＳ−６９０９
に準拠するしゅう動摩耗試験により、研磨材を不織布ナ
イロンブラシ（住友３Ｍ製スコッチブライト５１ライン
白）、研磨荷重を１ｋｇ／７０ｃｍ2とし、被膜の剥離
する研磨回数を求めた。<Coating adhesion strength test method> JIS-6909
Abrasive material was a non-woven nylon brush (Scotch Bright 51 line made by Sumitomo 3M, white line), the polishing load was 1 kg / 70 cm 2, and the number of times of polishing at which the coating was peeled off was determined by a sliding wear test according to.
【００３７】比較例１，２ 実施例１において、蒸着室滞留時間を比較例１では３０
秒、比較例２では１０秒とし、加熱ゾーン３の温度を４
００℃とし、ＴｉＣｌ4蒸気発生炉５の温度を３５℃と
したこと以外は同様にして、表１に示す厚さのＴｉＯ2
光触媒性被膜を形成し、同様に評価を行って結果を表１
に示した。Comparative Examples 1 and 2 In Example 1, the residence time in the vapor deposition chamber was 30 in Comparative Example 1.
Second, 10 seconds in Comparative Example 2, and the temperature of the heating zone 3 is set to 4 seconds.
TiO 2 having a thickness shown in Table 1 in the same manner except that the temperature of the TiCl 4 steam generating furnace 5 was 35 ° C.
A photocatalytic film was formed and evaluated in the same manner.
It was shown to.
【００３８】比較例３，４ 加熱ゾーンの温度を２００℃又は８５０℃としたこと以
外は、実施例１と同様にして光触媒タイルを製造し、同
様の評価テストを行った。結果を表１に示す。Comparative Examples 3 and 4 Photocatalytic tiles were manufactured in the same manner as in Example 1 except that the temperature of the heating zone was set at 200 ° C. or 850 ° C., and the same evaluation test was performed. Table 1 shows the results.
【００３９】比較例５ ＣＶＤ法ではなくゾル−ゲル法によりタイル表面に平均
して０．３ｍｇ／ｃｍ2の割合でＴｉＯ2を付着させた光
触媒タイルを製造し、同様の評価テストを行った。結果
を表１に示す。Comparative Example 5 A photocatalytic tile having TiO 2 deposited on the tile surface at an average rate of 0.3 mg / cm 2 was produced by the sol-gel method instead of the CVD method, and the same evaluation test was performed. Table 1 shows the results.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【発明の効果】以上詳述した通り、本発明の光触媒タイ
ル及びその製造方法によれば、干渉による虹彩現象の問
題がなく、しかも光触媒性能に優れ、かつ付着強度の高
い被膜を有し、汚れ防止ないし自己浄化作用等に優れた
光触媒タイルが提供される。As described above in detail, according to the photocatalytic tile and the method for producing the same of the present invention, there is no problem of iris phenomenon due to interference, and the coating has excellent photocatalytic performance and high adhesion strength. A photocatalytic tile excellent in prevention or self-cleaning action is provided.
【００４２】このような本発明の光触媒タイルは、各種
内外装用建材として有効に利用することができ、その表
面を長期に亘り、清浄かつ美麗に保つことができる。Such a photocatalyst tile of the present invention can be effectively used as various interior and exterior building materials, and its surface can be kept clean and beautiful for a long time.
【図面の簡単な説明】[Brief description of the drawings]
【図１】ＣＶＤによるＴｉＯ2蒸着膜の形成方法を説明
する系統図である。FIG. 1 is a system diagram for explaining a method of forming a TiO 2 deposited film by CVD.
１ タイル搬送ベルト ２ タイル ３ 加熱ゾーン ４ 蒸着室 ５ ＴｉＣｌ4蒸気発生炉 ６ 冷却ゾーンDESCRIPTION OF SYMBOLS 1 Tile conveyor belt 2 Tile 3 Heating zone 4 Deposition chamber 5 TiCl 4 Steam generating furnace 6 Cooling zone
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加藤 博道 愛知県常滑市鯉江本町５丁目１番地 株式 会社イナックス内 (72)発明者 杵島 健 愛知県常滑市鯉江本町５丁目１番地 株式 会社イナックス内 (72)発明者 大貫 徹 愛知県常滑市鯉江本町５丁目１番地 株式 会社イナックス内 (72)発明者 神谷 嘉夫 愛知県常滑市鯉江本町５丁目１番地 株式 会社イナックス内 (72)発明者 安永 政義 愛知県常滑市鯉江本町５丁目１番地 株式 会社イナックス内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiromichi Kato 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Ken Takeshima 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Inax Corporation (72) Inventor Toru Onuki 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Yoshio Kamiya 5-1-1 Koiehonmachi, Tokoname-shi, Aichi Prefecture Inax Corporation (72) Inventor Masayoshi Yasunaga 5-1-1 Koiehonmachi, Tokoname-city, Aichi Prefecture Inax Corporation
Claims (7)
てなる光触媒タイルにおいて、該被膜の厚みが０．８μ
ｍよりも大きいことを特徴とする光触媒タイル。1. A photocatalytic tile having a surface having a photocatalytic function formed on a surface thereof, wherein the thickness of the film is 0.8 μm.
A photocatalytic tile, wherein the tile is larger than m.
Ｏ2のみからなることを特徴とする光触媒タイル。2. The method according to claim 1, wherein the coating is substantially Ti.
A photocatalytic tile comprising only O 2 .
表面の全面を覆っていることを特徴とする光触媒タイ
ル。3. The photocatalytic tile according to claim 1, wherein the coating covers the entire surface of the tile.
Ｃｌ4蒸気発生炉で発生させたＴｉＣｌ4蒸気が導入され
る蒸着室にて、該ＴｉＣｌ4蒸気の加水分解で生じたＴ
ｉＯ2を該タイル表面に蒸着させることにより、タイル
表面に厚みが０．８μｍよりも大きい結晶質ＴｉＯ2を
含む被膜を形成することを特徴とする光触媒タイルの製
造方法。4. After heating the tile in a heating zone, the Ti
In a vapor deposition chamber into which TiCl 4 vapor generated in a Cl 4 vapor generating furnace is introduced, T generated by hydrolysis of the TiCl 4 vapor
A method for producing a photocatalytic tile, comprising forming a coating containing crystalline TiO 2 having a thickness of more than 0.8 μm on a tile surface by depositing iO 2 on the tile surface.
で３００〜８００℃に加熱することを特徴とする光触媒
タイルの製造方法。5. The method according to claim 4, wherein the tile is heated to 300 to 800 ° C. in a heating zone.
を５００〜７００℃とすると共に、ＴｉＣｌ4蒸気発生
炉の温度を４５℃以上とすることを特徴とする光触媒タ
イルの製造方法。6. The method for producing a photocatalytic tile according to claim 4, wherein the temperature of the heating zone is set to 500 to 700 ° C., and the temperature of the TiCl 4 steam generating furnace is set to 45 ° C. or higher.
て、蒸着により形成されたＴｉＯ2被膜を更に５００〜
９００℃で焼成することを特徴とする光触媒タイルの製
造方法。7. The TiO 2 film formed by vapor deposition according to claim 4, wherein
A method for producing a photocatalytic tile, comprising firing at 900 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11074053A JP2000072575A (en) | 1998-04-13 | 1999-03-18 | Photocatalytic tile and its production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-101235 | 1998-04-13 | ||
| JP10123598 | 1998-04-13 | ||
| JP11074053A JP2000072575A (en) | 1998-04-13 | 1999-03-18 | Photocatalytic tile and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000072575A true JP2000072575A (en) | 2000-03-07 |
Family
ID=26415194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11074053A Pending JP2000072575A (en) | 1998-04-13 | 1999-03-18 | Photocatalytic tile and its production |
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| Country | Link |
|---|---|
| JP (1) | JP2000072575A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003061828A1 (en) * | 2002-01-21 | 2003-07-31 | Sumitomo Titanium Corporation | Photocatalytic composite material and method for preparation thereof |
| JP2004057912A (en) * | 2002-07-26 | 2004-02-26 | Sumitomo Titanium Corp | Photocatalyst composite material and its production method |
-
1999
- 1999-03-18 JP JP11074053A patent/JP2000072575A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003061828A1 (en) * | 2002-01-21 | 2003-07-31 | Sumitomo Titanium Corporation | Photocatalytic composite material and method for preparation thereof |
| JP2004057912A (en) * | 2002-07-26 | 2004-02-26 | Sumitomo Titanium Corp | Photocatalyst composite material and its production method |
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