JPS6183106A - Method of preventing contamination of surface of solid material to be brought into contact with water - Google Patents
Method of preventing contamination of surface of solid material to be brought into contact with waterInfo
- Publication number
- JPS6183106A JPS6183106A JP59204182A JP20418284A JPS6183106A JP S6183106 A JPS6183106 A JP S6183106A JP 59204182 A JP59204182 A JP 59204182A JP 20418284 A JP20418284 A JP 20418284A JP S6183106 A JPS6183106 A JP S6183106A
- Authority
- JP
- Japan
- Prior art keywords
- water
- light
- metal oxide
- solid surface
- contact
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000011109 contamination Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 24
- 239000011343 solid material Substances 0.000 title abstract 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 230000003287 optical effect Effects 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 230000001678 irradiating effect Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims description 24
- 238000010186 staining Methods 0.000 claims description 8
- 239000000356 contaminant Substances 0.000 claims description 3
- -1 platinum group metals Chemical class 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 26
- 239000011521 glass Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 241000251468 Actinopterygii Species 0.000 abstract description 5
- 238000007654 immersion Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 3
- 239000005357 flat glass Substances 0.000 abstract description 2
- 244000005700 microbiome Species 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 25
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000010453 quartz Substances 0.000 description 16
- 241000195493 Cryptophyta Species 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000195628 Chlorophyta Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 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
- XHHXXUFDXRYMQI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;titanium Chemical compound [Ti].OCCN(CCO)CCO XHHXXUFDXRYMQI-UHFFFAOYSA-N 0.000 description 1
- SYMYWDHCQHTNJC-UHFFFAOYSA-J 3-oxobutanoate;zirconium(4+) Chemical compound [Zr+4].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O.CC(=O)CC([O-])=O SYMYWDHCQHTNJC-UHFFFAOYSA-J 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は水と接触する固体表面の汚損防止方法に関する
。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for preventing fouling of solid surfaces that come into contact with water.
この発明において固体表面とは水中浸漬型ランプの保護
ガラス、魚類等の飼育用水槽覗窓、光学測定■覗窓、鑑
賞用魚類水槽、噴水、池、人工流水路、又は貯水タンク
壁内面等であって水と接触することによって汚損される
おそれのある、透明ガラス、磁器、陶器、コンクリート
、金属等の無機材料、テフロン等の有機プラスチック材
料によって作成されている表面をいう。In this invention, solid surfaces include protective glass for underwater immersion lamps, observation windows for fish tanks, optical measurement inspection windows, ornamental fish tanks, fountains, ponds, artificial channels, or the inner surface of walls of water storage tanks. Surfaces made of inorganic materials such as transparent glass, porcelain, earthenware, concrete, and metal, and organic plastic materials such as Teflon, which are likely to be contaminated by contact with water.
（従来の技術）
従来水中浸漬型ランプの保護ガラス、鑑賞用魚類水槽等
を長期間使用すると保護ガラス表面あるいは水槽内面に
微生物が繁殖し、又は有機物が付着して汚損を生じ、透
明性、透光性が失われ又美観を損うので、各種の汚損防
止方法あるいは清掃方法が提案されている。例えば特開
昭５２−６５０９７、特開昭４８−１５７０９８におい
てはガラス壁面の汚損をワイパーを用いて機械的に清掃
する方法が提案され、特開昭５８−１１２１７０におい
ては培養槽内に浸漬された光源収納容器を２重にしエア
ーリフト方式で清掃用部材を循環させることで収納容器
を清掃する方法が提案されているが一般的には定期、不
定期に人力により清掃する方法がとられている。そのほ
か、特開昭５８−１５４５０２、特開昭５８−１７７９
０４においてはピリジニウム基を有する不溶性高分子化
合物、トリ有機錫含有重合体の汚損防止剤が提案されて
おり、又硫酸鋼又は塩素を用いる生物駆除法もよく知ら
れた方法である。(Prior art) When the protective glass of a conventional underwater immersion lamp, ornamental fish tank, etc. is used for a long period of time, microorganisms grow on the surface of the protective glass or the inside of the tank, or organic matter adheres to the surface of the protective glass, causing stains and impairing transparency. Since the luminosity is lost and the aesthetic appearance is impaired, various stain prevention methods or cleaning methods have been proposed. For example, in JP-A No. 52-65097 and JP-A No. 48-157098, a method of mechanically cleaning stains on the glass wall surface using a wiper was proposed, and in JP-A No. 58-112170, a method was proposed in which a glass wall surface was immersed in a culture tank. A method has been proposed to clean the storage container by doubling the light source storage container and circulating cleaning materials using an air lift method, but in general, cleaning is done manually on a regular or irregular basis. . In addition, JP-A-58-154502, JP-A-58-1779
In 2004, an antifouling agent made of an insoluble polymer compound having a pyridinium group and a triorganotin-containing polymer was proposed, and a biological disinfection method using sulfuric acid steel or chlorine is also a well-known method.
（解決しようとする問題点）
しかしながら前述の機械的方法による場合は、ガラス面
の形状により装置の構造をかえる必要があり、また面積
が広くなると、装置を大型化しなければならないので、
形あるいは面積の制約を受ける。(Problem to be solved) However, when using the mechanical method described above, it is necessary to change the structure of the device depending on the shape of the glass surface, and if the area becomes larger, the device must be larger.
Restricted by shape or area.
清掃用部材を循環させることによって収納容器を清掃す
る方法によれば光源収納容器を２重化する必要があり、
清掃部材の浮遊による光利用の効率の低下があり、光源
の浸漬形態によって、制限を受ける。According to the method of cleaning the storage container by circulating the cleaning member, it is necessary to double the light source storage container,
The floating of the cleaning member reduces the efficiency of light utilization, and is limited by the immersion form of the light source.
薬剤を使用する方法は、薬剤による環境への影響を考え
、使用する際細心の注意が必要であり、藻類の培養用に
使用される浸漬ランプの収納容器等の防汚には使用でき
ない等の問題点がある。The method of using chemicals requires careful consideration when using them, taking into account the impact of the chemicals on the environment. There is a problem.
（問題点を解決するための手段）
本発明は、従来の欠点ならびに問題点を除去、改善する
ことのできる水と接触する固体表面の汚損防止方法を提
供することを目的とするものであり、特許請求の範囲記
載の水と接触する固体表面の汚損防止方法を提供するこ
とによって前記目的を達成することができる。すなわち
この発明は水と接触する固体表面に汚損の生ずるおそれ
のある場合、前記固体表面に光中導性を有する金属酸化
物のなかから選ばれるいずれか少くとも１種以上を含む
層を形成させ、もしくは更に前記金ｉＲ酸化物に白金族
金属のなかから這ばれるいずれか少くとも１種以上を含
む金属を担持し、
前記固体表面に可視及び／又は紫外領域の波長を含む光
を連続あるいは非連続的に照射し、前記光中導性を有す
る金属酸化物を励起させることによって、前記固体表面
への汚損物の付着を防止する水と接触する固体表面の汚
損防止方法に関する。(Means for Solving the Problems) An object of the present invention is to provide a method for preventing fouling of solid surfaces that come into contact with water, which can eliminate and improve the conventional drawbacks and problems. The above object can be achieved by providing a method for preventing fouling of a solid surface that comes into contact with water as described in the claims. That is, in the case where there is a risk of staining the solid surface that comes into contact with water, the present invention forms a layer containing at least one selected from metal oxides having optical conductivity on the solid surface. or further, the gold iR oxide supports a metal containing at least one of platinum group metals, and the solid surface is continuously or non-continuously irradiated with light containing wavelengths in the visible and/or ultraviolet region. The present invention relates to a method for preventing contamination of a solid surface that comes into contact with water, which prevents contaminants from adhering to the solid surface by continuously irradiating and exciting the metal oxide having optical conductivity.
次に本発明について詳細に説明する。Next, the present invention will be explained in detail.
水中浸漬型ランプ保護窓、鑑賞用魚飼育用水槽ガラス、
光学測定用窓ガラス、噴水等長期間水と接触する個所の
汚損防止方法として、表面に光中導性を有する金ｉＡ酸
化物のなかから選ばれるいずれか少くとも１種以上を含
む層、もしくは更に前記金属酸化物に白金族金属のなか
から選ばれるいずれか少くとも１種以上を含む金属を担
持させる。Underwater immersion type lamp protection window, aquarium glass for ornamental fish breeding,
As a method for preventing staining of areas that come into contact with water for a long period of time, such as window glasses for optical measurements and fountains, a layer containing at least one selected from gold iA oxides having optical conductivity on the surface, or Furthermore, a metal containing at least one selected from platinum group metals is supported on the metal oxide.
光中導性を有する金属酸化物としては、Ｔｉｅ、 ＋Ｚ
ｒＯ＋ ＺｎＯ、ｓｎｏ 、ｔｏ 、５ｒＴｉＯ，
＋Ｆｅ２Ｏ３１！２８
■２０５等があり、付着させる方法としては、表面に有
機金属化合物を塗布したのち焼成する方法、ＣＶＤ法、
スパッタリング法、蒸気法、粉末吹付法等を用いること
ができる。例えばＴ１０．の場合はチタン化合物（チタ
ンテドライブプロボキシド、チタンテトラブトキシド、
チタニウムアセチルアセトナート、トリエタノールアミ
ンチタニウム、チタンキレート化合物、４塩化チタン等
）を含む水又は有機溶媒の溶液に表面処理を行うものを
浸漬し、引上げ乾燥後、必要なときは更に加水分解し酸
化性ガス雰囲気下３５０〜ＷＯＯ″Ｃで焼成するか、チ
タン化合物溶液を刷子によって表面に塗布し、乾燥後、
必要なときは更に加水分解し酸化性ガス雰囲気下３５０
〜７００℃で焼成することによって表面に光中導性を有
する酸化チタン層を形成できる。又ＣＶＤ法、吹きつけ
法を用いて有機チタン化合物を加熱された表面上で分解
酸化反応を起こさせることにより酸化チタン層を形成し
てもよく、金属チタン、酸化チタンをターゲットとした
スパッタリング法により表面に酸化チタン層を形成して
もよい。前述のようにして作った金属酸化物に白金族金
属を担持させるのは常法によって行うことができる。例
えば白金の場合は塩化白金酸を付着したのち熱分解する
方法、還元剤により還元する方法、光沈着法等によって
金属酸化物に対し０．００１〜１．０ｆｔ％の白金族金
属を担持させる。Examples of metal oxides having optical conductivity include Tie, +Z
rO+ ZnO, sno, to, 5rTiO,
+Fe2O31!28 ■205, etc., and the methods for adhering include applying an organic metal compound to the surface and then firing, CVD method,
A sputtering method, a steam method, a powder spraying method, etc. can be used. For example, T10. In the case of titanium compounds (titanate drive propoxide, titanium tetrabutoxide,
The object to be surface-treated is immersed in a solution of water or an organic solvent containing titanium acetylacetonate, titanium triethanolamine, titanium chelate compound, titanium tetrachloride, etc., pulled up and dried, and then further hydrolyzed and oxidized if necessary. Either by firing at 350~WOO''C in a gas atmosphere, or by applying a titanium compound solution to the surface with a brush and drying,
If necessary, further hydrolyze and 350°C under an oxidizing gas atmosphere.
By firing at ~700°C, a titanium oxide layer having optical conductivity can be formed on the surface. Further, a titanium oxide layer may be formed by causing a decomposition oxidation reaction of an organic titanium compound on a heated surface using a CVD method or a spraying method, or by a sputtering method using metallic titanium or titanium oxide as a target. A titanium oxide layer may be formed on the surface. A platinum group metal can be supported on the metal oxide prepared as described above by a conventional method. For example, in the case of platinum, 0.001 to 1.0 ft % of platinum group metal is supported on the metal oxide by applying chloroplatinic acid and then thermally decomposing it, reducing it with a reducing agent, photodeposition method, or the like.
前述の如き方法で表面を処理された場合は、その物体が
水中において長時間使用されるとき、金属酸化物が光励
起される可視及び／又は紫外領域の波長の光を連続的に
又は非連続的に金４酸化物層に照射し、同時に必要な場
合は空気を水中に泡出させることによって、表面での微
生物繁殖と、有機物付着による汚損を防止できる。従っ
てガラス窓を使用しても透明度は失われないので、水中
ランプにガラス窓を使用するとき水中ランプからの光は
長期間使用しても、表面汚損によって減衰することもな
く、噴水等の表面が汚損により美観をそこねることもな
い。また透明な石英板、ガラス板等有効な光を透過する
材料表面に金属酸化物層を形成させた場合には、光照射
は金属酸化物を付着させた側からでも、反対の材料側か
らでもよい。If the surface has been treated in the manner described above, when the object is used in water for a long time, the metal oxide will be exposed to light in the visible and/or ultraviolet wavelength range, either continuously or discontinuously, to photoexcite it. By irradiating the gold tetraoxide layer and at the same time bubbling air into the water if necessary, it is possible to prevent microbial growth on the surface and contamination due to organic matter adhesion. Therefore, even if a glass window is used, transparency will not be lost, so when using a glass window for an underwater lamp, the light from the underwater lamp will not be attenuated by surface contamination even if used for a long period of time, and it can be used on surfaces such as fountains. However, it does not lose its beauty due to stains. In addition, when a metal oxide layer is formed on the surface of a material that transmits effective light, such as a transparent quartz plate or glass plate, the light can be irradiated either from the side on which the metal oxide is attached or from the opposite side of the material. good.
（作用）
表面で微生物繁殖と、有機物付着による汚損が防止でき
る詳しい作用機構は不明であるが、光半導体である金属
酸化物に光エネルギーが吸収され、光半導体中の電子が
励起されることにより始まる光電気化学的作用によって
汚損が防止されると推考される。(Action) The detailed mechanism of action that prevents microbial growth and contamination due to organic matter adhesion on the surface is unknown, but light energy is absorbed by the metal oxide, which is a photosemiconductor, and electrons in the photosemiconductor are excited. It is assumed that fouling is prevented by the photoelectrochemical action that begins.
更に本発明を実施例について詳しく説明する。Further, the present invention will be explained in detail with reference to examples.
実施例１
透明石英ガラス試験片（ｚａｘ７ａｃｍ）の片面に白金
を担持させた酸化チタン層を形成した試料を用いて微生
物汚損試験を行なった。Example 1 A microbial staining test was conducted using a sample in which a titanium oxide layer supporting platinum was formed on one side of a transparent quartz glass test piece (zax7acm).
試料：イソプロピルアルコー／Ｉ／１００部にチタンテ
トライソプロポキシド５部、酢酸１０部を混合した溶液
に片面をビニールテープで覆った石英ガラス板を浸漬し
、引上げ速度２０ ｃｍ ／ ｍｉｎで引上げ、１１０
℃の乾燥話中で１時間乾燥した後、空気雰囲気下、４８
０℃で１時間電気炉中で焼成することで、石英ガラス板
表面に透明な酸化チタン層を形成した。さらにこの試料
を塩化白金酸／エタノール溶液（５０ｐｐｍ Ｉ）ｔ
）に浸漬し、引上げ後１２００″Ｃで熱分解することで
白金を担持した酸化チタン層を表面にもつ石英ガラス板
試料を得た。Sample: A quartz glass plate covered with vinyl tape on one side was immersed in a solution of 100 parts of isopropyl alcohol/I, 5 parts of titanium tetraisopropoxide, and 10 parts of acetic acid, and pulled up at a pulling speed of 20 cm/min.
After drying for 1 hour at 48°C in an air atmosphere,
By firing in an electric furnace at 0° C. for 1 hour, a transparent titanium oxide layer was formed on the surface of the quartz glass plate. Furthermore, this sample was added to a chloroplatinic acid/ethanol solution (50 ppm I).
), and after being pulled up and thermally decomposed at 1200''C, a quartz glass plate sample having a titanium oxide layer supporting platinum on its surface was obtained.
試験方法：第１図に示す如き装置によって試験を行った
。同図において容器本体１の上部にカバー２が載置され
、カバー２に試料４を気密に張り付ける窓ａが設けられ
ている。窓３上に、試験片４として酸化チタン層を形成
し白金を担持させた石英板試験片と、比較対照試料とし
て未処理の石英板が張り付けである。本体１中には水５
が充されており、試験片４と水５とが試験面で接触する
ようになっている。水５中には空気がバイブロを通して
吹き込めるようになっている。上記の装置でバイブロよ
り空気を通しながら野外で約１ケ月間太陽光線が照射さ
れる条件下で、人工光線を使用しないで放置した。Test method: The test was conducted using an apparatus as shown in FIG. In the figure, a cover 2 is placed on top of a container body 1, and a window a is provided in the cover 2 to allow a sample 4 to be pasted in an airtight manner. A quartz plate test piece on which a titanium oxide layer was formed and platinum was supported as a test piece 4 and an untreated quartz plate were pasted on the window 3 as a comparison sample. There is water 5 in the main body 1.
The test piece 4 and water 5 are brought into contact with each other on the test surface. Air can be blown into the water 5 through a vibro. With the above device, air was passed through the vibro, and the specimens were left outdoors under conditions of sunlight irradiation for about one month without using artificial light.
結果：試験結果が第２図Ａ、Ｂに示され′Ｃいる。Results: The test results are shown in Figures 2A and B.
第２図Ａは未処理石英板を３４日間放置したときの透過
率変化であって、第２図Ｂは表面に酸化チタン層を付着
させた石英板を３４日間放置したときの透過率の変化で
ある。いずれの図においても縦軸に透過率、横軸に波長
が示され、実線で試験前、破線で試験後の透過率が示し
である。図において明かなように、対照として用いた未
処理石英板では全体に藻が付着して、透明度がなくなり
、透過率が著しく低下しているのに反し、表面を白金を
担持した酸化チタンで処理した石英板では藻の付着が認
められず、透過率も変化しなかった。Figure 2A shows the change in transmittance when an untreated quartz plate is left for 34 days, and Figure 2B shows the change in transmittance when a quartz plate with a titanium oxide layer attached to its surface is left for 34 days. It is. In both figures, the vertical axis shows the transmittance and the horizontal axis shows the wavelength, the solid line shows the transmittance before the test, and the broken line shows the transmittance after the test. As is clear from the figure, the untreated quartz plate used as a control has algae attached to the entire surface, loses its transparency, and has a significant drop in transmittance, whereas the surface is treated with platinum-supported titanium oxide. No algae was observed on the quartz plate, and the transmittance did not change.
実施例２
実施例１と同様な方法で作成した、表面に白金を担持し
た酸化チタン層を有する石英板試料を用いて、下記に示
す試験方法により表面の汚損試験を行った。Example 2 Using a quartz plate sample prepared in the same manner as in Example 1 and having a titanium oxide layer carrying platinum on its surface, a surface staining test was conducted according to the test method shown below.
試験方法：第８図に示す如き装置によって試験を行なっ
た。同図に示されるように、容器本体１の内壁面には白
金を担持した酸化チタン層をつけた石英板と比鮫用未処
理石英板の試験片４をとりつけたアクリル板８が徨り付
けられ試験片４が覆われる程度に藻類培養液５が満たさ
れている。藻類培望液５はバイブ４を通して空気を通さ
れる。上記の装置でパイプ４より空気を通しながら野外
で約１ケ月間太陽光線が培譬液５を逸して照射される条
件下で、人工光線を使用しないで放置した。Test method: The test was conducted using an apparatus as shown in FIG. As shown in the figure, an acrylic plate 8 on which a test piece 4 of a quartz plate with a titanium oxide layer supporting platinum and an untreated quartz plate for Japanese sharks is attached is attached to the inner wall surface of the container body 1. The algae culture solution 5 is filled to such an extent that the test piece 4 is covered. Air is passed through the algae culture solution 5 through the vibrator 4. With the above device, the culture solution 5 was allowed to pass through air through the pipe 4 outdoors for about one month under conditions in which sunlight was irradiated through the culture solution 5 without using artificial light.
試験結果；試験結果が第４１ｆｆｌＡ 、 Ｂに示され
ている。第４図Ａは未処理石英板を１８日間放置したと
きの透過率変化であって、第４図Ｂは表面に酸化チタン
層を付着させた石英板を１８日間放置したときの透過率
変化である。図の様式は実施例１と同様であるので説明
を省略する。同図において明らかな様に未処理石英板で
は全体に藻が付着して透明度がなくなり、透過率が著し
く低下しているのに反し、表面を白金を担持した酸化チ
′タンで処理した石英板では藻の付着はわずかに認めら
れる程度であった。Test results: The test results are shown in sections 41fflA and B. Figure 4A shows the change in transmittance when an untreated quartz plate is left for 18 days, and Figure 4B shows the change in transmittance when a quartz plate with a titanium oxide layer attached to its surface is left for 18 days. be. The format of the diagram is the same as that of Example 1, so the explanation will be omitted. As is clear from the figure, the untreated quartz plate has algae attached to the entire surface and loses its transparency, resulting in a significant drop in transmittance, whereas the quartz plate whose surface has been treated with titanium oxide carrying platinum However, only a slight amount of algae was observed.
実施例３
実施例１と同じ試験を室内で太陽光線のかわりにＩＯＷ
ブラックランプを光源とする光を照射することで行なっ
た。１ケ月間経たのち、試料を肉眼視察した結果、未処
理石英板は全体に緑藻が付着し、透明性が失なわれたが
白金を担持した酸化チタン層を有する石英板では、わず
かに藻の付着が認められる程度であり、透明性の変化が
認められなかった。Example 3 The same test as Example 1 was performed indoors using IOW instead of sunlight.
This was done by irradiating light from a black lamp as a light source. After one month, we visually inspected the samples and found that the untreated quartz plate had green algae all over it and lost its transparency, but the quartz plate with the platinum-supported titanium oxide layer showed only a slight amount of algae. Adhesion was only observed, and no change in transparency was observed.
実施例４
５ Ｘ ５ Ｘ Ｇ、５ ｃｍのタイルを実施例１と同
様に処理し、表面に光半導性を有する酸化チタン層を形
成した。ついで硝酸パテジウム水溶液に浸漬したのち、
還元剤としてアスコルビン酸を加え加温処理を行なって
表面にパラジウムを担持した酸化チタン層を持つタイル
を得た。このタイルを第５図に示す試験装置で試験を行
なった。同図で示されるように、容器本体１の内壁面に
白金を担持した酸化チタン層を付けたタイルと比較用未
処理タイルの試験片４を張り付け、ポンプ３によって容
器内に水が汲み込まれ、左端から溢れ出るようになって
いる。表面の汚損状況を野外で水を通して太陽光線を試
験片に照射し、約１ケ月間放置後、観察した。その結果
、未処理タイル表面には緑藻が全体的に付着したのに対
し、酸化チタン層を付けたタイル表面には藻の付層が認
められなかった。Example 4 A 5 x 5 x G, 5 cm tile was treated in the same manner as in Example 1 to form a titanium oxide layer having optical semiconductivity on the surface. Then, after immersing it in an aqueous solution of Patedium Nitrate,
Ascorbic acid was added as a reducing agent and a heating treatment was performed to obtain a tile with a titanium oxide layer carrying palladium on the surface. This tile was tested using the testing apparatus shown in FIG. As shown in the figure, a test specimen 4 of a tile with a titanium oxide layer supporting platinum and a comparative untreated tile was pasted on the inner wall surface of a container body 1, and water was pumped into the container by a pump 3. , overflowing from the left edge. The surface staining condition was observed by irradiating the test piece with sunlight through water in the field and leaving it for about one month. As a result, green algae were found to be completely attached to the surface of the untreated tiles, whereas no layer of algae was observed on the surface of the tiles coated with the titanium oxide layer.
実施例５
実施例４と同様の実験を白金を担持した酸化ジルコニウ
ム層を表面にもつタイル板について行なった。酸化ジル
コニウム層の形成はジルコニウムアセチルアセテート・
ベンゼン・石油エーテル・アルコール溶液を用いての熱
分解法により行なった。Example 5 An experiment similar to Example 4 was conducted on a tile board having a zirconium oxide layer supporting platinum on its surface. The zirconium oxide layer is formed using zirconium acetylacetate.
This was carried out by a thermal decomposition method using a benzene/petroleum ether/alcohol solution.
その結表、未処理タイル表面は１ケ月後全体が藻で覆わ
れたのに対し、酸化ジルコニウム層が形成されているタ
イル表面には、わずかに藻の付着実施例６
実施例４と同様の実験をタイル板上にスパッタリング法
で酸化チタン層を形成せしめた試料について行った。As a result, the untreated tile surface was completely covered with algae after one month, whereas the tile surface with the zirconium oxide layer had a slight amount of algae adhering to it. Experiments were conducted on a sample in which a titanium oxide layer was formed on a tile board by sputtering.
その結果、未処理タイル表面は１ケ月後全体が藻で覆わ
れたのに対し、酸化チタン層が形成されているタイル表
面は藻の付着量は僅少であった。As a result, the entire untreated tile surface was covered with algae after one month, while the amount of algae adhering to the tile surface on which the titanium oxide layer had been formed was small.
実施例７
実施例鴫と同様の実験をタイル板上に実施例１と同様な
方法で酸化チタン層を形成後、鉄塩溶液に浸漬、酸化雰
囲気中で加熱することにより酸化チタン、酸化鉄層を形
成させ、更に白金を０．００１ｗｔ％担持させた試料に
ついて行なった。Example 7 A titanium oxide layer was formed on a tile board in the same manner as in Example 1, and then a titanium oxide and iron oxide layer were formed by immersing it in an iron salt solution and heating it in an oxidizing atmosphere. The test was conducted on a sample in which 0.001 wt% of platinum was supported.
その結果処理タイル表面は１ケ月後全体が藻で覆われた
のに対し、表面に酸化チタン、酸化鉄層を形成させ、更
に白金を担持させた試料では藻の付着は殆んど認められ
なかった。As a result, the entire treated tile surface was covered with algae after one month, whereas on the sample where titanium oxide and iron oxide layers were formed on the surface and platinum was further supported, almost no algae was observed. Ta.
（発明の効果）
前述の如く水と接触する固体表面に汚損が生じ透明性、
透光性および美観を失うおそれのある場合、又汚損によ
って衛生上の問題が生ずるとき、前記水と接触している
固体表面に光半導性を有する金属酸化物のなかから選ば
れるいずれか少くとも１種以上を含む層を形成させ、も
しくは更に前記金属酸化物に白金族金屑のなかから選ば
れるいずれか少くとも１種以上を含む金属を担持し、前
記固体表面に可視及び／又は紫外領域の波長を含む光を
照射することにより、固体表面は長時間水と接触してい
ても汚損することがない。従って従来性なわれていたよ
うな定期、非定期の人力による非能率な清掃作業や、機
械的な大がかりな清浄装置が不必要となり、又汚損する
対象物に凹凸があって、清掃作業に困難性がある場合に
も適用でき、形状に左右されない利点がある。又薬品等
を使用しないので環境に悪影響を及ぼすこともないので
極めて有効な汚損防止方法であり、美観上、衛生上の効
果は極めて大きい。(Effect of the invention) As mentioned above, staining occurs on the solid surface that comes into contact with water, reducing transparency and
When there is a risk of loss of translucency and aesthetic appearance, or when hygiene problems arise due to contamination, the least of the metal oxides selected from metal oxides having optical semiconductivity on the solid surface in contact with water. or the metal oxide further supports a metal containing at least one selected from platinum group metal scraps, and the solid surface is coated with visible and/or ultraviolet rays. By irradiating the solid surface with light containing wavelengths in this range, the solid surface will not become contaminated even if it is in contact with water for a long time. This eliminates the need for inefficient regular and non-regular manual cleaning operations and large-scale mechanical cleaning equipment, which were conventionally used, and also makes cleaning difficult due to the unevenness of objects to be soiled. It has the advantage that it can be applied even when there is a certain shape, and it is not affected by the shape. Furthermore, since no chemicals are used, there is no adverse effect on the environment, so it is an extremely effective method for preventing stains, and has extremely large aesthetic and hygienic effects.
第１図、第３図は本発明の試験装置、第２図、第４図は
本発明の効果を示す透過率変化図、第５図は本発明の試
験装置の他の一例を示している。
ｌ・・・容器、２・・・カバー、３・・・試験用窓、４
・・・試験片、５・・・水または培養液、６・・・空気
パイプ、７・・・ポンプ、８・・・試料装置用アクリル
板。FIGS. 1 and 3 show the test device of the present invention, FIGS. 2 and 4 show transmittance change diagrams showing the effects of the present invention, and FIG. 5 shows another example of the test device of the present invention. . l... Container, 2... Cover, 3... Test window, 4
...Test piece, 5.Water or culture solution, 6.Air pipe, 7.Pump, 8.Acrylic plate for sample device.
Claims (1)
場合において： 前記固体表面に光半導性を有する金属酸化 物のなかから選ばれるいずれか少くとも１種以上を含む
層を形成し； 前記固体表面に可視及び／又は紫外領域の 波長を含む光を照射し、前記光半導性を有する金属酸化
物を光励起させることによつて；前記固体表面への汚損
物の付着を防止する ことを特徴とする水と接触する固体表面の汚損防止方法
。 ２、水と接触する固体表面に汚損の生ずるおそれのある
場合において； 前記固体表面に光半導性を有する金属酸化 物のなかから選ばれるいずれか少くとも１種以上を含む
層を形成し、更に前記金属酸化物に白金族金属のなかか
ら選ばれるいずれか少くとも１種以上を含む金属を担持
し； 前記固体表面に可視及び／又は紫外領域の 波長を含む光を照射し、前記光半導性を有する金属酸化
物を光励起させることによつて；前記固体表面への汚損
物の付着を防止する ことを特徴とする水と接触する固体表面の汚損防止方法
。[Claims] L: In the case where there is a risk of staining the solid surface that comes into contact with water: The solid surface contains at least one selected from metal oxides having optical semiconductivity. forming a layer; irradiating the solid surface with light containing wavelengths in the visible and/or ultraviolet region to optically excite the metal oxide having optical semiconductivity; removing contaminants from the solid surface; A method for preventing fouling of solid surfaces that come into contact with water, characterized by preventing adhesion. 2. In cases where there is a risk of staining the solid surface that comes into contact with water; forming a layer containing at least one selected from metal oxides having optical semiconductivity on the solid surface; Further, the metal oxide supports a metal containing at least one selected from platinum group metals; the solid surface is irradiated with light having a wavelength in the visible and/or ultraviolet region, and the light half is A method for preventing contamination of a solid surface that comes into contact with water, the method comprising: preventing contaminants from adhering to the solid surface by optically exciting a conductive metal oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59204182A JPS6183106A (en) | 1984-10-01 | 1984-10-01 | Method of preventing contamination of surface of solid material to be brought into contact with water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59204182A JPS6183106A (en) | 1984-10-01 | 1984-10-01 | Method of preventing contamination of surface of solid material to be brought into contact with water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6183106A true JPS6183106A (en) | 1986-04-26 |
| JPS621922B2 JPS621922B2 (en) | 1987-01-16 |
Family
ID=16486193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59204182A Granted JPS6183106A (en) | 1984-10-01 | 1984-10-01 | Method of preventing contamination of surface of solid material to be brought into contact with water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6183106A (en) |
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| JPH09291232A (en) * | 1996-04-24 | 1997-11-11 | Suzuki Sogyo Co Ltd | Material for preventing adhesion of aquatic organism |
| WO1998041589A1 (en) * | 1997-03-14 | 1998-09-24 | Matsushita Electric Works, Ltd. | Antifouling silicone emulsion coating composition, process for producing the same and antifouling article coated therewith |
| WO1998055573A1 (en) * | 1997-06-04 | 1998-12-10 | Toto Ltd. | Method for surface pretreatment before formation of photocatalytic hydrophilic film, and detergent and undercoat composition for use in the same |
| US6090489A (en) * | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
| US6165256A (en) * | 1996-07-19 | 2000-12-26 | Toto Ltd. | Photocatalytically hydrophilifiable coating composition |
| JP2001121643A (en) * | 2000-08-17 | 2001-05-08 | Toto Ltd | Antistaining member |
| US6303229B2 (en) | 1998-04-10 | 2001-10-16 | Matsushita Electric Works, Ltd. | Hydrophilic inorganic coating film and composition made from alkoxysilane and silica |
| US6337129B1 (en) | 1997-06-02 | 2002-01-08 | Toto Ltd. | Antifouling member and antifouling coating composition |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| US6939611B2 (en) | 1994-10-31 | 2005-09-06 | Kanagawa Academy Of Science And Technology | Window glass employing titanium dioxide photocatalyst |
| US11584127B2 (en) | 2020-07-31 | 2023-02-21 | Canon Kabushiki Kaisha | Liquid ejection head and method for manufacturing the same |
-
1984
- 1984-10-01 JP JP59204182A patent/JPS6183106A/en active Granted
Cited By (36)
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| JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
| JPH05155726A (en) * | 1991-12-06 | 1993-06-22 | Agency Of Ind Science & Technol | Material for preventing proliferation of saprophytic bacteria |
| JPH07163887A (en) * | 1993-12-15 | 1995-06-27 | Nikon Corp | Fungicidal method of matter and matter protected from fungi |
| JPH0867835A (en) * | 1994-08-31 | 1996-03-12 | Matsushita Electric Works Ltd | Antimicrobial inorganic coating |
| WO1996013327A1 (en) * | 1994-10-31 | 1996-05-09 | Kanagawa Academy Of Science And Technology | Titanium oxide photocatalyst structure and method of manufacturing the same |
| US6939611B2 (en) | 1994-10-31 | 2005-09-06 | Kanagawa Academy Of Science And Technology | Window glass employing titanium dioxide photocatalyst |
| US7157840B2 (en) | 1994-10-31 | 2007-01-02 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| US7327074B2 (en) | 1994-10-31 | 2008-02-05 | Kanagawa Academy Of Science And Technology | Illuminating devices employing titanium dioxide photocatalysts |
| WO1996029375A1 (en) * | 1995-03-20 | 1996-09-26 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
| EP1712531A2 (en) * | 1995-03-20 | 2006-10-18 | Toto Ltd. | Use of material having ultrahydrohilic and photocatalytic surface |
| EP1712531A3 (en) * | 1995-03-20 | 2010-08-18 | Toto Ltd. | Use of material having ultrahydrohilic and photocatalytic surface |
| DE19681289C5 (en) * | 1995-03-20 | 2010-08-05 | Toto Ltd., Kita-Kyushu | Use of a composite material as a material, from the surface of adhering deposits are washed off by contact with rain |
| DE19681289B8 (en) * | 1995-03-20 | 2010-06-10 | Toto Ltd., Kita-Kyushu | Use of a composite material as a material, from the surface of adhering deposits are washed off by contact with rain |
| JP2009167097A (en) * | 1995-03-20 | 2009-07-30 | Toto Ltd | Photocatalytic member |
| US6013372A (en) * | 1995-03-20 | 2000-01-11 | Toto, Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with superhydrophilic photocatalytic surface, and method of making thereof |
| KR100342150B1 (en) * | 1995-03-20 | 2002-10-25 | 도토기키 가부시키가이샤 | A method of making the surface of a base material become superhydrophilic by photocatalyst, a base material having a superhydrophilic photocatalytic surface and a method of manufacturing the same |
| US6830785B1 (en) | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| EP1712530A2 (en) * | 1995-03-20 | 2006-10-18 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
| EP1712530A3 (en) * | 1995-03-20 | 2010-08-18 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
| CN1129659C (en) * | 1995-03-20 | 2003-12-03 | 东陶机器株式会社 | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydraphilic and photocatalytic surface, and process for producing said material |
| JPH08267646A (en) * | 1995-03-30 | 1996-10-15 | Toto Ltd | Stainproof member |
| JPH08309202A (en) * | 1995-05-22 | 1996-11-26 | Bridgestone Corp | Photocatalytic body |
| JPH0975841A (en) * | 1995-07-08 | 1997-03-25 | Toto Ltd | Method for water film formation with design material having ultrahigh hydrophilicity |
| JPH0977574A (en) * | 1995-07-08 | 1997-03-25 | Toto Ltd | Concrete structure |
| US6090489A (en) * | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
| JPH09228320A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Self-cleaning handrail, and method of cleaning handrail |
| US6524664B1 (en) | 1996-03-21 | 2003-02-25 | Toto Ltd. | Photocatalytically hydrophilifying and hydrophobifying material |
| JPH09291232A (en) * | 1996-04-24 | 1997-11-11 | Suzuki Sogyo Co Ltd | Material for preventing adhesion of aquatic organism |
| US6165256A (en) * | 1996-07-19 | 2000-12-26 | Toto Ltd. | Photocatalytically hydrophilifiable coating composition |
| US6221498B1 (en) | 1997-03-14 | 2001-04-24 | Matsushita Electric Works, Ltd. | Antifouling silicone emulsion coating-composition, process for producing the same and antifouling article coated therewith |
| WO1998041589A1 (en) * | 1997-03-14 | 1998-09-24 | Matsushita Electric Works, Ltd. | Antifouling silicone emulsion coating composition, process for producing the same and antifouling article coated therewith |
| US6337129B1 (en) | 1997-06-02 | 2002-01-08 | Toto Ltd. | Antifouling member and antifouling coating composition |
| WO1998055573A1 (en) * | 1997-06-04 | 1998-12-10 | Toto Ltd. | Method for surface pretreatment before formation of photocatalytic hydrophilic film, and detergent and undercoat composition for use in the same |
| US6303229B2 (en) | 1998-04-10 | 2001-10-16 | Matsushita Electric Works, Ltd. | Hydrophilic inorganic coating film and composition made from alkoxysilane and silica |
| JP2001121643A (en) * | 2000-08-17 | 2001-05-08 | Toto Ltd | Antistaining member |
| US11584127B2 (en) | 2020-07-31 | 2023-02-21 | Canon Kabushiki Kaisha | Liquid ejection head and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS621922B2 (en) | 1987-01-16 |
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