JPH09310185A - Photocatalyst-coated metallic sheet and its production - Google Patents
Photocatalyst-coated metallic sheet and its productionInfo
- Publication number
- JPH09310185A JPH09310185A JP8146587A JP14658796A JPH09310185A JP H09310185 A JPH09310185 A JP H09310185A JP 8146587 A JP8146587 A JP 8146587A JP 14658796 A JP14658796 A JP 14658796A JP H09310185 A JPH09310185 A JP H09310185A
- Authority
- JP
- Japan
- Prior art keywords
- metal plate
- photocatalyst
- sio
- tio
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002184 metal Substances 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 67
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000009792 diffusion process Methods 0.000 claims abstract description 8
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 41
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 27
- 229910000077 silane Inorganic materials 0.000 claims description 14
- -1 silane compound Chemical class 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000005641 methacryl group Chemical group 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 229910052681 coesite Inorganic materials 0.000 abstract 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract 5
- 229910052682 stishovite Inorganic materials 0.000 abstract 5
- 229910052905 tridymite Inorganic materials 0.000 abstract 5
- 150000004756 silanes Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 36
- 239000000758 substrate Substances 0.000 description 22
- 238000000354 decomposition reaction Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011247 coating layer Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 240000008415 Lactuca sativa Species 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 235000012045 salad Nutrition 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ACQXJDHTMKUEQK-UHFFFAOYSA-N N'-benzyl-N'-ethenyl-2-(trimethoxysilylmethyl)butane-1,4-diamine hydrochloride Chemical compound Cl.CO[Si](CC(CN)CCN(Cc1ccccc1)C=C)(OC)OC ACQXJDHTMKUEQK-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、有機物や水の分解に有
効な光触媒作用を呈する光触媒被覆金属板及びその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocatalyst-coated metal plate exhibiting a photocatalytic effect effective for decomposing organic substances and water, and a method for producing the same.
【０００２】[0002]
【従来の技術】光触媒粒子に、バンドギャップ以上のエ
ネルギーをもつ波長の光を照射すると、光励起によって
伝導帯に電子が、価電子帯に正孔が生じる。この光励起
により発生した正孔の持つ強い酸化力は、有機物や水の
分解等に利用されている。しかし、光触媒を粒子状態の
ままで使用することは、その取扱いや回収を困難にし、
流出や飛散が避けられない。そのため、光触媒は、金属
等の基板に固定して使用されている。このような金属板
としては、金属板に光触媒を直接被覆したものが特開平
３−８４４８号公報に、高反射率表面をもつ担体上に光
透過性のよい電荷分離槽を設けた後で光触媒粒子を担持
させたものが特開平７−８８３６７号公報に紹介されて
いる。基板に対する光触媒の固定には、基板上で光触媒
粒子を４００℃以上の温度で焼結して焼き付ける方法，
加熱分解で光触媒となる物質を４００℃程度の温度に加
熱した基板上に吹き付ける方法等が採用されている。ま
た、基板に光触媒粒子とフッ素系ポリマーとの混合物を
積層，圧着する方法，光触媒粒子を懸濁させた樹脂塗料
を付着させる方法等も知られている。2. Description of the Related Art When photocatalyst particles are irradiated with light having a wavelength of energy greater than the band gap, photoexcitation produces electrons in the conduction band and holes in the valence band. The strong oxidizing power of the holes generated by this photoexcitation is utilized for decomposition of organic substances and water. However, using the photocatalyst in the particulate state makes its handling and recovery difficult,
Inflow and scattering are unavoidable. Therefore, the photocatalyst is used by being fixed to a substrate such as a metal. As such a metal plate, a metal plate directly coated with a photocatalyst is disclosed in Japanese Patent Laid-Open No. 3-8448, and a photocatalyst is provided after a charge separation tank having good light transmittance is provided on a carrier having a high reflectance surface. A material carrying particles is introduced in JP-A-7-88367. For fixing the photocatalyst to the substrate, a method of sintering and baking the photocatalyst particles on the substrate at a temperature of 400 ° C. or higher,
For example, a method of spraying a substance that becomes a photocatalyst by thermal decomposition onto a substrate heated to a temperature of about 400 ° C. is used. Also known are a method of laminating a mixture of photocatalyst particles and a fluoropolymer on a substrate and pressure bonding, a method of attaching a resin coating material in which the photocatalyst particles are suspended, and the like.
【０００３】[0003]
【発明が解決しようとする課題】従来の方法で光触媒層
を設けようとすると、十分な光触媒活性を呈する光触媒
被覆金属板を得ることができなかった。たとえば、樹脂
等に混合して光触媒粒子を塗布すると、光触媒表面の一
部が樹脂等で覆われるため、光触媒粒子の全表面を触媒
作用面として使用できない。他方、加熱焼付けにより光
触媒のみで金属板を被覆することもできるが、この方法
では、形成された光触媒被覆層の触媒活性が著しく低下
する。また、特開平７−８８３６７号公報のように鏡面
仕上げした金属板等の高反射率金属板を基板に使用する
ものでは、エチレン分解等の特殊な用途に使用可能に過
ぎず、金属板を鏡面仕上げするにはかなりコスト高とな
るため、建材等に使用される通常の金属板には適用でき
ない。本発明は、このような問題を解消すべく案出され
たものであり、ＳｉＯ2 系の下地層を形成することによ
り、鏡面仕上げを必要とすることなく、通常の金属板を
基板として使用し、十分な触媒活性を呈する光触媒被覆
金属板を得ることを目的とする。When a photocatalyst layer is provided by the conventional method, a photocatalyst-coated metal plate exhibiting sufficient photocatalytic activity cannot be obtained. For example, when the photocatalyst particles are mixed with a resin or the like and coated, the photocatalyst surface is partially covered with the resin or the like, so that the entire surface of the photocatalyst particles cannot be used as a catalytic surface. On the other hand, the metal plate can be coated with only the photocatalyst by heating and baking, but in this method, the catalytic activity of the formed photocatalyst coating layer is significantly reduced. Further, in the case of using a high-reflectance metal plate such as a mirror-finished metal plate as a substrate as in JP-A-7-88367, it can only be used for special applications such as ethylene decomposition, and the metal plate is mirror-finished. Since it is considerably expensive to finish, it cannot be applied to ordinary metal plates used for building materials. The present invention has been devised to solve such a problem. By forming an SiO 2 -based underlayer, a normal metal plate is used as a substrate without the need for mirror-finishing. The object is to obtain a photocatalyst-coated metal plate exhibiting sufficient catalytic activity.
【０００４】[0004]
【課題を解決するための手段】本発明の光触媒被覆金属
板は、その目的を達成するため、金属板表面に金属拡散
抑制用のＳｉＯ2 下地層を介してＴｉＯ2 層が形成され
ていることを特徴とする。この光触媒被覆金属板は、金
属板表面に塗布したシラン化合物又はＳｉＯ2 ゾルを熱
処理し、金属板表面にＳｉＯ2 前駆体又はＳｉＯ2 から
なる下地層を形成した後、有機チタン化合物又はチタニ
アゾルを塗布して熱処理し、金属板からの金属拡散をＳ
ｉＯ2 下地層で抑制しながらＴｉＯ2 を金属板に焼き付
けることにより製造される。シラン化合物として、Ｘ−
Ｓｉ（ＯＲ）3 の構造をもつものが使用される。式中、
Ｘはビニル基，エポキシ基，アミノ基，メタクリル基又
はメルカプト基を示し、Ｒはアルキル基を示す。有機チ
タン化合物には、チタンアルコキシド又はチタンβジケ
トネートが使用される。In order to achieve the object, the photocatalyst-coated metal plate of the present invention has a TiO 2 layer formed on the surface of the metal plate via a SiO 2 underlayer for suppressing metal diffusion. Is characterized by. In this photocatalyst-coated metal plate, a silane compound or SiO 2 sol applied to the surface of the metal plate is heat-treated to form a base layer made of a SiO 2 precursor or SiO 2 on the surface of the metal plate, and then an organotitanium compound or titania sol is applied. And heat treatment to diffuse metal from the metal plate
It is manufactured by baking TiO 2 on a metal plate while suppressing it with an iO 2 underlayer. As a silane compound, X-
Those having the structure of Si (OR) 3 are used. Where:
X represents a vinyl group, an epoxy group, an amino group, a methacryl group or a mercapto group, and R represents an alkyl group. Titanium alkoxide or titanium β-diketonate is used as the organic titanium compound.
【０００５】シラン化合物又はＳｉＯ2 ゾルを金属板表
面に塗布した後、好ましくは１５０〜８５０℃で熱処理
するとき、Ｓｉ−Ｏの網目構造をもつ親水性又は親油性
の被覆層が金属板の表面に形成される。このＳｉＯ2 系
被覆層を下地としてＴｉＯ2層を形成するとき、触媒活
性を低下させることなく光触媒被覆層が形成される。光
触媒被覆層は、たとえば有機チタン化合物又はチタニア
ゾルを塗布した後、４００〜８５０℃で熱処理すること
により形成される。シラン化合物，ＳｉＯ2 ゾル，有機
チタン化合物，ＴｉＯ2 ゾル等は、浸漬，スプレー，泳
動電着等の方法で基体の金属板表面に施される。When a silane compound or SiO 2 sol is applied on the surface of a metal plate and then heat-treated at 150 to 850 ° C., a hydrophilic or lipophilic coating layer having a Si—O network structure is formed on the surface of the metal plate. Is formed. When the TiO 2 layer is formed using this SiO 2 -based coating layer as a base, the photocatalyst coating layer is formed without lowering the catalytic activity. The photocatalyst coating layer is formed, for example, by applying an organotitanium compound or titania sol and then performing heat treatment at 400 to 850 ° C. The silane compound, SiO 2 sol, organic titanium compound, TiO 2 sol, etc. are applied to the surface of the metal plate of the substrate by a method such as dipping, spraying, or electrophoretic deposition.
【０００６】[0006]
【作用】本発明者等は、金属板にＴｉＯ2 層を直接形成
する場合に触媒活性が低下する原因を種々調査した。そ
の結果、ＴｉＯ2 層を形成する加熱処理時に、金属板か
ら金属が拡散することによって電子，正孔の再結合中心
がＴｉＯ2 層中に形成されることに原因があるとの結論
を得た。すなわち、ＴｉＯ2 系の光触媒では、光による
励起が不純物によって大きな影響を受ける。不純物によ
る悪影響は、金属の種類にもよって異なるが、０．１モ
ル％以下でも現れる。そこで、本発明においては、金属
板からの金属拡散を抑制するために金属板表面にＳｉＯ
2 層を形成している。ＳｉＯ2 層は、加熱処理時に基板
から拡散する金属の拡散速度を遅くし、その上に形成さ
れる光触媒層が本来もつ光触媒作用を良好に維持する。The present inventors investigated various causes of the decrease in catalytic activity when the TiO 2 layer was formed directly on the metal plate. As a result, obtained at the time of heat treatment for forming the TiO 2 layer, electron by diffusing metal from the metal plate, the conclusion that recombination centers of the hole is caused to be formed in two layers of TiO . That is, in the TiO 2 -based photocatalyst, the excitation by light is greatly affected by the impurities. The adverse effect of impurities varies depending on the type of metal, but appears even at 0.1 mol% or less. Therefore, in the present invention, SiO is formed on the surface of the metal plate in order to suppress metal diffusion from the metal plate.
Two layers are formed. The SiO 2 layer slows down the diffusion rate of the metal that diffuses from the substrate during the heat treatment, and maintains the photocatalytic action originally possessed by the photocatalytic layer formed thereon.
【０００７】[0007]
【実施の形態】下地層のシラン化合物中の反応基として
親水基をもつものを使用し、１５０〜４００℃で加熱処
理することにより金属板表面に親水性のあるＳｉＯ2 皮
膜を形成する。水系ＴｉＯ2 ゾルを用いてこの下地層の
上にＴｉＯ2 コーティングを施すと、濡れ性が良く均一
なコーティングを施すことができる。６００〜８５０℃
で加熱処理すると、ＴｉＯ2 系皮膜の密着性が向上する
と共に、下地層に含まれる有機物が消失し、ＳｉＯ2 か
らなる均質な下地層が形成される。他方、反応基として
親油基をもつシラン化合物を使用すると、１５０〜４０
０℃の加熱処理で表面に親油基をもつ皮膜が形成され
る。チタンアルコキシド等の有機チタン化合物を有機溶
媒に溶解させた溶液を用いて下地層の上にＴｉＯ2 コー
ティングを施すと、濡れ性が良好で均一なコーティング
が施される。コーティング後、４００〜８５０℃で加熱
処理すると、ＴｉＯ2 系皮膜の密着性が向上すると共
に、下地層に含まれる有機物が消失し、ＳｉＯ2 からな
る均質な下地層が形成される。BEST MODE FOR CARRYING OUT THE INVENTION A hydrophilic silane is used as a reactive group in a silane compound of an underlayer, and a hydrophilic SiO 2 film is formed on the surface of a metal plate by heat treatment at 150 to 400 ° C. By applying a TiO 2 coating on this underlayer using an aqueous TiO 2 sol, a good wettability and uniform coating can be applied. 600-850 ° C
The heat treatment improves the adhesion of the TiO 2 -based film, eliminates organic substances contained in the underlayer, and forms a uniform underlayer made of SiO 2 . On the other hand, when a silane compound having a lipophilic group as a reactive group is used, it is 150 to 40
A film having a lipophilic group is formed on the surface by heat treatment at 0 ° C. When a TiO 2 coating is applied on the underlayer using a solution prepared by dissolving an organic titanium compound such as titanium alkoxide in an organic solvent, good wettability and uniform coating are applied. When heat treatment is performed at 400 to 850 ° C. after coating, the adhesion of the TiO 2 -based film is improved, organic substances contained in the underlayer disappear, and a uniform underlayer made of SiO 2 is formed.
【０００８】下地層形成時に８５０℃を超える温度で熱
処理すると、形成されたＳｉＯ2 層にクラックが生じ易
い。ＳｉＯ2 層にクラックが生成すると、皮膜が剥離し
易くなり、長期間にわたって安定した油分解特性が持続
しない。また、１５０℃に達しない熱処理温度では、金
属板に対する密着性が劣り、衝撃や異物等との接触によ
って被覆層が金属板から容易に剥離する。表層形成時に
８５０℃を超える温度で熱処理すると、ＴｉＯ2 層がア
ナターゼ構造からルチル構造に変化し、光触媒としての
機能が損なわれる。しかし、４００℃に達しない熱処理
温度では、密着性が劣り、衝撃や異物等との接触によっ
て被覆層が金属板から容易に剥離する。この点、特開平
７−８８３６７号公報で開示されている方法では、シリ
カ層形成時には１５０℃で３時間乾燥させ、ＴｉＯ2 層
形成時にはＴｉＯ2 単独ではなくシリカバインダーを２
０％含有させ、１５０℃で３〜６時間乾燥させ、場合に
よっては５００℃で１時間の焼成を行っている。この方
法では、長時間の処理が必要であると共に、ＴｉＯ2 層
の密着性を上げるためのシリカバインダーを必要とする
ため、触媒活性がＴｉＯ2 単独より低下する。If the heat treatment is performed at a temperature higher than 850 ° C. when the underlayer is formed, cracks are easily generated in the formed SiO 2 layer. When a crack is generated in the SiO 2 layer, the film is easily peeled off, and stable oil decomposition characteristics are not maintained for a long period of time. Further, at a heat treatment temperature which does not reach 150 ° C., the adhesion to the metal plate is poor, and the coating layer is easily peeled off from the metal plate due to impact or contact with foreign matter. When heat-treated at a temperature higher than 850 ° C. when forming the surface layer, the TiO 2 layer changes from the anatase structure to the rutile structure, and the function as a photocatalyst is impaired. However, at a heat treatment temperature that does not reach 400 ° C., the adhesion is poor and the coating layer is easily peeled off from the metal plate due to impact or contact with foreign matter. In this respect, according to the method disclosed in JP-A-7-88367, the silica layer is dried at 150 ° C. for 3 hours, and when the TiO 2 layer is formed, the TiO 2 alone is used instead of the silica binder.
It is contained at 0%, dried at 150 ° C. for 3 to 6 hours, and in some cases baked at 500 ° C. for 1 hour. In this method, long-term treatment is required and a silica binder for increasing the adhesion of the TiO 2 layer is required, so that the catalytic activity is lower than that of TiO 2 alone.
【０００９】[0009]
実施例１：板厚０．６ｍｍのＳＵＳ４３０ステンレス鋼
板を基板としシランカップリング液に浸漬し、０．１ｍ
／秒の速度で引き上げ、１００〜９００℃で１０分間加
熱した。これにより、基板表面に膜厚０．１５μｍのＳ
ｉＯ2 層が形成された。なお、シランカップリング液と
しては、親水基をもつシランカップリング剤としてＮ−
β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノ
プロピルトリメトキシシラン塩酸塩を使用し、エタノー
ルを用いて濃度２０％に調製したものを使用した。次い
で、水系ＴｉＯ2 ゾルに浸漬し、０．５ｍ／秒の速度で
引き上げ、乾燥後に６００〜９００℃で２分間焼成し
た。形成されたＴｉＯ2 層は、１．２μｍの厚みをもっ
ていた。Example 1: A SUS430 stainless steel plate having a plate thickness of 0.6 mm was used as a substrate and immersed in a silane coupling liquid to give a thickness of 0.1 m.
It was pulled up at a rate of / sec and heated at 100 to 900 ° C. for 10 minutes. As a result, S with a thickness of 0.15 μm is formed on the substrate surface.
An iO 2 layer was formed. The silane coupling liquid is N-as a silane coupling agent having a hydrophilic group.
β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride was used, and the one prepared to a concentration of 20% with ethanol was used. Then, it was dipped in an aqueous TiO 2 sol, pulled up at a speed of 0.5 m / sec, dried, and calcined at 600 to 900 ° C. for 2 minutes. The formed TiO 2 layer had a thickness of 1.2 μm.
【００１０】処理された各試料について、膜の密着性及
び油分解特性を調査した。密着性は、碁盤目テープ剥離
試験で調査し、全く剥離しないものを○，僅かでも剥離
したものを×として評価した。油分解特性試験では、２
ｍｇ／ｃｍ2 のサラダ油を塗布した後、ブラックライト
を照射し、８ｍＷ／ｃｍ2 のＵＶ強度で油分解し、重量
変化を測定した。そして、ガラス基板上のＴｉＯ2 膜と
同じ油分解特性を示し、ＴｉＯ2 膜がアナターゼ構造を
もつものを○，ガラス基板上のＴｉＯ2 膜と同じ油分解
特性を示すものの、ＴｉＯ2 膜がルチル構造をもつもの
を△，ガラス基板上のＴｉＯ2 膜よりも油分解特性が低
下したものを×として評価した。例として、試験番号４
の試験片にサラダ油を２ｍｇ／ｃｍ2 塗布した後、紫外
線強度８ｍＷ／ｃｍ2 のブラックライトを照射し、照射
時間と油分解率との関係を調査した。その結果、試験番
号４では、図１に示すようにガラス基板上にＴｉＯ2 を
１．２μｍの膜厚で形成したものとほぼ同じ油分解特性
を示した。For each treated sample, the adhesion and oil degradation properties of the membrane were investigated. Adhesion was examined by a cross-cut tape peeling test, and those that did not peel at all were evaluated as ◯, and those that peeled even slightly were evaluated as x. 2 in oil decomposition test
After applying mg / cm 2 of salad oil, it was irradiated with black light to decompose oil with a UV intensity of 8 mW / cm 2 , and the weight change was measured. Then, show the same oil breakdown characteristics as TiO 2 film on a glass substrate, ○ those TiO 2 film has an anatase structure, while indicating same oil breakdown characteristics as TiO 2 film on a glass substrate, is TiO 2 film rutile Those having a structure were evaluated as Δ, and those having a lower oil decomposition property than the TiO 2 film on the glass substrate were evaluated as x. As an example, test number 4
After applying 2 mg / cm 2 of salad oil to the test piece of No. 2 , the sample was irradiated with black light having an ultraviolet intensity of 8 mW / cm 2 , and the relationship between the irradiation time and the oil decomposition rate was investigated. As a result, in Test No. 4, as shown in FIG. 1, almost the same oil decomposition characteristics as those obtained by forming TiO 2 with a film thickness of 1.2 μm on the glass substrate were shown.
【００１１】 [0011]
【００１２】実施例２：板厚０．６ｍｍのＳＵＳ４３０
ステンレス鋼板を基板とし、シランカップリング浴に浸
漬し、０．１ｍ／秒の速度で引き上げ、１００〜９００
℃で１０分間加熱した。カップリング浴としては、親油
基をもつシランカップリング剤としてビニルトリメトキ
シシランを使用し、イソプロパノールで濃度２０％に調
製したものを使用した。次いで、１Ｍチタンテトライソ
プロポキシド−０．２Ｍ ＨＣｌ−０．５Ｍ Ｈ2 Ｏ−
１５Ｍエタノール溶液に浸漬し、０．２ｍ／分の速度で
引き上げ、３００〜９００℃で１分間焼成した。焼成後
の試験片表面を観察すると、膜厚０．１５μｍのＳｉＯ
2 層，膜厚０．３μｍのＴｉＯ2 層が形成されていた。
得られた皮膜の密着性及び油分解特性を、処理条件との
関係で表２に示す。なお、表２における油分解特性は、
表１と同様に評価した。Example 2: SUS430 having a plate thickness of 0.6 mm
Using a stainless steel plate as a substrate, immersing it in a silane coupling bath and pulling it up at a speed of 0.1 m / sec to 100 to 900
Heated at 0 ° C for 10 minutes. As the coupling bath, one prepared by using vinyltrimethoxysilane as a silane coupling agent having a lipophilic group and adjusting the concentration to 20% with isopropanol was used. Then, 1M titanium tetraisopropoxide-0.2M HCl-0.5MH 2 O-
It was immersed in a 15 M ethanol solution, pulled up at a speed of 0.2 m / min, and baked at 300 to 900 ° C. for 1 minute. Observing the surface of the test piece after firing, it was found that
Two layers, a TiO 2 layer having a thickness of 0.3 μm was formed.
The adhesiveness and oil decomposition characteristics of the obtained film are shown in Table 2 in relation to the processing conditions. The oil decomposition characteristics in Table 2 are
It evaluated similarly to Table 1.
【００１３】 [0013]
【００１４】実施例３：板厚０．４ｍｍのＳＵＳ４３０
ステンレス鋼板を基板として、ＳｉＯ2 ゾルをスプレー
コーティングした後、５００℃で５分間焼成しＳｉＯ2
層を形成した。次いで、水系ＴｉＯ2 ゾルをスプレーコ
ーティングして乾燥した後、７００℃で２分間焼成し
た。得られた被覆材は、ＳｉＯ2 層が０．３μｍの膜
厚，ＴｉＯ2層が４μｍの膜厚をもっていた。この被覆
金属板を使用して実施例１と同様な条件下で油分解特性
を調査した結果、ガラス基板上に膜厚４μｍのＴｉＯ2
層を被覆したものと同じ油分解特性を示した。Example 3: SUS430 having a plate thickness of 0.4 mm
The stainless steel plate as a substrate was spray-coated with SiO 2 sol, and baked for 5 minutes at 500 ° C. SiO 2
A layer was formed. Next, after spray coating an aqueous TiO 2 sol and drying, it was baked at 700 ° C. for 2 minutes. In the obtained coating material, the SiO 2 layer had a film thickness of 0.3 μm and the TiO 2 layer had a film thickness of 4 μm. Using this coated metal plate, the oil decomposition characteristics were investigated under the same conditions as in Example 1, and as a result, TiO 2 with a film thickness of 4 μm was formed on the glass substrate.
It showed the same oil-degrading properties as the layer coating.
【００１５】実施例４：板厚０．５ｍｍの溶融アルミニ
ウムめっき鋼板を金属基体とし、メチルトリメトキシシ
ランのシランカップリング剤に浸漬した。カップリング
液から０．１ｍ／秒の速度で引き上げ、２００℃で２０
分間乾燥させた。その後、１Ｍチタンアセチルアセトネ
ート−０．２Ｍ ＨＣｌ−０．５Ｍ Ｈ2 Ｏ−１５Ｍ
エタノール溶液に浸漬し、０．２ｍ／分の速度で引き上
げ、５００℃で１分間焼成した。得られた被覆材は、
０．１５μｍのＳｉＯ2 層及び０．３μｍのＴｉＯ2 層
をもっていた。この被覆金属板を使用して実施例１と同
様な条件下で油分解特性を調査した結果、ガラス基板上
に膜厚０．３μｍのＴｉＯ2 層を被覆したものと同じ油
分解特性を示した。Example 4 A hot-dip aluminum-plated steel sheet having a thickness of 0.5 mm was used as a metal substrate and immersed in a silane coupling agent of methyltrimethoxysilane. It is pulled up from the coupling liquid at a speed of 0.1 m / sec and kept at 200 ° C for 20
Allow to dry for minutes. Then, 1M titanium acetylacetonate -0.2M HCl-0.5M H 2 O- 15M
It was immersed in an ethanol solution, pulled up at a speed of 0.2 m / min, and baked at 500 ° C. for 1 minute. The obtained covering material is
It had a 0.15 μm SiO 2 layer and a 0.3 μm TiO 2 layer. As a result of investigating the oil decomposition characteristics using this coated metal plate under the same conditions as in Example 1, the same oil decomposition characteristics as those obtained by coating a TiO 2 layer having a film thickness of 0.3 μm on a glass substrate were shown. .
【００１６】比較例１：水系ＴｉＯ2 ゾルにＳＵＳ４３
０ステンレス鋼を浸漬し、０．５ｍ／秒の速度で引き上
げることによりＴｉＯ2 コーティングを施した。そし
て、乾燥後、７００℃で２分間焼成し、光触媒被覆金属
板を作成した。この光触媒被覆金属板の触媒活性を調査
するため、サラダ油２ｍｇ／ｃｍ2 を塗布した状態でブ
ラックライトを照射する油分解実験に供した。その結
果、図１に示すように、ガラス基板上に被覆された同一
膜厚のＴｉＯ2 層に比較して油分解特性が著しく低下し
た。Comparative Example 1: SUS43 was added to an aqueous TiO 2 sol.
A TiO 2 coating was applied by dipping 0 stainless steel and pulling it up at a speed of 0.5 m / sec. Then, after drying, it was baked at 700 ° C. for 2 minutes to prepare a photocatalyst-coated metal plate. In order to investigate the catalytic activity of this photocatalyst-coated metal plate, it was subjected to an oil-decomposition experiment in which 2 mg / cm 2 of salad oil was applied and black light was irradiated. As a result, as shown in FIG. 1, the oil decomposition characteristics were significantly reduced as compared with the TiO 2 layer of the same thickness coated on the glass substrate.
【００１７】比較例２：１Ｍ チタンテトライソプロポ
キシド−０．２Ｍ ＨＣｌ−０．５Ｍ Ｈ2 Ｏ−１５Ｍ
エタノールの組成をもつゾルゲル浴にＳＵＳ４３０ス
テンレス鋼を浸漬し、０．２ｍ／秒の速度で引き上げる
ことによりＴｉＯ2 コーティングを施した。そして、乾
燥後、７００℃で２分間焼成して光触媒被覆金属板を作
成した。この光触媒被覆金属板の触媒活性を調査するた
め、サラダ油２ｍｇ／ｃｍ2 を塗布した状態でブラック
ライトを照射する油分解実験に供した。その結果、図１
に示すように、ガラス基板上に被覆された同一膜厚のＴ
ｉＯ2 層に比較して油分解特性が著しく低下した。Comparative Example 2: 1M Titanium tetraisopropoxide-0.2M HCl-0.5M H 2 O-15M
The TiO 2 coating was applied by immersing SUS430 stainless steel in a sol-gel bath having a composition of ethanol and pulling it up at a speed of 0.2 m / sec. Then, after drying, it was baked at 700 ° C. for 2 minutes to prepare a photocatalyst-coated metal plate. In order to investigate the catalytic activity of this photocatalyst-coated metal plate, it was subjected to an oil-decomposition experiment in which 2 mg / cm 2 of salad oil was applied and black light was irradiated. As a result, FIG.
As shown in FIG.
The oil decomposition characteristics were significantly reduced as compared with the iO 2 layer.
【００１８】[0018]
【発明の効果】以上に説明したように、本発明の光触媒
被覆金属板は、ＳｉＯ2 層を介してＴｉＯ2 層を形成し
ているので、焼成時に素地金属板からの金属元素が拡散
することがＳｉＯ2 層で抑制され、触媒活性の低下がな
いＴｉＯ2 層が金属板表面に形成される。このようにし
て得られた光触媒被覆金属板は、高位に安定した触媒活
性を長期間持続し、厨房用器具，多数の人が出入りする
建築物用の建材等として衛生面に関する要求が高い用途
に使用される。As described above, in the photocatalyst-coated metal plate of the present invention, the TiO 2 layer is formed via the SiO 2 layer, so that the metal element from the base metal plate diffuses during firing. Is suppressed by the SiO 2 layer, and a TiO 2 layer having no reduction in catalytic activity is formed on the surface of the metal plate. The photocatalyst-coated metal plate thus obtained has a high level of stable catalytic activity for a long period of time, and is used for kitchen appliances, building materials for buildings where many people come and go, and other applications with high hygiene requirements. used.
【図１】 金属板表面にＳｉＯ2 層を介してＴｉＯ2 層
を被覆したものの油分解特性を、直接ＴｉＯ2 層を形成
した金属板及びガラス基板の油分解特性と比較したグラ
フFIG. 1 is a graph comparing the oil decomposition characteristics of a metal plate surface coated with a TiO 2 layer through a SiO 2 layer and the oil decomposition characteristics of a metal plate and a glass substrate on which a TiO 2 layer is directly formed.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小浦 節子 千葉県市川市高谷新町７番１号 日新製鋼 株式会社技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Setsuko Koura 7-1 Takatani Shinmachi, Ichikawa City, Chiba Nisshin Steel Co., Ltd. Technical Research Institute
Claims (6)
下地層を介してＴｉＯ2 層が形成されている光触媒被覆
金属板。1. A metal plate surface made of SiO 2 for suppressing metal diffusion.
A photocatalyst-coated metal plate having a TiO 2 layer formed via an underlayer.
ＳｉＯ2 ゾルを熱処理し、金属板表面にＳｉＯ2 前駆体
又はＳｉＯ2 からなる下地層を形成した後、有機チタン
化合物又はチタニアゾルを塗布して熱処理し、金属板か
らの金属拡散をＳｉＯ2 下地層で抑制しながらＴｉＯ2
を金属板に焼き付けることを特徴とする光触媒被覆金属
板の製造方法。2. A silane compound or SiO 2 sol applied on the surface of a metal plate is heat treated to form a base layer made of a SiO 2 precursor or SiO 2 on the surface of the metal plate, and then an organic titanium compound or titania sol is applied. Heat treatment is performed to suppress the metal diffusion from the metal plate by the SiO 2 underlayer, and the TiO 2
A method for producing a photocatalyst-coated metal plate, comprising: baking a metal plate on a metal plate.
−Ｓｉ（ＯＲ）3 （ただし、Ｘはビニル基，エポキシ
基，アミノ基，メタクリル基又はメルカプト基を示し、
Ｒはアルキル基を示す）の構造をもつシラン化合物を使
用する光触媒被覆金属板の製造方法。3. The silane compound according to claim 2, which is X
-Si (OR) 3 (where X represents a vinyl group, an epoxy group, an amino group, a methacryl group or a mercapto group,
R is an alkyl group) A method for producing a photocatalyst-coated metal plate using a silane compound having a structure.
ンアルコキシド又はチタンβジケトネートである光触媒
被覆金属板の製造方法。4. A method for producing a photocatalyst-coated metal plate, wherein the organotitanium compound according to claim 2 is titanium alkoxide or titanium β-diketonate.
ラン化合物又はＳｉＯ2 ゾルを、１５０〜８５０℃で熱
処理する光触媒被覆金属板の製造方法。5. A method for producing a photocatalyst-coated metal plate, which comprises heat-treating the silane compound or SiO 2 sol according to claim 1 applied on the surface of a metal plate at 150 to 850 ° C.
タニアゾルを塗布した後、４００〜８５０℃で熱処理す
る光触媒被覆金属板の製造方法。6. A method for producing a photocatalyst-coated metal plate, which comprises applying the organotitanium compound or titania sol according to claim 1 and then heat-treating at 400 to 850 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14658796A JP3384930B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing photocatalyst-coated metal plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14658796A JP3384930B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing photocatalyst-coated metal plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09310185A true JPH09310185A (en) | 1997-12-02 |
| JP3384930B2 JP3384930B2 (en) | 2003-03-10 |
Family
ID=15411093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14658796A Expired - Fee Related JP3384930B2 (en) | 1996-05-16 | 1996-05-16 | Method for producing photocatalyst-coated metal plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3384930B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11181969A (en) * | 1997-12-24 | 1999-07-06 | Sumitomo Metal Ind Ltd | High reflectivity surface treated plate excellent in pollution resistance |
| JP2002080980A (en) * | 2000-06-20 | 2002-03-22 | Mitsubishi Heavy Ind Ltd | Metallic base material having photocatalytic film, its production method and method for hydrophilizing surface of metallic base material |
| JP2008043949A (en) * | 2007-09-04 | 2008-02-28 | Nippon Soda Co Ltd | Photocatalyst-carrying structure manufacturing method and photocatalyst-carrying structure obtained by the same |
| JP2008523979A (en) * | 2004-12-17 | 2008-07-10 | アルミン | Amorphous composite structures for photocatalysis |
| JP2016176103A (en) * | 2015-03-19 | 2016-10-06 | 大日製罐株式会社 | Surface treated steel sheet, metal container, production method of surface treated steel sheet, rust-resistance imparting method, slidability improvement method, ablation prevention method, scratch-filled property improvement method and chemical-resistance imparting method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06278241A (en) * | 1992-09-22 | 1994-10-04 | Takenaka Komuten Co Ltd | Building material |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
-
1996
- 1996-05-16 JP JP14658796A patent/JP3384930B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06278241A (en) * | 1992-09-22 | 1994-10-04 | Takenaka Komuten Co Ltd | Building material |
| JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11181969A (en) * | 1997-12-24 | 1999-07-06 | Sumitomo Metal Ind Ltd | High reflectivity surface treated plate excellent in pollution resistance |
| JP2002080980A (en) * | 2000-06-20 | 2002-03-22 | Mitsubishi Heavy Ind Ltd | Metallic base material having photocatalytic film, its production method and method for hydrophilizing surface of metallic base material |
| JP2008523979A (en) * | 2004-12-17 | 2008-07-10 | アルミン | Amorphous composite structures for photocatalysis |
| JP2008043949A (en) * | 2007-09-04 | 2008-02-28 | Nippon Soda Co Ltd | Photocatalyst-carrying structure manufacturing method and photocatalyst-carrying structure obtained by the same |
| JP2016176103A (en) * | 2015-03-19 | 2016-10-06 | 大日製罐株式会社 | Surface treated steel sheet, metal container, production method of surface treated steel sheet, rust-resistance imparting method, slidability improvement method, ablation prevention method, scratch-filled property improvement method and chemical-resistance imparting method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3384930B2 (en) | 2003-03-10 |
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