JP2000096212A - Photocatalyst film coated member and its production - Google Patents
Photocatalyst film coated member and its productionInfo
- Publication number
- JP2000096212A JP2000096212A JP10272664A JP27266498A JP2000096212A JP 2000096212 A JP2000096212 A JP 2000096212A JP 10272664 A JP10272664 A JP 10272664A JP 27266498 A JP27266498 A JP 27266498A JP 2000096212 A JP2000096212 A JP 2000096212A
- Authority
- JP
- Japan
- Prior art keywords
- film
- substrate
- titanium dioxide
- coated
- photocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 42
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 12
- 239000005361 soda-lime glass Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 16
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 239000001913 cellulose Substances 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 150000002605 large molecules Chemical class 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000003729 Neprilysin Human genes 0.000 description 1
- 108090000028 Neprilysin Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RJRPCMREZGLMKP-UHFFFAOYSA-N [Ti].O=C=O Chemical compound [Ti].O=C=O RJRPCMREZGLMKP-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は抗菌部材、防汚部
材、大気や水の浄化部材などに用いられる、光触媒膜被
覆部材と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 photocatalytic film-coated member used for an antibacterial member, an antifouling member, a member for purifying air or water, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、空気浄化や汚水浄化などの環境浄
化に二酸化チタン（ＴｉＯ2）光触媒を利用する試みが
活発となっている。これは二酸化チタンにエネルギーギ
ャップ以上のエネルギーを持つ光を照射することにより
生じた電子と正孔の酸化、還元作用により、空気中や水
中の悪臭物質、有害物質などを分解、除去するものであ
る。また、二酸化チタンの超親水性を防汚、防滴防曇に
利用する試みも行われている。2. Description of the Related Art In recent years, attempts to use a titanium dioxide (TiO 2 ) photocatalyst for environmental purification such as air purification and sewage purification have become active. It decomposes and removes odorous substances and harmful substances in the air and water by oxidizing and reducing electrons and holes generated by irradiating titanium dioxide with light having energy greater than the energy gap. . Attempts have also been made to use the superhydrophilicity of titanium dioxide for antifouling and drip-proof and anti-fog.
【０００３】これらの目的で二酸化チタンを利用する場
合、なんらかの基材の上に二酸化チタン膜を被覆した形
で用いられることが多い。基材上に二酸化チタン膜を被
覆する方法としては、二酸化チタン粉末をＳｉＯ2など
の無機バインダを用いて固定する方法、有機チタン化合
物の熱分解法、ゾルゲル法、あるいはスパッタリング
法、真空アーク蒸着法などのＰＶＤ法がある。[0003] When titanium dioxide is used for these purposes, it is often used in the form of a titanium dioxide film coated on some substrate. As a method of coating a titanium dioxide film on a substrate, a method of fixing titanium dioxide powder using an inorganic binder such as SiO 2 , a thermal decomposition method of an organic titanium compound, a sol-gel method, a sputtering method, a vacuum arc evaporation method And the like.
【０００４】真空アーク蒸着法は、Ｏ2を含む雰囲気中
でＴｉターゲットをアーク蒸発させることにより、基材
上に二酸化チタンを形成する方法であり、電学論Ａ、１
１７巻、８号（平成９年）第８６６頁〜第８７２頁に
は、真空アーク蒸着法により基材温度を室温で形成した
アモルファスの二酸化チタン膜を大気中あるいは真空中
において２５０℃以上で熱処理するか、あるいはアーク
電流の一部を基材固定台に流し、二酸化チタン成膜時の
基材固定台表面の温度を４５０℃とすることにより、光
触媒活性が高いことが知られているアナターゼ型結晶構
造の二酸化チタン膜を形成することが記載されている。[0004] The vacuum arc evaporation method is a method of forming titanium dioxide on a substrate by arc-evaporating a Ti target in an atmosphere containing O 2.
Vol. 17, No. 8 (1997), pages 866 to 872, heat treatment of an amorphous titanium dioxide film formed at a substrate temperature of room temperature by a vacuum arc vapor deposition method at 250 ° C. or higher in air or vacuum. Or, by flowing a part of the arc current to the substrate fixing table, and setting the temperature of the substrate fixing table surface at the time of titanium dioxide film formation to 450 ° C., the anatase type known to have high photocatalytic activity It is described that a titanium dioxide film having a crystalline structure is formed.
【０００５】[0005]
【発明が解決しようとする課題】無機バインダを用いて
二酸化チタン粉末を固定する方法は、安価であり、バイ
ンダの量を増やすことにより、室温から１５０℃の低温
で光触媒膜を形成することが可能なため、耐熱性の低い
基材上を用いることができるという利点があるが、光触
媒膜の硬度、基材との密着強度が低いという課題があ
る。The method of fixing titanium dioxide powder using an inorganic binder is inexpensive, and a photocatalytic film can be formed at a low temperature from room temperature to 150 ° C. by increasing the amount of the binder. Therefore, there is an advantage that a substrate having low heat resistance can be used, but there is a problem that the hardness of the photocatalytic film and the adhesion strength to the substrate are low.
【０００６】有機チタン化合物の熱分解法は、光触媒膜
の形成に基材を４５０℃以上に加熱する必要があり、耐
熱性の低い基材を用いることができないという課題があ
る。The thermal decomposition method of an organic titanium compound has a problem that a substrate must be heated to 450 ° C. or more to form a photocatalytic film, and a substrate having low heat resistance cannot be used.
【０００７】ゾルゲル法も基材の温度を４５０℃以上に
する必要があり、耐熱性の低い基材が使えないという課
題があり、また１回のコーティングで形成可能な光触媒
膜の厚さが薄く、光触媒活性や膜強度が優れた厚さ０．
５μｍ以上の二酸化チタン膜を形成するには、何回もコ
ーティングを繰り返す必要があり、短時間、低コストで
光触媒膜を形成できないという課題がある。[0007] The sol-gel method also requires the temperature of the substrate to be 450 ° C. or higher, so that a substrate having low heat resistance cannot be used, and the thickness of the photocatalytic film that can be formed by one coating is small. Thickness excellent in photocatalytic activity and film strength.
In order to form a titanium dioxide film having a thickness of 5 μm or more, coating must be repeated many times, and there is a problem that a photocatalytic film cannot be formed in a short time at low cost.
【０００８】スパッタ法は、高硬度、高密着強度の光触
媒膜を形成可能であるが、光触媒膜の成膜速度が遅く、
短時間、低コストで光触媒膜を形成できないという課題
がある。[0008] The sputtering method can form a photocatalytic film having high hardness and high adhesion strength. However, the film forming speed of the photocatalytic film is low.
There is a problem that a photocatalytic film cannot be formed in a short time at low cost.
【０００９】真空アーク蒸着法も二酸化チタン膜を形成
可能であるが、光触媒活性の優れたアナターゼ型結晶構
造の二酸化チタン膜を得るためには、基材固定台の温度
を４５０℃以上にする必要があるため、４５０℃以上の
温度で耐熱性のある基材でないと使用できないという課
題がある。また、成膜速度が十分でなく、成膜に要する
時間が長くなり、高コストになるという課題がある。さ
らに、真空アーク蒸着法により基材温度を室温で形成し
たアモルファスの二酸化チタン膜を２５０℃以上で熱処
理することによっても、アナターゼ型二酸化チタン膜を
得ているが、この方法では工程が長時間かつ高コストに
なるという課題がある。Although a titanium dioxide film can be formed by the vacuum arc evaporation method, the temperature of the substrate fixing base must be set to 450 ° C. or higher in order to obtain a titanium dioxide film having an anatase type crystal structure having excellent photocatalytic activity. Therefore, there is a problem that the substrate cannot be used unless the substrate has a heat resistance at a temperature of 450 ° C. or higher. Further, there is a problem that the film formation speed is not sufficient, the time required for film formation is long, and the cost is high. Furthermore, an anatase-type titanium dioxide film is obtained by heat-treating an amorphous titanium dioxide film formed at a substrate temperature of room temperature by a vacuum arc vapor deposition method at 250 ° C. or higher. There is a problem of high cost.
【００１０】このように、従来は、耐熱温度４００℃以
下の基材上に高硬度、高密着強度の二酸化チタンの光触
媒膜を形成した光触媒膜被覆部材を低コストで実現する
ことができなかった。As described above, conventionally, a photocatalyst film-coated member in which a titanium dioxide photocatalyst film having high hardness and high adhesion strength was formed on a substrate having a heat resistance temperature of 400 ° C. or lower could not be realized at low cost. .
【００１１】[0011]
【課題を解決するための手段】本発明の目的は、高硬
度、高密着強度の光触媒膜を被覆した部材を低コストで
提供することにある。An object of the present invention is to provide a member coated with a photocatalytic film having high hardness and high adhesion strength at low cost.
【００１２】本発明の請求項１における光触媒膜被覆部
材は、基材の耐熱温度が４００℃以下である基材上に、
直接あるいは中間層を介して、真空アーク蒸着法により
形成された光触媒膜が、アナターゼ型結晶構造を有する
二酸化チタンであることを特徴とする。The photocatalyst film-coated member according to claim 1 of the present invention is provided on a substrate having a heat resistant temperature of 400 ° C. or less.
The photocatalytic film formed by vacuum arc evaporation directly or through an intermediate layer is titanium dioxide having an anatase crystal structure.
【００１３】請求項２における光触媒膜被覆部材は、上
記した請求項１の構成において、耐熱温度が４００℃以
下である基材が高分子化合物であることを特徴とする。A photocatalyst film-coated member according to a second aspect of the present invention is characterized in that, in the constitution of the first aspect, the base material having a heat-resistant temperature of 400 ° C. or less is a polymer compound.
【００１４】請求項３における光触媒膜被覆部材は、基
材であるソーダライムガラス上に直接、真空アーク蒸着
法により形成された光触媒膜が、アナターゼ型結晶構造
を有する二酸化チタンであることを特徴とする。According to a third aspect of the present invention, the photocatalyst film-coated member is characterized in that the photocatalyst film formed directly on soda lime glass as a base material by a vacuum arc vapor deposition method is titanium dioxide having an anatase type crystal structure. I do.
【００１５】請求項４における光触媒膜被覆部材の製造
方法は、少なくともＡｒとＯ2を含む雰囲気ガス中で、
雰囲気ガスの全圧力が５〜１００ｍＴｏｒｒ、全圧力に
対するＯ2分圧の割合が５〜９５％、アーク電流が５５
〜１５０Ａ、基材温度が０〜４００℃にて、Ｔｉターゲ
ットをアーク蒸発させることにより、基材上にアナター
ゼ型二酸化チタン膜を形成させることを特徴とする。The method for manufacturing a photocatalyst film coating member in the fourth aspect, in an atmospheric gas containing at least Ar and O 2,
The total pressure of the atmosphere gas is 5 to 100 mTorr, the ratio of the partial pressure of O 2 to the total pressure is 5 to 95%, and the arc current is 55%.
An anatase type titanium dioxide film is formed on a substrate by arc-evaporating a Ti target at a temperature of up to 150 A and a substrate temperature of 0 to 400 ° C.
【００１６】[0016]
【作用】本発明の光触媒膜被覆部材は、耐熱温度４００
℃以下の基材上に直接あるいは、中間層を介して光触媒
膜が被覆された構造を有し、光触媒膜が真空アーク蒸着
法により形成されたアナターゼ型結晶構造を有する二酸
化チタンであることを特徴とする。我々は、真空アーク
蒸着法を用いて、耐熱温度４００℃以下の基材上におい
ても、アナターゼ型の結晶構造を有する二酸化チタン膜
を形成可能にすべく、実験と検討を重ねた結果、以下の
方法によれば実現可能なこと、及び高速成膜が可能なこ
とを見出した。The photocatalyst film-coated member of the present invention has a heat resistant temperature of 400.
It has a structure in which a photocatalyst film is coated directly on a substrate at a temperature of not more than ℃ or through an intermediate layer, and the photocatalyst film is titanium dioxide having an anatase type crystal structure formed by a vacuum arc vapor deposition method. And We conducted experiments and studies using a vacuum arc evaporation method to form a titanium dioxide film having an anatase-type crystal structure even on a substrate with a heat-resistant temperature of 400 ° C or lower. It has been found that the method is feasible and that high-speed film formation is possible.
【００１７】まず、成膜時の雰囲気ガスとしては、少な
くともＡｒとＯ2を含むガスを用いる。雰囲気ガスの全
圧力は５〜１００ｍＴｏｒｒとする。全圧力がこれ以上
小さいと、アーク放電が不安定となり、これ以上大きい
と成膜速度が遅くなるため、望ましくない。全圧力が１
０〜５０ｍＴｏｒｒの範囲であれば、さらに望ましい。
全圧力に対するＯ2分圧の割合は５〜９５％とする。こ
れ以上Ｏ2分圧の割合が小さいと、形成された膜の酸素
の組成が化学量論比組成よりも小さくなりすぎ、これ以
上大きいと、成膜速度が低くなるため望ましくない。Ｏ
2分圧の割合が２０〜７５％の範囲であれば、さらに望
ましい。First, a gas containing at least Ar and O 2 is used as an atmosphere gas during film formation. The total pressure of the atmosphere gas is 5 to 100 mTorr. If the total pressure is lower than this, the arc discharge becomes unstable, and if the total pressure is higher than this, the film-forming speed becomes slow, which is not desirable. Total pressure is 1
It is more preferable that the pressure is in the range of 0 to 50 mTorr.
The proportion of O 2 partial pressure to the total pressure is 5 to 95%. If the ratio of the partial pressure of O 2 is smaller than this, the composition of oxygen in the formed film becomes too small than the stoichiometric composition. O
More preferably, the ratio of the two partial pressures is in the range of 20 to 75%.
【００１８】ターゲットにはＴｉを使用し、アーク電流
が５５〜１５０Ａでアーク蒸発させて成膜を行う。アー
ク電流がこれ以上小さいと放電が不安定となり、また成
膜速度も低くなるため望ましくない。これ以上大きいと
形成された膜中にドロップレットと呼ばれるＴｉ粒子が
多く含まれるようになり、また基材の温度も上昇するた
め望ましくない。Using Ti as a target, a film is formed by arc evaporation at an arc current of 55 to 150 A. If the arc current is smaller than this, the discharge becomes unstable, and the film forming rate becomes low, which is not desirable. If it is larger than this, a large amount of Ti particles called droplets will be contained in the formed film, and the temperature of the base material will increase, which is not desirable.
【００１９】これらの条件範囲で成膜を行うことによ
り、基材の温度が０〜４００℃でもアナターゼ型の結晶
構造の二酸化チタン膜を形成することができるが、成膜
条件がこれらの範囲からはずれると、アナターゼ型の二
酸化チタン膜を合成することができなくなる。By forming a film under these conditions, a titanium dioxide film having an anatase type crystal structure can be formed even at a substrate temperature of 0 to 400 ° C. If it deviates, an anatase type titanium dioxide film cannot be synthesized.
【００２０】本発明では成膜中にヒーター等を用いて基
材を加熱する必要はないが、より結晶性の優れた膜を得
るために、基材の種類に応じて耐熱温度以下の範囲で基
材の加熱を行っても良い。基材を加熱せずに成膜を行っ
た場合においても、成膜中の基材へのイオンや中性粒子
の衝突により、基材の温度は室温から上昇するが、前記
の条件範囲で成膜を行えば、４００℃よりも基材温度が
上昇することはない。前記の条件範囲内で条件を最適化
すれば、基材の温度を１５０℃以下にすることも可能で
あり、このような温度範囲では使用可能な基材の種類が
大きく増えるため、さらに望ましい。また、基材固定台
を冷却水などを用いて冷却してもよい。In the present invention, it is not necessary to heat the substrate using a heater or the like during the film formation. The substrate may be heated. Even when a film is formed without heating the substrate, the temperature of the substrate increases from room temperature due to collision of ions and neutral particles with the substrate during film formation. If a film is formed, the substrate temperature will not rise above 400 ° C. By optimizing the conditions within the above-mentioned condition range, the temperature of the base material can be set to 150 ° C. or lower. In such a temperature range, the types of usable base materials greatly increase, which is more preferable. Further, the substrate fixing base may be cooled using cooling water or the like.
【００２１】本発明によると、アーク放電により生じた
イオンが加速されて基材上に入射することにより二酸化
チタン膜を形成するため、非常に密着強度の優れた膜が
得られる。基材との密着強度をさらに向上させる目的
で、基材に負電位のバイアスを印加して成膜を行っても
よい。また、緻密な多結晶膜となるため、非常に高い硬
度が得られる。さらに、２〜１０μｍ／ｈの非常に速い
速度で成膜が可能なため、低コストで光触媒膜胆持部材
を形成することができる。According to the present invention, the ions generated by the arc discharge are accelerated and incident on the substrate to form a titanium dioxide film, so that a film having extremely excellent adhesion strength can be obtained. For the purpose of further improving the adhesion strength to the substrate, the film may be formed by applying a negative potential bias to the substrate. Further, a very high hardness can be obtained because of the dense polycrystalline film. Further, since the film can be formed at a very high speed of 2 to 10 μm / h, the photocatalytic film supporting member can be formed at low cost.
【００２２】本発明においては、基材の温度４００℃以
下でも充分に結晶性の優れたアナターゼ型二酸化チタン
膜を得ることができるため、耐熱性の低い基材も使用す
ることが可能となる。ここで述べる耐熱温度とは、熱に
よる基材の変形、変質が生じない最高温度を示してい
る。本発明では、例えば、セルロース、ナイロン、ポリ
カーボネート、ポリエステル、ポリプロピレン、ポリエ
チレン、ポリウレタン、ポリイミド、フッ素樹脂などの
耐熱性の低い有機高分子化合物上、あるいはシリコーン
などの無機高分子化合物上にも光触媒膜を被覆すること
が可能である。これらの高分子化合物は、構造部材とし
てさまざまな用途に利用されており、これらを基材とし
て使用することにより、光触媒の用途を大幅に広げるこ
とができるため、特に望ましい。In the present invention, an anatase type titanium dioxide film having sufficiently excellent crystallinity can be obtained even at a substrate temperature of 400 ° C. or lower, so that a substrate having low heat resistance can be used. The heat-resistant temperature described here indicates the maximum temperature at which deformation and deterioration of the base material due to heat do not occur. In the present invention, for example, cellulose, nylon, polycarbonate, polyester, polypropylene, polyethylene, polyurethane, polyimide, a low heat-resistant organic high molecular compound such as fluororesin, or a photocatalytic film on an inorganic high molecular compound such as silicone. It is possible to coat. These polymer compounds are used in various applications as structural members, and the use of these as a base material is particularly desirable because the use of photocatalysts can be greatly expanded.
【００２３】これらの高分子化合物を基材に用いる場合
は、これらの基材上に直接二酸化チタンを成膜すると、
フッ素樹脂など一部を除き、光触媒により基材が分解さ
れるため、基材上にＳｉＯ2や金属等の光触媒に分解さ
れない無機物質の中間層を形成し、中間層を介してその
上に二酸化チタンを成膜する。中間層はアモルファスで
も良いため、真空アーク蒸着法以外にも、スパッタ法、
真空蒸着法、イオンプレーティング法等の方法を用いる
ことができる。When these polymer compounds are used for a substrate, a titanium dioxide film is formed directly on the substrate,
Since the base material is decomposed by the photocatalyst except for a part such as a fluororesin, an intermediate layer of an inorganic substance that is not decomposed by the photocatalyst such as SiO 2 or a metal is formed on the base material, and a carbon dioxide Titanium is deposited. Since the intermediate layer may be amorphous, in addition to the vacuum arc evaporation method, the sputtering method,
Methods such as a vacuum evaporation method and an ion plating method can be used.
【００２４】窓ガラスなどに一般に用いられているソー
ダライムガラス上に高温で二酸化チタンを形成すると、
基材中のＮａイオンが二酸化チタン膜に拡散して、触媒
活性が失われることが知られている。そのため、従来は
ソーダライムガラス上にＳｉＯ2などの中間層を形成
し、中間層上に二酸化チタン膜を形成していた。本発明
では低温で二酸化チタン膜が形成可能なため、ソーダラ
イムガラス上に直接、高硬度、高密着強度の二酸化チタ
ン膜を形成することができるため、短時間、低コストで
光触媒膜被覆部材を実現できる。When titanium dioxide is formed at high temperature on soda lime glass generally used for window glass, etc.,
It is known that Na ions in the base material diffuse into the titanium dioxide film and the catalytic activity is lost. Therefore, conventionally, an intermediate layer such as SiO 2 was formed on soda lime glass, and a titanium dioxide film was formed on the intermediate layer. In the present invention, since a titanium dioxide film can be formed at a low temperature, a titanium dioxide film having high hardness and high adhesion strength can be formed directly on soda lime glass. realizable.
【００２５】光触媒性能を向上させる目的で、二酸化チ
タンの表面にＰｔ、Ｐｄ、Ａｕ、Ａｇ、Ｒｕ、Ｒｈ、Ｆ
ｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎなどの金属あるいはこれら
の金属の酸化物を単独あるいは複数を組み合わせて担持
させても良い。特に二酸化チタンの表面にＰｔ、Ｐｄ、
Ａｕなどの貴金属の粒径１〜１００ｎｍの微粒子を担持
させたものは、光触媒性能が高いため特に望ましいこと
が知られている。二酸化チタンの表面にこれらの金属あ
るいは金属酸化物を担持させる方法としては、アークイ
オンプレーティング法以外に、含浸法、光析出法、化学
析出法、同時沈殿法、混練法、振り混ぜ法、金属粉添加
法、真空蒸着法、スパッタ法などの技術を用いることが
できる。For the purpose of improving the photocatalytic performance, Pt, Pd, Au, Ag, Ru, Rh, F
Metals such as e, Co, Ni, Cu, and Zn or oxides of these metals may be supported alone or in combination. In particular, Pt, Pd,
It is known that a carrier supporting fine particles of a noble metal such as Au having a particle diameter of 1 to 100 nm is particularly desirable because of its high photocatalytic performance. Methods for supporting these metals or metal oxides on the surface of titanium dioxide include, besides arc ion plating, impregnation, light precipitation, chemical deposition, simultaneous precipitation, kneading, shaking, metal Techniques such as a powder addition method, a vacuum evaporation method, and a sputtering method can be used.
【００２６】[0026]
【発明の実施の形態】（実施例１） 真空アーク蒸着法
を用い、以下のようにしてソーダライムガラス上に直接
二酸化チタン膜を形成した。雰囲気ガスにＡｒ＋Ｏ2、
ターゲットにＴｉを用い、全圧力を５０ｍＴｏｒｒ、全
圧力に対するＯ2分圧の割合を５０％、アーク電流を１
２０Ａで、３０分間成膜を行った。基材の加熱および基
材へのバイアスの印加は行わなかった。成膜開始３０分
後の基材の温度は５０℃であった。(Example 1) A titanium dioxide film was directly formed on soda lime glass using a vacuum arc evaporation method as follows. Ar + O 2 ,
Using Ti as the target, the total pressure was 50 mTorr, the ratio of the O 2 partial pressure to the total pressure was 50%, and the arc current was 1
Film formation was performed at 20 A for 30 minutes. The substrate was not heated and no bias was applied to the substrate. The temperature of the substrate 30 minutes after the start of film formation was 50 ° C.
【００２７】成膜後のサンプルはＸ線回折により、アナ
ターゼ型結晶構造をもつことが確認された。膜厚は２μ
ｍであり、４μｍ／ｈの高速成膜ができていることが確
認された。ビッカーズ硬度計により膜の硬度を評価した
ところ、ビッカーズ硬度１１００の高硬度膜が得られて
いることが確認された。スクラッチ試験機を用い膜の密
着強度を評価したところ、荷重７０Ｎまで膜の剥離はみ
られず、優れた密着強度を示した。The sample after film formation was confirmed by X-ray diffraction to have an anatase crystal structure. The film thickness is 2μ
m, and a high-speed film formation of 4 μm / h was confirmed. When the hardness of the film was evaluated using a Vickers hardness meter, it was confirmed that a high hardness film having a Vickers hardness of 1100 was obtained. When the adhesive strength of the film was evaluated using a scratch tester, no peeling of the film was observed up to a load of 70 N, indicating excellent adhesive strength.
【００２８】（実施例２） ポリエステルフィルム上
に、ＳｉＯ2中間層を介して二酸化チタン膜を形成し
た。まず、ポリエステルフィルム上にＲＦマグネトロン
スパッタ法を用いて、ＳｉＯ2中間層を形成した。雰囲
気ガスにＡｒ＋Ｏ2、ターゲットにＳｉを用い、全圧力
を５ｍＴｏｒｒ、全圧力に対するＯ2分圧の割合を５０
％、ＲＦ電力を２００Ｗで、基板加熱を行わずに３０分
間成膜を行った。成膜したＳｉＯ2膜はＸ線回折により
アモルファスであることが確認された。膜厚は０．１μ
ｍであった。(Example 2) A titanium dioxide film was formed on a polyester film via an intermediate layer of SiO 2 . First, an SiO 2 intermediate layer was formed on a polyester film by using an RF magnetron sputtering method. Ar + O 2 was used as the atmosphere gas and Si was used as the target. The total pressure was 5 mTorr, and the ratio of the O 2 partial pressure to the total pressure was 50.
%, An RF power of 200 W, and a film was formed for 30 minutes without heating the substrate. X-ray diffraction confirmed that the formed SiO 2 film was amorphous. The film thickness is 0.1μ
m.
【００２９】次にこの中間層上に真空アーク蒸着法によ
り、実施例１と同じようにして、３０分間ＴｉＯ2膜を
成膜した。成膜開始３０分後の基材の温度は５０℃であ
った。Next, a TiO 2 film was formed on this intermediate layer for 30 minutes by the vacuum arc evaporation method in the same manner as in Example 1. The temperature of the substrate 30 minutes after the start of film formation was 50 ° C.
【００３０】成膜後の二酸化チタン膜はＸ線回折によ
り、アナターゼ型結晶構造をもつことが確認された。二
酸化チタン膜の膜厚は２μｍであり、４μｍ／ｈの高速
成膜ができていることが確認された。同じようにしてシ
リコン基板上に作製した膜の硬度を、ビッカーズ硬度計
により評価したところ、ビッカーズ硬度１０２０の高硬
度膜が得られていることが確認された。碁盤目テープ法
により膜の密着強度を評価したところ、膜の剥離は全く
みられず、優れた密着強度を示した。The titanium dioxide film after film formation was confirmed by X-ray diffraction to have an anatase type crystal structure. The thickness of the titanium dioxide film was 2 μm, and it was confirmed that high-speed film formation of 4 μm / h was achieved. When the hardness of the film formed on the silicon substrate in the same manner was evaluated by a Vickers hardness meter, it was confirmed that a high hardness film having a Vickers hardness of 1020 was obtained. When the adhesive strength of the film was evaluated by the cross-cut tape method, no peeling of the film was observed at all, and excellent adhesive strength was exhibited.
【００３１】[0031]
【発明の効果】以上説明したように、本発明によると耐
熱温度が４００℃以下の基材上、あるいはソーダライム
ガラス上に高硬度、高密着強度のアナターゼ型二酸化チ
タン膜を形成した光触媒膜被覆部材を低コストで実現す
ることができる。As described above, according to the present invention, a photocatalytic film coating with a high hardness and high adhesion strength anatase type titanium dioxide film formed on a substrate having a heat resistant temperature of 400 ° C. or lower or on soda lime glass. The member can be realized at low cost.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 辻岡 正憲 兵庫県伊丹市昆陽北一丁目１番１号 住友 電気工業株式会社伊丹製作所内 Ｆターム(参考） 4G059 AA11 AC30 EA04 EB03 4G069 AA03 AA08 BA04A BA04B BA14A BA14B BA48A BA48C CA01 CD10 DA06 EA08 EC22X EC22Y FA03 FB02 4K029 AA09 BA48 BD00 CA04 EA03 EA05 EA08 EA09 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Masanori Tsujioka 1-1-1, Koyokita-Kita, Itami-shi, Hyogo F-term in Itami Works, Sumitomo Electric Industries, Ltd. 4G059 AA11 AC30 EA04 EB03 4G069 AA03 AA08 BA04A BA04B BA14A BA14B BA48A BA48C CA01 CD10 DA06 EA08 EC22X EC22Y FA03 FB02 4K029 AA09 BA48 BD00 CA04 EA03 EA05 EA08 EA09
Claims (4)
触媒膜が被覆された部材であって、該基材の耐熱温度が
４００℃以下であり、該光触媒膜が真空アーク蒸着法に
より形成されたアナターゼ型結晶構造を有する二酸化チ
タンであることを特徴とする、光触媒膜被覆部材。1. A member in which a photocatalytic film is coated on a substrate directly or via an intermediate layer, wherein the heat resistant temperature of the substrate is 400 ° C. or less, and the photocatalytic film is formed by a vacuum arc vapor deposition method. A photocatalyst film-coated member, characterized in that it is titanium dioxide having an anatase-type crystal structure.
徴とする、請求項１に記載の光触媒膜被覆部材。2. The photocatalyst film-coated member according to claim 1, wherein the substrate is a polymer compound.
被覆された部材であって、該光触媒膜が真空アーク蒸着
法により形成されたアナターゼ型結晶構造を有する二酸
化チタンであることを特徴とする、光触媒膜被覆部材。3. A member in which a photocatalytic film is directly coated on soda lime glass, wherein the photocatalytic film is titanium dioxide having an anatase type crystal structure formed by a vacuum arc evaporation method. Photocatalyst film covering member.
触媒膜が被覆された部材の製造方法であって、真空アー
ク蒸着法を用い、少なくともＡｒとＯ2を含む雰囲気ガ
ス中で、該雰囲気ガスの全圧力が５〜１００ｍＴｏｒ
ｒ、該全圧力に対するＯ2分圧の割合が５〜９５％、ア
ーク電流が５５〜１５０Ａ、基材温度が０〜４００℃に
て、Ｔｉターゲットをアーク蒸発させることにより、基
材上に二酸化チタン膜を形成させることを特徴とする、
光触媒膜被覆部材の製造方法。4. A method for producing a member in which a photocatalyst film is coated on a substrate directly or via an intermediate layer, wherein the member is formed by a vacuum arc vapor deposition method in an atmosphere gas containing at least Ar and O 2. Atmospheric gas total pressure is 5-100 mTorr
r, the ratio of the O 2 partial pressure to the total pressure is 5 to 95%, the arc current is 55 to 150 A, the substrate temperature is 0 to 400 ° C., and the Ti target is arc-evaporated to form a carbon dioxide on the substrate. Characterized by forming a titanium film,
A method for producing a photocatalyst film-coated member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10272664A JP2000096212A (en) | 1998-09-28 | 1998-09-28 | Photocatalyst film coated member and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10272664A JP2000096212A (en) | 1998-09-28 | 1998-09-28 | Photocatalyst film coated member and its production |
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| Publication Number | Publication Date |
|---|---|
| JP2000096212A true JP2000096212A (en) | 2000-04-04 |
Family
ID=17517076
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10272664A Pending JP2000096212A (en) | 1998-09-28 | 1998-09-28 | Photocatalyst film coated member and its production |
Country Status (1)
| Country | Link |
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