JP2002302646A - Sound insulating wall and method for washing sound insulating wall - Google Patents

Sound insulating wall and method for washing sound insulating wall

Info

Publication number
JP2002302646A
JP2002302646A JP2002020533A JP2002020533A JP2002302646A JP 2002302646 A JP2002302646 A JP 2002302646A JP 2002020533 A JP2002020533 A JP 2002020533A JP 2002020533 A JP2002020533 A JP 2002020533A JP 2002302646 A JP2002302646 A JP 2002302646A
Authority
JP
Japan
Prior art keywords
coating
monovalent organic
functional group
formula
organic groups
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
Application number
JP2002020533A
Other languages
Japanese (ja)
Other versions
JP3882625B2 (en
Inventor
Makoto Hayakawa
信 早川
Mitsuhide Shimobukikoshi
光秀 下吹越
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toto Ltd
Original Assignee
Toto Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP2002020533A priority Critical patent/JP3882625B2/en
Publication of JP2002302646A publication Critical patent/JP2002302646A/en
Application granted granted Critical
Publication of JP3882625B2 publication Critical patent/JP3882625B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24HEATING; RANGES; VENTILATING
    • F24FAIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/20Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
    • F24F8/22Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00Coatings; Surface treatments
    • F28F2245/02Coatings; Surface treatments hydrophilic

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic coating composition which has excellent long-term storage stability and can render the surface of a member highly hydrophilic, and simultaneously, retains the hydrophilicity. SOLUTION: The photocatalytic hydrophilic coating composition comprises titanium oxide particles whose surfaces have been coated with (a) a film-forming element composed of a siloxane to be represented by the average composition formula: RpSiXqO(4-p-q)/2 (wherein R is a functional group composed of one or more monovalent organic groups or a functional group composed of two or more kinds selected from between a monovalent organic group and hydrogen; X is an alkoxy group or a halogen atom; 0<p<2; and 0<q<4) and forming a silicone resin when cured and (b) a partially hydrolyzable silane derivative to be presented by the formula: RpSiX4-p (wherein R and X are the same as defined for (a); and p is 1 or 2).

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、部材表面を高度の
親水性になし、かつ維持することの可能な塗膜を形成す
るための親水性コ−ティング組成物に関する。より詳し
くは、本発明は、鏡、ガラス、レンズ、プリズムその他
の透明部材の表面を高度に親水化することにより、部材
の曇りや水滴形成を防止することの可能な塗膜を形成す
るための防曇性コ−ティング組成物に関する。本発明
は、また、建物や窓ガラスや機械装置や物品の表面を高
度に親水化することにより、表面が汚れるのを防止し、
又は表面を水を用いて清浄化することの可能な塗膜を形
成するための易清浄性コ−ティング組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic coating composition for forming a coating film capable of making and maintaining the surface of a member highly hydrophilic. More specifically, the present invention provides a highly hydrophilic surface of a mirror, glass, lens, prism or other transparent member to form a coating film capable of preventing clouding and water droplet formation of the member. The present invention relates to an antifogging coating composition. The present invention also prevents the surface from being stained by highly hydrophilizing the surface of a building, a window glass, a mechanical device or an article,
Alternatively, the present invention relates to an easy-cleaning coating composition for forming a coating film whose surface can be cleaned using water.

【0002】[0002]

【従来の技術】寒冷時に自動車その他の乗物の風防ガラ
スや窓ガラス、建物の窓ガラス、眼鏡のレンズ、及び各
種計器盤のカバ−ガラスが凝縮湿分で曇るのはしばしば
経験されることである。また、浴室や洗面所の鏡や眼鏡
のレンズが湯気で曇ることも良く遭遇される。物品の表
面に曇りが生じるのは、表面が雰囲気の露点以下の温度
に置かれると雰囲気中の湿分が凝縮して表面に結露し、
水滴状に成長するからである。凝縮水滴が充分に細か
く、それらの直径が可視光の波長の1/2程度であれ
ば、水滴は光を散乱し、ガラスや鏡は見掛け上不透明と
なり、やはり可視性が失われる。湿分の凝縮が更に進行
し、細かい凝縮水滴が互いに融合してより大きな離散し
た水滴に成長すれば、水滴と表面との界面並びに水滴と
空気との界面における光の屈折により、それらの表面は
翳り、ぼやけ、斑模様になり、或いは曇る。その結果、
ガラスのような透明物品では透視像が歪んで透視性が低
下し、鏡では反射像が乱される。更に、車両の風防ガラ
スや窓ガラス、建物の窓ガラス、車両のバックミラ−、
眼鏡のレンズ、マスクやヘルメットのシ−ルドが降雨や
水しぶきを受け、離散した多数の水滴が表面に付着する
と、それらの表面は翳り、ぼやけ、斑模様になり、或い
は曇り、やはり可視性が失われる。ここで用いる“防
曇”の用語は、このような曇りや凝縮水滴の成長や水滴
の付着による光学的障害を防止する技術を広く意味す
る。言うまでもなく、上記“曇り”は安全性や種々の作
業の能率に深い影響を与える。例えば、車両の風防ガラ
スや窓ガラス、車両のバックミラ−が、寒冷時や雨天に
翳り或いは曇ると、視界の確保が困難となり、交通の安
全性が損われる。内視鏡レンズやデンタルミラ−、歯科
用レ−ザ−治療器の集束レンズが曇ると、的確な診断、
手術、処置の障害となる。計器盤のカバ−ガラスが曇る
とデ−タの読みが困難となる。
BACKGROUND OF THE INVENTION It is often experienced that in cold weather, windshields and glazings of automobiles and other vehicles, glazings of buildings, lenses of eyeglasses, and cover glass of various instrument panels are fogged by condensed moisture. . In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. The fogging on the surface of the article is that if the surface is placed at a temperature below the dew point of the atmosphere, the moisture in the atmosphere will condense and condense on the surface,
This is because they grow like water drops. If the condensed water droplets are sufficiently fine and their diameter is about half the wavelength of visible light, the water droplets will scatter light and the glass or mirror will be apparently opaque, again losing visibility. If the condensation of moisture progresses further and the fine condensed water droplets fuse together and grow into larger discrete water droplets, their surfaces will be refracted by the refraction of light at the water droplet-surface interface and the water droplet-air interface. Dark, blurred, mottled or cloudy. as a result,
In a transparent article such as glass, the perspective image is distorted and the transparency is reduced, and the reflected image is disturbed by a mirror. Furthermore, windshields and window glasses of vehicles, window glasses of buildings, back mirrors of vehicles,
If eyeglass lenses, masks, or helmet shields are subjected to rainfall or splashes, and a large number of discrete water droplets adhere to the surface, those surfaces may become dark, blurred, mottled, or cloudy, and still lose visibility. Will be As used herein, the term "anti-fog" broadly refers to a technique for preventing optical hindrance due to such fogging, growth of condensed water droplets, and adhesion of water droplets. Needless to say, the above "clouding" has a profound effect on safety and efficiency of various operations. For example, if the windshield or window glass of the vehicle or the back mirror of the vehicle is shaded or clouded in cold weather or rainy weather, it is difficult to secure a view, and traffic safety is impaired. If the focusing lens of the endoscope lens, dental mirror, or dental laser treatment device becomes cloudy, accurate diagnosis,
It will hinder surgery and treatment. If the cover glass of the instrument panel becomes fogged, it becomes difficult to read the data.

【0003】他方、建築及び塗料の分野においては、環
境汚染に伴い、建築外装材料や屋外建造物やその塗膜の
汚れが問題となっている。大気中に浮遊する煤塵や粒子
は晴天には建物の屋根や外壁に堆積する。堆積物は降雨
に伴い雨水により流され、建物の外壁を流下する。更
に、雨天には浮遊煤塵は雨によって持ち運ばれ、建物の
外壁や屋外建造物の表面を流下する。その結果、表面に
は、雨水の道筋に沿って汚染物質が付着する。表面が乾
燥すると、表面には縞状の汚れが現れる。建築外装材料
や塗膜の汚れは、カ−ボンブラックのような燃焼生成物
や、都市煤塵や粘土粒子のような無機質物質の汚染物質
からなる。このような汚染物質の多様性が防汚対策を複
雑にしているものと考えられる(橘高義典著“外壁仕上
材料の汚染の促進試験方法”、日本建築学会構造系論文
報告集、第404号、1989年10月、p.15−2
4)。従来の通念では、上記建築外装などの汚れを防止
するためにはポリテトラフルオロエチレン(PTFE)
のような撥水性の塗料が好ましいと考えられていたが、
最近では、疎水性成分を多く含む都市煤塵に対しては、
塗膜の表面を出来るだけ親水性にするのがよいと考えら
れている(高分子、44巻、1995年5月号、p.3
07)。そこで、親水性のグラフトポリマ−で建物を塗
装することが提案されている(新聞“化学工業日報”、
1995年1月30日)。報告によれば、この塗膜は水
との接触角に換算して30〜40゜の親水性を呈する。
しかしながら、粘土鉱物で代表される無機質塵埃の水と
の接触角は20゜から50゜であり、水との接触角が3
0〜40゜のグラフトポリマ−に対して親和性を有し、
その表面に付着しやすいので、このグラフトポリマ−の
塗膜は無機質塵埃による汚れを防止することができない
と考えられる。
On the other hand, in the field of construction and paints, stains on building exterior materials, outdoor buildings and their coatings have become a problem with environmental pollution. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface. Soil on building exterior materials and coatings consists of combustion products such as carbon black and inorganic contaminants such as urban dust and clay particles. It is considered that the diversity of such contaminants complicates antifouling measures (Yoshinori Tachibana, "Method of Accelerated Testing of Contamination of Exterior Wall Finishing Materials", Journal of Architectural Institute of Japan, Structural Transactions, No. 404, October 1989, pp. 15-2
4). According to conventional wisdom, polytetrafluoroethylene (PTFE) is used to prevent the above-mentioned dirt on the building exterior.
Although water-repellent paint such as was considered preferable,
Recently, for urban dust containing many hydrophobic components,
It is considered that the surface of the coating film should be made as hydrophilic as possible (Polymer, vol. 44, May 1995, p. 3).
07). Therefore, it has been proposed to paint a building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily",
Jan. 30, 1995). According to reports, this coating exhibits a hydrophilicity of 30 to 40 ° in contact angle with water.
However, the contact angle of inorganic dust represented by clay minerals with water is 20 ° to 50 °, and the contact angle with water is 3 °.
Having an affinity for a graft polymer of 0 to 40 °;
It is considered that the coating of the graft polymer cannot prevent contamination by inorganic dust because it easily adheres to the surface.

【0004】[0004]

【発明が解決しようとする課題】本発明の目的は、部材
表面を高度の親水性になし、かつ維持することの可能な
塗膜を形成するための、保存安定性に優れた親水性コ−
ティング組成物を提供することにある。本発明の他の目
的は、鏡、ガラス、レンズ、プリズムその他の透明部材
の表面を高度に親水化することにより、部材の曇りや水
滴形成を防止することの可能な塗膜を形成するための、
保存安定性に優れた防曇性コ−ティング組成物を提供す
ることである。本発明の他の目的は、建物や窓ガラスや
機械装置や物品の表面を高度に親水化することにより、
表面が汚れるのを防止し、又は表面を水を用いて清浄化
することの可能な塗膜を形成するための、保存安定性に
優れた易清浄性コ−ティング組成物を提供することであ
る。
SUMMARY OF THE INVENTION An object of the present invention is to provide a hydrophilic coating having excellent storage stability for forming a coating film capable of maintaining and maintaining the surface of a member to a high degree of hydrophilicity.
The object of the present invention is to provide a sting composition. Another object of the present invention is to form a coating film capable of preventing clouding and water droplet formation of the member by making the surface of a mirror, glass, lens, prism or other transparent member highly hydrophilic. ,
An object of the present invention is to provide an antifogging coating composition having excellent storage stability. Another object of the present invention is to make the surfaces of buildings, windowpanes, machinery and articles highly hydrophilic,
It is an object of the present invention to provide an easy-to-clean coating composition excellent in storage stability for preventing a surface from being soiled or forming a coating film whose surface can be cleaned with water. .

【0005】[0005]

【課題を解決するための手段】本発明は、光触媒を含有
する表面層を形成した部材において、光触媒を光励起す
ると、部材の表面が高度に親水化されるという発見に基
づく。この現象は以下に示す機構により進行すると考え
られる。すなわち、光触媒の価電子帯上端と伝導帯下端
とのエネルギ−ギャップ以上のエネルギ−を有する光が
光触媒に照射されると、光触媒の価電子帯中の電子が励
起されて伝導電子と正孔が生成し、そのいずれかまたは
双方の作用により、表面に極性が付与される。それによ
り、表面に、水が化学吸着し、さらに、その上に物理吸
着水層が形成され増加する。それにより、表面が水濡れ
角10゜以下の高度の親水性を呈するようになる。
SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the following mechanism. That is, when light having energy equal to or more than the energy gap between the upper end of the valence band and the lower end of the conduction band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited, and the conduction electrons and holes are generated. Produced and either or both actions impart polarity to the surface. As a result, water is chemically adsorbed on the surface, and a physically adsorbed water layer is formed thereon to increase. As a result, the surface exhibits a high degree of hydrophilicity with a water wetting angle of 10 ° or less.

【0006】本発明においては、平均組成式RpSiXq
O(4-p-q)/2(式中、Rは一価の有機基の1種若しくは
2種以上からなる官能基、又は、一価の有機基と水素基
から選ばれた2種以上からなる官能基であり、Xはアル
コキシ基、又は、ハロゲン原子であり、p及びqは0<
p<2、0<q<4を満足する数である)で表されるシ
ロキサンからなる塗膜形成要素であって、硬化させると
シリコ−ン樹脂の被膜を形成するものと;一般式RpS
iX4-p(式中、Rは一価の有機基の1種若しくは2種
以上からなる官能基、又は、一価の有機基と水素基から
選ばれた2種以上からなる官能基であり、Xはアルコキ
シ基、又は、ハロゲン原子であり、pは1または2であ
る)で表される加水分解性シラン誘導体で表面を被覆し
た酸化チタン粒子であって、前記塗膜形成要素中に分散
され、光励起によって前記被膜の表面のシリコ−ン分子
中のケイ素原子に結合した有機基を光触媒作用により少
なくとも部分的に水酸基に置換させ、さらに光励起に応
じて被膜の表面を親水化するための光触媒性酸化チタン
粒子;又は平均組成式RpSiXqO(4-p-q)/2(式中、
Rは一価の有機基の1種若しくは2種以上からなる官能
基、又は、一価の有機基と水素基から選ばれた2種以上
からなる官能基であり、Xはアルコキシ基、又は、ハロ
ゲン原子であり、p及びqは0<p<2、0<q<4を
満足する数である)で表されるシロキサンオリゴマ−で
表面を被覆した酸化チタン粒子であって、前記塗膜形成
要素中に分散され、光励起によって前記被膜の表面のシ
リコ−ン分子中のケイ素原子に結合した有機基を光触媒
作用により少なくとも部分的に水酸基に置換させ、さら
に光励起に応じて被膜の表面を親水化するための光触媒
性酸化チタン粒子;又は一般式SiX4(式中、Rは一
価の有機基の1種若しくは2種以上からなる官能基、又
は、一価の有機基と水素基から選ばれた2種以上からな
る官能基であり、Xはアルコキシ基、又は、ハロゲン原
子である)で表される4官能加水分解性シラン誘導体で
表面を被覆した酸化チタン粒子であって、前記塗膜形成
要素中に分散され、光励起によって前記被膜の表面のシ
リコ−ン分子中のケイ素原子に結合した有機基を光触媒
作用により少なくとも部分的に水酸基に置換させ、さら
に光励起に応じて被膜の表面を親水化するための光触媒
性酸化チタン粒子;若しくは平均組成式SiXqO(4-q)
/2(式中、Xはアルコキシ基、又は、ハロゲン原子であ
り、qは0<q<4を満足する数である)で表されるシ
リケ−トオリゴマ−で表面を被覆した酸化チタン粒子で
あって、前記塗膜形成要素中に分散され、光励起によっ
て前記被膜の表面のシリコ−ン分子中のケイ素原子に結
合した有機基を光触媒作用により少なくとも部分的に水
酸基に置換させ、さらに光励起に応じて被膜の表面を親
水化するための光触媒性酸化チタン粒子、を含有するこ
とを特徴とする光触媒性親水性コ−ティング組成物を提
供する。係るコ−ティング組成物により基材表面に塗膜
を形成すると、シリコ−ンの硬化反応により、基材表面
には光触媒性酸化物粒子とシリコ−ンを含有する表面層
が形成されるようになる。この場合、光触媒の光励起に
よってシリコ−ン分子中のケイ素原子に結合した有機基
を光触媒作用により少なくとも部分的に水酸基に置換さ
れ、さらにその上に光触媒の光励起に応じて物理吸着水
層が形成されることにより、表面が水濡れ角0゜に近い
親水性を呈するようになると共に、暗所に保持したとき
の親水維持性が向上する。本発明では、さらに光触媒性
酸化チタン粒子に、表面が予め上記加水分解性シラン誘
導体、又は上記シロキサンオリゴマ−、又は4官能加水
分解性シラン誘導体、若しくは上記シリケ−トオリゴマ
−で被覆されているようにしたので、光触媒性酸化チタ
ン粒子は中性液体中でも優れた分散安定性を発揮できる
ようになる。ところで、請求項1〜4の(a)で示され
るシロキサンポリマ−成分は、中性液体中で最も分散安
定性が良好なことから、上記被覆により、上記光触媒性
親水性コ−ティング組成物は、中性条件にすることによ
り、良好な保存安定性を発揮するようになる。その理由
は次のように考えられる。すなわち、光触媒性酸化チタ
ン粒子のみの場合は等電点は7付近にあり、中性条件で
は粒子表面の表面がほとんどゼロになり凝集しやすくな
るが、表面を上記物質により被覆することにより、粒子
表面の等電点が酸性側にずれて優れた分散安定性を発揮
できるようになると考えられる。
In the present invention, the average composition formula RpSiXq
O (4-pq) / 2 (wherein, R is a functional group composed of one or more monovalent organic groups, or two or more selected from monovalent organic groups and hydrogen groups) X is an alkoxy group or a halogen atom, and p and q are 0 <
a film forming element composed of a siloxane represented by the following formula: p <2, 0 <q <4), which forms a silicone resin film when cured;
iX4-p (wherein R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, X is an alkoxy group or a halogen atom, and p is 1 or 2), which is a titanium oxide particle whose surface is coated with a hydrolyzable silane derivative represented by the following formula: A photocatalytic activity for at least partially substituting an organic group bonded to a silicon atom in a silicon molecule on the surface of the coating by photoexcitation with a hydroxyl group by photocatalysis, and further hydrophilizing the surface of the coating in response to photoexcitation; Titanium oxide particles; or average composition formula RpSiXqO (4-pq) / 2 (wherein
R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and a hydrogen group, and X is an alkoxy group, or A halogen atom and p and q are numbers satisfying 0 <p <2 and 0 <q <4). The organic groups dispersed in the element and bonded to silicon atoms in the silicon molecules on the surface of the coating by photoexcitation are at least partially replaced by hydroxyl groups by photocatalysis, and the surface of the coating is hydrophilized by photoexcitation. Or a general formula SiX4 (where R is a functional group consisting of one or more monovalent organic groups, or a monovalent organic group and a hydrogen group) X is a functional group consisting of two or more Is an alkoxy group or a halogen atom), and is a titanium oxide particle whose surface is coated with a tetrafunctional hydrolyzable silane derivative represented by the following formula: Photocatalytic titanium oxide particles for at least partially substituting an organic group bonded to a silicon atom in a silicone molecule by photocatalysis with a hydroxyl group and further hydrophilizing the surface of the film in response to photoexcitation; or Formula SixXO (4-q)
/ 2 (wherein X is an alkoxy group or a halogen atom, and q is a number satisfying 0 <q <4), and is a titanium oxide particle whose surface is coated with a silicate oligomer. The organic group dispersed in the coating film forming element and bonded to a silicon atom in the silicon molecule on the surface of the coating film by photoexcitation is at least partially replaced with a hydroxyl group by photocatalysis, and further, in response to the photoexcitation. A photocatalytic hydrophilic coating composition comprising: photocatalytic titanium oxide particles for hydrophilizing the surface of a coating. When a coating film is formed on the surface of the substrate with the coating composition, a curing reaction of the silicon forms a surface layer containing the photocatalytic oxide particles and the silicon on the surface of the substrate. Become. In this case, the organic group bonded to the silicon atom in the silicon molecule is at least partially replaced by a hydroxyl group by photocatalysis by the photoexcitation of the photocatalyst, and a physically adsorbed water layer is formed thereon in response to the photoexcitation of the photocatalyst. By doing so, the surface exhibits hydrophilicity close to the water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. In the present invention, the photocatalytic titanium oxide particles may have a surface previously coated with the hydrolyzable silane derivative, the siloxane oligomer, or the tetrafunctional hydrolyzable silane derivative, or the silicate oligomer. As a result, the photocatalytic titanium oxide particles can exhibit excellent dispersion stability even in a neutral liquid. By the way, the siloxane polymer component represented by (a) in claims 1 to 4 has the best dispersion stability in a neutral liquid. Under the neutral condition, good storage stability is exhibited. The reason is considered as follows. That is, in the case of only the photocatalytic titanium oxide particles, the isoelectric point is around 7, and under neutral conditions, the surface of the particle surface becomes almost zero and easily aggregates. It is considered that the isoelectric point of the surface is shifted to the acidic side, so that excellent dispersion stability can be exhibited.

【0007】[0007]

【発明の実施の形態】本発明において、光触媒性酸化チ
タンとは、その結晶の伝導帯と価電子帯との間のエネル
ギ−ギャップよりも大きなエネルギ−(すなわち短い波
長)の光(励起光)を照射したときに、価電子帯中の電
子の励起(光励起)が生じて、伝導電子と正孔を生成し
うる酸化チタンをいい、例えば、アナタ−ゼ型酸化チタ
ン、ルチル型酸化チタン等の結晶性酸化チタンが好適に
利用できる。本発明における高度の親水性とは、水との
接触角に換算して10゜以下、好ましくは5゜以下の水
濡れ性を呈する状態をいう。
BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, photocatalytic titanium oxide refers to light (excitation light) having an energy (ie, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. Irradiates a titanium oxide capable of generating conduction electrons and holes by excitation of electrons in the valence band (photoexcitation) upon irradiation with, for example, an anatase type titanium oxide and a rutile type titanium oxide. Crystalline titanium oxide can be suitably used. The high hydrophilicity in the present invention means a state exhibiting water wettability of 10 ° or less, preferably 5 ° or less in terms of a contact angle with water.

【0008】請求項1〜4の(a)に記述されるシリコ
−ンは、平均組成式RpSiO(4-p)/2(式中、Rは一価
の有機基の1種若しくは2種以上からなる官能基、又
は、一価の有機基と水素基から選ばれた2種以上からな
る官能基であり、Xはアルコキシ基、又は、ハロゲン原
子であり、pは0<p<2を満足する数である)で表さ
れる樹脂である。この樹脂は後述するシリコ−ンの前駆
体を部分的に加水分解、脱水縮重合することにより得る
ことができる。
The silicone described in claims 1 to 4 (a) has an average composition formula RpSiO (4-p) / 2 (where R is one or more monovalent organic groups) Or a functional group consisting of two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p satisfies 0 <p <2. Is a number). This resin can be obtained by partially hydrolyzing and dehydrating polycondensation of a silicone precursor described later.

【0009】ここでシリコ−ンの前駆体としては、平均
組成式RpSiXqO(4-p-q)/2(式中、Rは一価の有機
基の1種若しくは2種以上からなる官能基、又は、一価
の有機基と水素基から選ばれた2種以上からなる官能基
であり、Xはアルコキシ基、又は、ハロゲン原子であ
り、p及びqは0<p<2、0<q<4を満足する数で
ある)で表されるシロキサンからなる塗膜形成要素、又
は一般式RpSiX4-p(式中、Rは一価の有機基の1種
若しくは2種以上からなる官能基、又は、一価の有機基
と水素基から選ばれた2種以上からなる官能基であり、
Xはアルコキシ基、又は、ハロゲン原子であり、pは1
または2である)で表される加水分解性シラン誘導体か
らなる塗膜形成要素、が好適に利用できる。
Here, the precursor of the silicone includes an average compositional formula RpSiXqO (4-pq) / 2 (where R is a functional group comprising one or more monovalent organic groups, or X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <q <4. A film-forming element comprising a siloxane represented by the following formula: or a general formula RpSiX4-p (wherein R is a functional group comprising one or more monovalent organic groups, or Functional group consisting of two or more selected from a valence organic group and a hydrogen group,
X is an alkoxy group or a halogen atom, and p is 1
Or 2), which is preferably composed of a hydrolyzable silane derivative represented by the formula (1).

【0010】ここで上記加水分解性シラン誘導体からな
る塗膜形成要素としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリブトキシシラン、エチルトリメトキシシ
ラン、エチルトリエトキシシラン、エチルトリプロポキ
シシラン、エチルトリブトキシシラン、フェニルトリメ
トキシシラン、フェニルトリエトキシシラン、フェニル
トリプロポキシシラン、フェニルトリブトキシシラン、
ジメチルジメトキシシラン、ジメチルジエトキシシラ
ン、ジメチルジプロポキシシラン、ジメチルジブトキシ
シラン、ジエチルジメトキシシラン、ジエチルジエトキ
シシラン、ジエチルジプロポキシシラン、ジエチルジブ
トキシシラン、フェニルメチルジメトキシシラン、フェ
ニルメチルジエトキシシラン、フェニルメチルジプロポ
キシシラン、フェニルメチルジブトキシシラン、n−プ
ロピルトリメトキシシラン、n−プロピルトリエトキシ
シラン、n−プロピルトリプロポキシシラン、n−プロ
ピルトリブトキシシラン、γ−グリコキシドキシプロピ
ルトリメトキシシラン、γ−アクリロキシプロピルトリ
メトキシシラン等が好適に利用できる。
Here, as the coating film forming element comprising the above hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.

【0011】また、上記シロキサンからなる塗膜形成要
素としては、上記加水分解性シラン誘導体の部分加水分
解及び脱水縮重合、又は上記加水分解性シラン誘導体の
部分加水分解物と、テトラメトキシシラン、テトラエト
キシシラン、テトラプロポキシシラン、テトラブトキシ
シラン、ジエトキシジメトキシシラン等の部分加水分解
物との脱水縮重合等で作製することができる。
The film-forming element composed of the above-mentioned siloxane includes partial hydrolysis and dehydration-condensation polymerization of the above-mentioned hydrolyzable silane derivative, or partially hydrolyzate of the above-mentioned hydrolyzable silane derivative, tetramethoxysilane and tetramethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.

【0012】請求項1の(b)に記述される酸化チタン
を被覆する加水分解性シラン誘導体は、一般式RpSi
X4-p(式中、Rは一価の有機基の1種若しくは2種以
上からなる官能基、又は、一価の有機基と水素基から選
ばれた2種以上からなる官能基であり、Xはアルコキシ
基、又は、ハロゲン原子であり、pは1または2であ
る)で表される加水分解性シラン誘導体である。
The hydrolyzable silane derivative covering the titanium oxide described in claim 1 (b) has a general formula RpSi
X4-p (wherein, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups; X is an alkoxy group or a halogen atom, and p is 1 or 2).

【0013】ここで上記加水分解性シラン誘導体として
は、メチルトリメトキシシラン、メチルトリエトキシシ
ラン、メチルトリプロポキシシラン、メチルトリブトキ
シシラン、エチルトリメトキシシラン、エチルトリエト
キシシラン、エチルトリプロポキシシラン、エチルトリ
ブトキシシラン、フェニルトリメトキシシラン、フェニ
ルトリエトキシシラン、フェニルトリプロポキシシラ
ン、フェニルトリブトキシシラン、ジメチルジメトキシ
シラン、ジメチルジエトキシシラン、ジメチルジプロポ
キシシラン、ジメチルジブトキシシラン、ジエチルジメ
トキシシラン、ジエチルジエトキシシラン、ジエチルジ
プロポキシシラン、ジエチルジブトキシシラン、フェニ
ルメチルジメトキシシラン、フェニルメチルジエトキシ
シラン、フェニルメチルジプロポキシシラン、フェニル
メチルジブトキシシラン、n−プロピルトリメトキシシ
ラン、n−プロピルトリエトキシシラン、n−プロピル
トリプロポキシシラン、n−プロピルトリブトキシシラ
ン、γ−グリコキシドキシプロピルトリメトキシシラ
ン、γ−アクリロキシプロピルトリメトキシシラン等が
好適に利用できる。
Here, the hydrolyzable silane derivatives include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, and ethyltrimethoxysilane. Tributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane Silane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, Ludipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ- Acryloxypropyltrimethoxysilane and the like can be suitably used.

【0014】請求項2の(b)に記述される酸化チタン
を被覆するシロキサンオリゴマ−は、平均組成式RpS
iXqO(4-p-q)/2(式中、Rは一価の有機基の1種若し
くは2種以上からなる官能基、又は、一価の有機基と水
素基から選ばれた2種以上からなる官能基であり、Xは
アルコキシ基、又は、ハロゲン原子であり、p及びqは
0<p<2、0<q<4を満足する数である)で表され
るシロキサンオリゴマ−であり、上記加水分解性シラン
誘導体の部分加水分解及び脱水縮重合、又は上記加水分
解性シラン誘導体の部分加水分解物と、テトラメトキシ
シラン、テトラエトキシシラン、テトラプロポキシシラ
ン、テトラブトキシシラン、ジエトキシジメトキシシラ
ン等の部分加水分解物との脱水縮重合等で作製すること
ができる加水分解性シラン誘導体の2〜10量体をい
う。
The siloxane oligomer coated with titanium oxide described in claim 2 (b) has an average composition formula RpS
iXqO (4-pq) / 2 (wherein R is a functional group consisting of one or more monovalent organic groups, or two or more selected from monovalent organic groups and hydrogen groups) A functional group, X is an alkoxy group or a halogen atom, and p and q are numbers satisfying 0 <p <2, 0 <q <4). Partial hydrolysis and dehydration condensation polymerization of a hydrolyzable silane derivative, or a partial hydrolyzate of the above hydrolyzable silane derivative, and tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane, etc. It refers to a dimer to dimer of a hydrolyzable silane derivative which can be produced by dehydration-condensation polymerization with a partial hydrolyzate.

【0015】請求項3の(b)に記述される酸化チタン
を被覆する4官能加水分解性シラン誘導体は、一般式S
iX4(式中、Rは一価の有機基の1種若しくは2種以
上からなる官能基、又は、一価の有機基と水素基から選
ばれた2種以上からなる官能基であり、Xはアルコキシ
基、又は、ハロゲン原子である)で表される4官能加水
分解性シラン誘導体である。
The tetrafunctional hydrolyzable silane derivative covering titanium oxide described in claim 3 (b) is represented by the general formula S
iX4 (wherein, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is A tetrafunctional hydrolyzable silane derivative represented by an alkoxy group or a halogen atom).

【0016】ここで上記4官能加水分解性シラン誘導体
としては、テトラメトキシシラン、テトラエトキシシラ
ン、テトラプロポキシシラン、テトラブトキシシラン、
ジエトキシジメトキシシラン等が好適に利用できる。
Here, the tetrafunctional hydrolyzable silane derivative includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
Diethoxydimethoxysilane and the like can be suitably used.

【0017】請求項4の(b)に記述される酸化チタン
を被覆するシリケ−トオリゴマ−は、平均組成式SiX
qO(4-q)/2(式中、Xはアルコキシ基、又は、ハロゲン
原子であり、qは0<q<4を満足する数である)で表
されるシリケ−トオリゴマ−であり、上記4官能加水分
解性シラン誘導体の部分加水分解及び脱水縮重合等で作
製することができる4官能加水分解性シランの2〜10
量体をいう。
The silicate oligomer for coating titanium oxide described in claim 4 (b) has an average composition formula of Six
a silicate oligomer represented by qO (4-q) / 2 (where X is an alkoxy group or a halogen atom, and q is a number satisfying 0 <q <4); Two to ten tetrafunctional hydrolyzable silanes that can be produced by partial hydrolysis and dehydration condensation polymerization of tetrafunctional hydrolyzable silane derivatives
Refers to a monomer.

【0018】酸化チタン粒子への上記被覆物の固定方法
は、例えば、スプレ−コ−ティング法、ディップコ−テ
ィング法、フロ−コ−ティング法、スピンコ−ティング
法、ロ−ルコ−ティング法、刷毛塗り、スポンジ塗り等
の方法で被覆後、熱処理等の方法で固定する。
Examples of the method of fixing the above-mentioned coating on titanium oxide particles include spray coating, dip coating, flow coating, spin coating, roll coating, and brush. After coating with a method such as coating or sponge coating, the coating is fixed by a method such as heat treatment.

【0019】コ−ティング組成物には、Ag、Cu、Z
nのような金属を添加することができる。前記金属を添
加した場合、塗膜により形成される表面層は、表面に付
着した細菌や黴を暗所でも死滅させることができる。
The coating composition includes Ag, Cu, Z
A metal such as n can be added. When the metal is added, the surface layer formed by the coating film can kill bacteria and fungi attached to the surface even in a dark place.

【0020】コ−ティング組成物には、Pt、Pd、R
u、Rh、Ir、Osのような白金族金属を添加するこ
とができる。前記金属を添加した場合、塗膜により形成
される表面層は、光触媒の酸化還元活性を増強でき、有
機物汚れの分解性、有害気体や悪臭の分解性を向上させ
ることができる。
The coating composition includes Pt, Pd, R
A platinum group metal such as u, Rh, Ir, Os can be added. When the metal is added, the surface layer formed by the coating film can enhance the oxidation-reduction activity of the photocatalyst, and can improve the decomposability of organic contaminants and harmful gases and odors.

【0021】コ−ティング組成物は、その他に水、エタ
ノ−ル、プロパノ−ル等の溶媒や、塩酸、硝酸、硫酸、
酢酸、マレイン酸等のシリコ−ンの前駆体の加水分解を
促進する触媒や、トリブチルアミン、ヘキシルアミンな
どの塩基性化合物類、アルミニウムトリイソプロポキシ
ド、テトライソプロピルチタネ−トなどの酸性化合物類
等のシリコ−ンの前駆体を硬化させる触媒や、シランカ
ップリング剤等のコ−ティング液の分散性を向上させる
界面活性剤などを添加してもよい。
The coating composition may further contain a solvent such as water, ethanol or propanol, hydrochloric acid, nitric acid, sulfuric acid, or the like.
Catalysts that promote hydrolysis of silicone precursors such as acetic acid and maleic acid, basic compounds such as tributylamine and hexylamine, and acidic compounds such as aluminum triisopropoxide and tetraisopropyl titanate For example, a catalyst for curing the precursor of the silicone such as silane coupling agent or a surfactant for improving the dispersibility of the coating liquid such as a silane coupling agent may be added.

【0022】本発明のコ−ティング組成物の利用方法
は、基本的には、基材表面にコ−ティング組成物を塗布
し、硬化させて塗膜を形成することによる。
The method of using the coating composition of the present invention is basically based on applying the coating composition to the surface of a substrate and curing the coating composition to form a coating film.

【0023】上記コ−ティング組成物の塗布方法として
は、スプレ−コ−ティング法、ディップコ−ティング
法、フロ−コ−ティング法、スピンコ−ティング法、ロ
−ルコ−ティング法、刷毛塗り、スポンジ塗り等の方法
が好適に利用できる。硬化方法としては、熱処理、室温
放置、紫外線照射等により重合させて行うことができ
る。
The coating method of the above-mentioned coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.

【0024】上記方法で部材表面に塗膜を形成すると、
部材表面は光触媒の光励起に応じて親水性を呈するよう
になる。ここで、光触媒の光励起により、基材表面が高
度に親水化されるためには、励起光の照度は0.001
mW/cm2以上あればよいが、0.01mW/cm2以
上だと好ましく、0.1mW/cm2以上だとより好ま
しい。光触媒の光励起に用いる光源としては、太陽光、
室内照明、蛍光灯、水銀灯、白熱電灯、キセノンラン
プ、高圧ナトリウムランプ、メタルハライドランプ、B
LBランプ等が好適に利用できる。
When a coating film is formed on the member surface by the above method,
The surface of the member becomes hydrophilic in response to the photoexcitation of the photocatalyst. Here, in order for the substrate surface to be highly hydrophilized by photoexcitation of the photocatalyst, the illuminance of the excitation light must be 0.001.
mW / cm2 or more may be sufficient, but it is preferably 0.01 mW / cm2 or more, and more preferably 0.1 mW / cm2 or more. Light sources used for photoexcitation of the photocatalyst include sunlight,
Interior lighting, fluorescent lamp, mercury lamp, incandescent lamp, xenon lamp, high-pressure sodium lamp, metal halide lamp, B
An LB lamp or the like can be suitably used.

【0025】部材表面に塗膜により形成される表面層の
膜厚は、0.4μm以下にするのが好ましい。そうすれ
ば、光の乱反射による白濁を防止することができ、表面
層は実質的に透明となる。さらに、表面層の膜厚を、
0.2μm以下にすると一層好ましい。そうすれば、光
の干渉による表面層の発色を防止することができる。ま
た、表面層が薄ければ薄いほどその透明度は向上する。
更に、膜厚を薄くすれば、表面層の耐摩耗性が向上す
る。
The thickness of the surface layer formed by the coating film on the member surface is preferably 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, the thickness of the surface layer is
It is more preferable that the thickness be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.

【0026】PCT/JP96/00733号に示した
ように、部材表面が水との接触角に換算して10゜以下
の状態であれば、空気中の湿分や湯気が結露しても、凝
縮水が個々の水滴を形成せずに一様な水膜になる傾向が
顕著になる。従って、表面に光散乱性の曇りを生じない
傾向が顕著になる。同様に、窓ガラスや車両用バックミ
ラ−や車両用風防ガラスや眼鏡レンズやヘルメットのシ
−ルドが降雨や水しぶきを浴びた場合に、離散した目障
りな水滴が形成されずに、高度の視界と可視性を確保
し、車両や交通の安全性を保証し、種々の作業や活動の
能率を向上させる効果が飛躍的に向上する。また、同様
にPCT/JP96/00733号に示したように、部
材表面が水との接触角に換算して10゜以下、好ましく
は5゜以下の状態であれば、都市煤塵、自動車等の排気
ガスに含有されるカ−ボンブラック等の燃焼生成物、油
脂、シ−ラント溶出成分等の疎水性汚染物質、及び無機
粘土質汚染物質双方が付着しにくく、付着しても降雨や
水洗により簡単に落せる状態になる。
As shown in PCT / JP96 / 00733, if the surface of the member is not more than 10 ° in terms of the contact angle with water, even if moisture or steam in the air is condensed, it will not condense. Water tends to form a uniform water film without forming individual water droplets. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly, when a window glass, a vehicle back mirror, a vehicle windshield, an eyeglass lens, or a shield of a helmet is subjected to rainfall or splashing, discrete unsightly water droplets are not formed, and high visibility and visibility are achieved. As a result, the effects of ensuring safety, ensuring the safety of vehicles and traffic, and improving the efficiency of various tasks and activities are greatly improved. Similarly, as shown in PCT / JP96 / 00733, if the surface of the member is less than or equal to 10 °, preferably less than or equal to 5 ° in terms of the contact angle with water, exhaust from city dust, automobiles, etc. Combustion products such as carbon black contained in gas, hydrophobic contaminants such as oils and fats, sealant eluting components, etc., and inorganic clay contaminants are unlikely to adhere to each other. It is in a state where it can be dropped.

【0027】部材表面が上記高度の親水性を呈し、かつ
その状態を維持するようになれば、上記防曇効果、表面
清浄化効果の他、帯電防止効果(ほこり付着防止効
果)、断熱効果、水中での気泡付着防止効果、熱交換器
における効率向上効果、生体親和性向上効果等が発揮さ
れるようになる。
If the surface of the member exhibits the above-mentioned high hydrophilicity and maintains the state, the anti-fogging effect, the surface cleaning effect, the antistatic effect (dust adhesion preventing effect), the heat insulating effect, The effect of preventing bubbles from adhering in water, the effect of improving efficiency in a heat exchanger, the effect of improving biocompatibility, and the like are exhibited.

【0028】本発明が適用可能な基材としては、防曇効
果を期待する場合には透明な部材であり、その材質はガ
ラス、プラスチック等が好適に利用できる。適用可能な
基材を用途でいえば、車両用後方確認ミラ−、浴室用
鏡、洗面所用鏡、歯科用鏡、道路鏡のような鏡;眼鏡レ
ンズ、光学レンズ、照明用レンズ、半導体用レンズ、複
写機用レンズ、車両用後方確認カメラレンズのようなレ
ンズ;プリズム;建物や監視塔の窓ガラス;自動車、鉄
道車両、航空機、船舶、潜水艇、雪上車、ロ−プウエイ
のゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の
窓ガラス;自動車、オ−トバイ、鉄道車両、航空機、船
舶、潜水艇、雪上車、スノ−モ−ビル、ロ−プウエイの
ゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の風
防ガラス;防護用ゴ−グル、スポ−ツ用ゴ−グル、防護
用マスクのシ−ルド、スポ−ツ用マスクのシ−ルド、ヘ
ルメットのシ−ルド、冷凍食品陳列ケ−スのガラス、中
華饅頭等の保温食品の陳列ケ−スのガラス;計測機器の
カバ−、車両用後方確認カメラレンズのカバ−、レ−ザ
−歯科治療器等の集束レンズ、車間距離センサ−等のレ
−ザ−光検知用センサ−のカバ−、赤外線センサ−のカ
バ−;カメラ用フィルタ−、及び上記物品表面に貼着さ
せるためのフィルム、シ−ト、シ−ル等を含む。
The substrate to which the present invention can be applied is a transparent member when an anti-fogging effect is expected, and glass, plastic, and the like can be suitably used as the material. Speaking of applicable base materials, mirrors such as rearview mirrors for vehicles, mirrors for bathrooms, mirrors for toilets, dental mirrors, road mirrors; spectacle lenses, optical lenses, illumination lenses, semiconductor lenses Lenses such as copier lenses, rear view camera lenses for vehicles; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, lowway gondola, amusement parks Gondolas, vehicle windows such as spaceships; cars, motorbikes, railway vehicles, aircraft, ships, submarines, snowmobiles, snowmobiles, lowway gondola, amusement park gondola, space Windshield for vehicles such as ships; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display Case glass, Chinese bun, etc. Glass for display case of warm food; Cover for measuring equipment, Cover for rear view camera lens for vehicle, Focusing lens for laser dental treatment device, etc., Laser light detection for inter-vehicle distance sensor, etc. Cover for an infrared sensor, a cover for an infrared sensor, a filter for a camera, and a film, a sheet, a seal, and the like to be attached to the surface of the article.

【0029】本発明が適用可能な基材としては、表面清
浄化効果を期待する場合にはその材質は、例えば、金
属、セラミック、ガラス、プラスチック、木、石、セメ
ント、コンクリ−ト、繊維、布帛、それらの組合せ、そ
れらの積層体が好適に利用できる。適用可能な基材を用
途でいえば、建材、建物外装、建物内装、窓枠、窓ガラ
ス、構造部材、乗物の外装及び塗装、機械装置や物品の
外装、防塵カバ−及び塗装、交通標識、各種表示装置、
広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガ−ドレ
−ルの外装及び塗装、トンネル内装及び塗装、碍子、太
陽電池カバ−、太陽熱温水器集熱カバ−、ビニ−ルハウ
ス、車両用照明灯のカバ−、住宅設備、便器、浴槽、洗
面台、照明器具、照明カバ−、台所用品、食器、食器洗
浄器、食器乾燥器、流し、調理レンジ、キッチンフ−
ド、換気扇、及び上記物品表面に貼着させるためのフィ
ルム、シ−ト、シ−ル等を含む。
When a surface cleaning effect is expected as a substrate to which the present invention can be applied, the material may be, for example, metal, ceramic, glass, plastic, wood, stone, cement, concrete, fiber, Fabrics, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, windowpanes, structural members, vehicle exteriors and coatings, machinery and articles exteriors, dustproof covers and coatings, traffic signs, Various display devices,
Advertising towers, noise barriers for roads, noise barriers for railways, bridges, exterior and coating of garages, tunnel interiors and coatings, insulators, solar battery covers, solar water heater collector covers, vinyl houses, vehicle lighting Light covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures, lighting covers, kitchen utensils, dishes, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods
And a film, a sheet, a seal, and the like for attaching to the surface of the article.

【0030】本発明が適用可能な基材としては、帯電防
止効果を期待する場合にはその材質は、例えば、金属、
セラミック、ガラス、プラスチック、木、石、セメン
ト、コンクリ−ト、繊維、布帛、それらの組合せ、それ
らの積層体が好適に利用できる。適用可能な基材を用途
でいえば、ブラウン管、磁気記録メディア、光記録メデ
ィア、光磁気記録メディア、オ−ディオテ−プ、ビデオ
テ−プ、アナログレコ−ド、家庭用電気製品のハウジン
グや部品や外装及び塗装、OA機器製品のハウジングや
部品や外装及び塗装、建材、建物外装、建物内装、窓
枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装
置や物品の外装、防塵カバ−及び塗装、及び上記物品表
面に貼着させるためのフィルム、シ−ト、シ−ル等を含
む。
As a substrate to which the present invention can be applied, when an antistatic effect is expected, its material is, for example, metal,
Ceramic, glass, plastic, wood, stone, cement, concrete, fiber, fabric, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable substrates, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housings and parts for household electrical appliances, Exterior and painting, OA equipment product housing and parts and exterior and painting, building materials, building exterior, building interior, window frames, window glass, structural members, vehicle exterior and painting, mechanical equipment and articles exterior, dustproof cover and Includes films, sheets, seals, etc. for painting and sticking to the surface of the article.

【0031】[0031]

【実施例】塩素法にて作製した酸化チタン粒子をγ−グ
リコキシドプロピルトリメトキシシランで表面処理した
後、pH7の水中に分散させた。この分散液と、シロキ
サン樹脂塗料を混合後、エタノ−ルで希釈し、3時間撹
拌し、コ−ティング液を得た。このコ−ティング液を1
か月17℃で放置したが分散性は良好であった。またこ
のコ−ティング液を石英ガラス板に塗布し、150℃で
硬化させた試料に、3日間紫外線照度0.5mW/cm
2のBLBランプを照射したところ、水との接触角は0
゜になった。
EXAMPLE Titanium oxide particles produced by the chlorine method were surface-treated with γ-glycoxide propyltrimethoxysilane, and then dispersed in water having a pH of 7. After mixing the dispersion and the siloxane resin coating, the mixture was diluted with ethanol and stirred for 3 hours to obtain a coating liquid. Apply this coating liquid to 1
After standing at 17 ° C. for a month, the dispersibility was good. The coating liquid was applied to a quartz glass plate and cured at 150 ° C., and the sample was cured at 150 ° C. for 3 days with an illuminance of 0.5 mW / cm.
When the BLB lamp of No. 2 was irradiated, the contact angle with water was 0
It became ゜.

【0032】[0032]

【発明の効果】本発明の光触媒性親水性コ−ティング組
成物によれば、優れた長期保存安定性を有するととも
に、部材表面を高度の親水性になし、かつ維持すること
ができる。
The photocatalytic hydrophilic coating composition of the present invention has excellent long-term storage stability and can maintain and maintain the surface of the member to a high degree of hydrophilicity.

─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成14年1月29日(2002.1.2
9)
[Submission date] January 29, 2002 (2002.1.2
9)

【手続補正1】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】全文[Correction target item name] Full text

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【書類名】 明細書[Document Name] Statement

【発明の名称】 遮音壁および遮音壁の洗浄方法Patent application title: Sound insulation wall and method for cleaning sound insulation wall

【特許請求の範囲】[Claims]

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、表面を水を用いて
清浄化することの可能な塗膜を形成した道路又は鉄道の
遮音壁に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a road or railroad sound insulating wall having a coating film whose surface can be cleaned with water.

【0002】[0002]

【従来の技術】建築及び塗料の分野においては、環境汚
染に伴い、建築外装材料や屋外建造物やその塗膜の汚れ
が問題となっている。大気中に浮遊する煤塵や粒子は晴
天には建物の屋根や外壁に堆積する。堆積物は降雨に伴
い雨水により流され、建物の外壁を流下する。更に、雨
天には浮遊煤塵は雨によって持ち運ばれ、建物の外壁や
屋外建造物の表面を流下する。その結果、表面には、雨
水の道筋に沿って汚染物質が付着する。表面が乾燥する
と、表面には縞状の汚れが現れる。建築外装材料や塗膜
の汚れは、カ−ボンブラックのような燃焼生成物や、都
市煤塵や粘土粒子のような無機質物質の汚染物質からな
る。このような汚染物質の多様性が防汚対策を複雑にし
ているものと考えられる(橘高義典著“外壁仕上材料の
汚染の促進試験方法”、日本建築学会構造系論文報告
集、第404号、1989年10月、p.15−2
4)。従来の通念では、上記建築外装などの汚れを防止
するためにはポリテトラフルオロエチレン(PTFE)
のような撥水性の塗料が好ましいと考えられていたが、
最近では、疎水性成分を多く含む都市煤塵に対しては、
塗膜の表面を出来るだけ親水性にするのがよいと考えら
れている(高分子、44巻、1995年5月号、p.3
07)。そこで、親水性のグラフトポリマ−で建物を塗
装することが提案されている(新聞“化学工業日報”、
1995年1月30日)。報告によれば、この塗膜は水
との接触角に換算して30〜40゜の親水性を呈する。
しかしながら、粘土鉱物で代表される無機質塵埃の水と
の接触角は20゜から50゜であり、水との接触角が3
0〜40゜のグラフトポリマ−に対して親和性を有し、
その表面に付着しやすいので、このグラフトポリマ−の
塗膜は無機質塵埃による汚れを防止することができない
と考えられる。
2. Description of the Related Art In the field of construction and paints, contamination of architectural exterior materials, outdoor buildings and coating films thereof has become a problem due to environmental pollution. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface. Soil on building exterior materials and coatings consists of combustion products such as carbon black and inorganic contaminants such as urban dust and clay particles. It is considered that the diversity of such contaminants complicates antifouling measures (Yoshinori Tachibana, "Method of Accelerated Testing of Contamination of Exterior Wall Finishing Materials", Journal of Architectural Institute of Japan, Structural Transactions, No. 404, October 1989, pp. 15-2
4). According to conventional wisdom, polytetrafluoroethylene (PTFE) is used to prevent the above-mentioned dirt on the building exterior.
Although water-repellent paint such as was considered preferable,
Recently, for urban dust containing many hydrophobic components,
It is considered that the surface of the coating film should be made as hydrophilic as possible (Polymer, vol. 44, May 1995, p. 3).
07). Therefore, it has been proposed to paint a building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily",
Jan. 30, 1995). According to reports, this coating exhibits a hydrophilicity of 30 to 40 ° in contact angle with water.
However, the contact angle of inorganic dust represented by clay minerals with water is 20 ° to 50 °, and the contact angle with water is 3 °.
Having an affinity for a graft polymer of 0 to 40 °;
It is considered that the coating of the graft polymer cannot prevent contamination by inorganic dust because it easily adheres to the surface.

【0003】[0003]

【発明が解決しようとする課題】本発明の目的は、表面
を高度に親水化することにより、表面が汚れるのを防止
し、又は表面を水を用いて清浄化することの可能な塗膜
を形成するための、保存安定性に優れた道路又は鉄道の
遮音壁を提供することである。
SUMMARY OF THE INVENTION An object of the present invention is to provide a coating film that can be prevented from being soiled or that can be cleaned with water by making the surface highly hydrophilic. An object of the present invention is to provide a road or railroad sound insulation wall having excellent storage stability to be formed.

【0004】[0004]

【課題を解決するための手段】本発明は、光触媒を含有
する表面層を形成した部材において、光触媒を光励起す
ると、部材の表面が高度に親水化されるという発見に基
づく。この現象は以下に示す機構により進行すると考え
られる。すなわち、光触媒の価電子帯上端と伝導帯下端
とのエネルギ−ギャップ以上のエネルギ−を有する光が
光触媒に照射されると、光触媒の価電子帯中の電子が励
起されて伝導電子と正孔が生成し、そのいずれかまたは
双方の作用により、表面に極性が付与される。それによ
り、表面に、水が化学吸着し、さらに、その上に物理吸
着水層が形成され増加する。それにより、表面が水濡れ
角10゜以下の高度の親水性を呈するようになる。
SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the following mechanism. That is, when light having energy equal to or more than the energy gap between the upper end of the valence band and the lower end of the conduction band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited, and the conduction electrons and holes are generated. Produced and either or both actions impart polarity to the surface. As a result, water is chemically adsorbed on the surface, and a physically adsorbed water layer is formed thereon to increase. As a result, the surface exhibits a high degree of hydrophilicity with a water wetting angle of 10 ° or less.

【0005】本発明に係る道路又は鉄道の遮音壁は、表
面を半導体光触媒含有層で被覆してなり、前記光触媒含
有層は光触媒の粒子が分散されたシリコーンによって形
成されており、前記光触媒含有層のシリコーン分子のケ
イ素原子に結合した有機基が光触媒の作用により少なく
とも部分的に水酸基に置換されたシリコーン誘導体で形
成されており、前記光触媒が太陽光によって光励起され
るに応じて前記層の表面が親水化され、もって、疎水性
の汚染物質が遮音壁の表面に付着するのが防止され、若
しくは、遮音壁が降雨にさらされた時に遮音壁の表面に
付着した汚れが雨水により洗い流される構成とした。
[0005] The sound insulating wall of a road or a railway according to the present invention has a surface coated with a semiconductor photocatalyst containing layer, and the photocatalyst containing layer is formed of silicone in which photocatalyst particles are dispersed. The organic group bonded to the silicon atom of the silicone molecule is formed of a silicone derivative at least partially substituted with a hydroxyl group by the action of a photocatalyst, and the surface of the layer becomes hydrophilic as the photocatalyst is photoexcited by sunlight. Thus, hydrophobic contaminants are prevented from adhering to the surface of the sound insulation wall, or dirt attached to the surface of the sound insulation wall is washed away by rainwater when the sound insulation wall is exposed to rainfall.

【0006】また、本発明に係る道路又は鉄道の遮音壁
は、表面を半導体光触媒含有層で被覆してなり、前記光
触媒含有層はTiO2、ZnO、SnO2、SrTi
3、WO3、Bi23、Fe23からなる群から選ばれ
た1種の光触媒を含み、前記光触媒含有層は、更に、P
t、Pd、Rh、Ru、Os、Irからなる群から選ば
れた1種の金属を含み、前記光触媒が太陽光によって光
励起されるに応じて前記層の表面が親水化され、もっ
て、疎水性の汚染物質が遮音壁の表面に付着するのが防
止され、若しくは、遮音壁が降雨にさらされた時に遮音
壁の表面に付着した汚れが雨水により洗い流される構成
とした。
The sound insulation wall of a road or a railway according to the present invention has a surface coated with a semiconductor photocatalyst containing layer, and the photocatalyst containing layer is made of TiO 2 , ZnO, SnO 2 , SrTi.
O 3 , WO 3 , Bi 2 O 3 , and Fe 2 O 3 , wherein the photocatalyst-containing layer includes one type of photocatalyst selected from the group consisting of
a metal selected from the group consisting of t, Pd, Rh, Ru, Os, and Ir, wherein the surface of the layer is hydrophilized when the photocatalyst is photoexcited by sunlight, and The contaminants are prevented from adhering to the surface of the sound insulating wall, or the dirt adhering to the surface of the sound insulating wall is washed away by rainwater when the sound insulating wall is exposed to rainfall.

【0007】前記遮音壁の少なくとも一部を透明な材料
とし、前記光触媒含有層を透明とする構成が考えられ、
光触媒含有層はTiO2、ZnO、SnO2、SrTiO
3、WO3、Bi23、Fe23からなる群から選ばれた
1種の光触媒を含み、より具体的にはアナターゼ型チタ
ニアとすることができる。また、前記光触媒含有層は、
更に、Pt、Pd、Rh、Ru、Os、Irからなる群
から選ばれた1種の金属を含むようにしてもよい。
It is conceivable that at least a part of the sound insulating wall is made of a transparent material and the photocatalyst containing layer is made transparent.
The photocatalyst containing layer is made of TiO 2 , ZnO, SnO 2 , SrTiO
3 , one photocatalyst selected from the group consisting of WO 3 , Bi 2 O 3 , and Fe 2 O 3 , and more specifically, anatase-type titania. Further, the photocatalyst containing layer,
Further, one kind of metal selected from the group consisting of Pt, Pd, Rh, Ru, Os, and Ir may be included.

【0008】また、本発明に係る道路又は鉄道の遮音壁
の洗浄方法は、半導体光触媒含有層によって被覆された
遮音壁を道路又は鉄道の側部に設置し、前記遮音壁を太
陽の照射にさらすことにより太陽光によって光触媒を励
起させて前記層の表面を親水化させ、前記遮音壁を降雨
にさらすことにより前記層の表面に付着した汚れを雨水
により洗い流させるようにした。
Further, the method for cleaning a sound insulating wall of a road or a railway according to the present invention comprises installing a sound insulating wall covered with a semiconductor photocatalyst-containing layer on a side of a road or a railway, and exposing the sound insulating wall to solar radiation. The photocatalyst is excited by light to hydrophilize the surface of the layer, and the sound insulation wall is exposed to rain so that dirt attached to the surface of the layer is washed away with rainwater.

【0009】本発明に係る道路又は鉄道の遮音壁の他の
洗浄方法は、半導体光触媒含有層によって被覆された遮
音壁を道路又は鉄道の側部に設置し、前記遮音壁を太陽
の照射にさらすことにより太陽光によって光触媒を励起
させて前記層の表面を親水化させ、前記層の表面に水を
供給することにより前記層の表面に付着した汚染物質を
洗い流すようにした。
Another method for cleaning a road or railroad sound insulation wall according to the present invention is to install a sound insulation wall covered with a semiconductor photocatalyst containing layer on a side of a road or railroad and to expose the sound insulation wall to the sun's radiation. The photocatalyst was excited by light to hydrophilize the surface of the layer, and water was supplied to the surface of the layer to wash away contaminants attached to the surface of the layer.

【0010】前記水の供給は例えば遮音壁に水を噴射す
ることにより行い、前記水の噴射は例えば走行中の作業
車から行う。
[0010] The supply of the water is performed by, for example, injecting water to a sound insulation wall, and the water is injected, for example, from a traveling work vehicle.

【0011】[0011]

【発明の実施の形態】本発明に係る道路用または鉄道用
遮音壁として適用可能な基材としては、防曇効果を期待
する場合には透明な部材であり、その材質はガラス、プ
ラスチック等が好適に利用でき、表面清浄化効果を期待
する場合にはその材質は、例えば、金属、セラミック、
ガラス、プラスチック、木、石、セメント、コンクリ−
ト、繊維、布帛、それらの組合せ、それらの積層体が好
適に利用できる。
BEST MODE FOR CARRYING OUT THE INVENTION A base material applicable to the sound insulation wall for roads or railways according to the present invention is a transparent member when an anti-fogging effect is expected, and the material is preferably glass, plastic or the like. When the surface cleaning effect is expected, the material is, for example, metal, ceramic,
Glass, plastic, wood, stone, cement, concrete
, Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used.

【0012】前記道路用または鉄道用遮音壁の表面は、
半導体光触媒含有層で被覆され、光触媒含有層は光触媒
の粒子が分散されたシリコーンによって形成され、光触
媒含有層のシリコーン分子のケイ素原子に結合した有機
基が光触媒の作用により少なくとも部分的に水酸基に置
換されたシリコーン誘導体で形成されている。
[0012] The surface of the road or railroad sound insulation wall is:
The photocatalyst-containing layer is formed of silicone in which photocatalyst particles are dispersed, and the organic group bonded to the silicon atom of the silicone molecule of the photocatalyst-containing layer is at least partially replaced with a hydroxyl group by the action of the photocatalyst. Formed with the silicone derivative.

【0013】本発明において、光触媒性酸化チタンと
は、その結晶の伝導帯と価電子帯との間のエネルギ−ギ
ャップよりも大きなエネルギ−(すなわち短い波長)の
光(励起光)を照射したときに、価電子帯中の電子の励
起(光励起)が生じて、伝導電子と正孔を生成しうる酸
化チタンをいい、例えば、アナタ−ゼ型酸化チタン、ル
チル型酸化チタン等の結晶性酸化チタンが好適に利用で
きる。本発明における高度の親水性とは、水との接触角
に換算して10゜以下、好ましくは5゜以下の水濡れ性
を呈する状態をいう。
In the present invention, the photocatalytic titanium oxide is irradiated with light (excitation light) having an energy (ie, shorter wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. Refers to titanium oxide that can generate conduction electrons and holes by excitation of electrons in the valence band (photoexcitation). For example, crystalline titanium oxide such as anatase-type titanium oxide and rutile-type titanium oxide Can be suitably used. The high hydrophilicity in the present invention means a state exhibiting water wettability of 10 ° or less, preferably 5 ° or less in terms of a contact angle with water.

【0014】またシリコ−ンは、平均組成式RpSiO
(4-p)/2(式中、Rは一価の有機基の1種若しくは2種
以上からなる官能基、又は、一価の有機基と水素基から
選ばれた2種以上からなる官能基であり、Xはアルコキ
シ基、又は、ハロゲン原子であり、pは0<p<2を満
足する数である)で表される樹脂である。この樹脂は後
述するシリコ−ンの前駆体を部分的に加水分解、脱水縮
重合することにより得ることができる。
Further, the silicon has an average composition formula of RpSiO.
(4-p) / 2 (wherein R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more selected from monovalent organic groups and hydrogen groups) X is an alkoxy group or a halogen atom, and p is a number satisfying 0 <p <2). This resin can be obtained by partially hydrolyzing and dehydrating polycondensation of a silicone precursor described later.

【0015】ここでシリコ−ンの前駆体としては、平均
組成式RpSiXqO(4-p-q)/2(式中、Rは一価の有機
基の1種若しくは2種以上からなる官能基、又は、一価
の有機基と水素基から選ばれた2種以上からなる官能基
であり、Xはアルコキシ基、又は、ハロゲン原子であ
り、p及びqは0<p<2、0<q<4を満足する数で
ある)で表されるシロキサンからなる塗膜形成要素、又
は一般式RpSiX4-p(式中、Rは一価の有機基の1種
若しくは2種以上からなる官能基、又は、一価の有機基
と水素基から選ばれた2種以上からなる官能基であり、
Xはアルコキシ基、又は、ハロゲン原子であり、pは1
または2である)で表される加水分解性シラン誘導体か
らなる塗膜形成要素、が好適に利用できる。
Here, the precursor of the silicone includes an average compositional formula RpSiXqO (4-pq) / 2 (where R is a functional group comprising one or more monovalent organic groups, or X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <q <4. A film-forming element comprising a siloxane represented by the following formula: or a general formula RpSiX4-p (wherein R is a functional group comprising one or more monovalent organic groups, or Functional group consisting of two or more selected from a valence organic group and a hydrogen group,
X is an alkoxy group or a halogen atom, and p is 1
Or 2), which is preferably composed of a hydrolyzable silane derivative represented by the formula (1).

【0016】ここで上記加水分解性シラン誘導体からな
る塗膜形成要素としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリブトキシシラン、エチルトリメトキシシ
ラン、エチルトリエトキシシラン、エチルトリプロポキ
シシラン、エチルトリブトキシシラン、フェニルトリメ
トキシシラン、フェニルトリエトキシシラン、フェニル
トリプロポキシシラン、フェニルトリブトキシシラン、
ジメチルジメトキシシラン、ジメチルジエトキシシラ
ン、ジメチルジプロポキシシラン、ジメチルジブトキシ
シラン、ジエチルジメトキシシラン、ジエチルジエトキ
シシラン、ジエチルジプロポキシシラン、ジエチルジブ
トキシシラン、フェニルメチルジメトキシシラン、フェ
ニルメチルジエトキシシラン、フェニルメチルジプロポ
キシシラン、フェニルメチルジブトキシシラン、n−プ
ロピルトリメトキシシラン、n−プロピルトリエトキシ
シラン、n−プロピルトリプロポキシシラン、n−プロ
ピルトリブトキシシラン、γ−グリコキシドキシプロピ
ルトリメトキシシラン、γ−アクリロキシプロピルトリ
メトキシシラン等が好適に利用できる。
Here, as the coating film forming element comprising the above hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.

【0017】また、上記シロキサンからなる塗膜形成要
素としては、上記加水分解性シラン誘導体の部分加水分
解及び脱水縮重合、又は上記加水分解性シラン誘導体の
部分加水分解物と、テトラメトキシシラン、テトラエト
キシシラン、テトラプロポキシシラン、テトラブトキシ
シラン、ジエトキシジメトキシシラン等の部分加水分解
物との脱水縮重合等で作製することができる。
The film-forming element composed of the siloxane includes partial hydrolysis and dehydration-condensation polymerization of the hydrolyzable silane derivative, or partial hydrolyzate of the hydrolyzable silane derivative, tetramethoxysilane, tetramethoxysilane, and tetramethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.

【0018】加水分解性シラン誘導体は、一般式RpS
iX4-p(式中、Rは一価の有機基の1種若しくは2種
以上からなる官能基、又は、一価の有機基と水素基から
選ばれた2種以上からなる官能基であり、Xはアルコキ
シ基、又は、ハロゲン原子であり、pは1または2であ
る)で表される加水分解性シラン誘導体である。
The hydrolyzable silane derivative has the general formula RpS
iX4-p (wherein R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, X is an alkoxy group or a halogen atom, and p is 1 or 2).

【0019】ここで上記加水分解性シラン誘導体として
は、メチルトリメトキシシラン、メチルトリエトキシシ
ラン、メチルトリプロポキシシラン、メチルトリブトキ
シシラン、エチルトリメトキシシラン、エチルトリエト
キシシラン、エチルトリプロポキシシラン、エチルトリ
ブトキシシラン、フェニルトリメトキシシラン、フェニ
ルトリエトキシシラン、フェニルトリプロポキシシラ
ン、フェニルトリブトキシシラン、ジメチルジメトキシ
シラン、ジメチルジエトキシシラン、ジメチルジプロポ
キシシラン、ジメチルジブトキシシラン、ジエチルジメ
トキシシラン、ジエチルジエトキシシラン、ジエチルジ
プロポキシシラン、ジエチルジブトキシシラン、フェニ
ルメチルジメトキシシラン、フェニルメチルジエトキシ
シラン、フェニルメチルジプロポキシシラン、フェニル
メチルジブトキシシラン、n−プロピルトリメトキシシ
ラン、n−プロピルトリエトキシシラン、n−プロピル
トリプロポキシシラン、n−プロピルトリブトキシシラ
ン、γ−グリコキシドキシプロピルトリメトキシシラ
ン、γ−アクリロキシプロピルトリメトキシシラン等が
好適に利用できる。
Here, the hydrolyzable silane derivatives include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyl Tributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane Silane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, Ludipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ- Acryloxypropyltrimethoxysilane and the like can be suitably used.

【0020】酸化チタンを被覆するシロキサンオリゴマ
−は、平均組成式RpSiXqO(4-p-q)/2(式中、Rは
一価の有機基の1種若しくは2種以上からなる官能基、
又は、一価の有機基と水素基から選ばれた2種以上から
なる官能基であり、Xはアルコキシ基、又は、ハロゲン
原子であり、p及びqは0<p<2、0<q<4を満足
する数である)で表されるシロキサンオリゴマ−であ
り、上記加水分解性シラン誘導体の部分加水分解及び脱
水縮重合、又は上記加水分解性シラン誘導体の部分加水
分解物と、テトラメトキシシラン、テトラエトキシシラ
ン、テトラプロポキシシラン、テトラブトキシシラン、
ジエトキシジメトキシシラン等の部分加水分解物との脱
水縮重合等で作製することができる加水分解性シラン誘
導体の2〜10量体をいう。
The siloxane oligomer covering the titanium oxide has an average composition formula RpSiXqO (4-pq) / 2 (where R is a functional group comprising one or more monovalent organic groups,
Or, it is a functional group composed of two or more kinds selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <q < 4, which is a number that satisfies the formula 4), wherein the hydrolyzable silane derivative is partially hydrolyzed and polycondensed by dehydration, or the hydrolyzable silane derivative is partially hydrolyzed with tetramethoxysilane. , Tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
It refers to a dimer to dimer of a hydrolyzable silane derivative that can be produced by dehydration polycondensation with a partial hydrolyzate such as diethoxydimethoxysilane.

【0021】酸化チタンを被覆する4官能加水分解性シ
ラン誘導体は、一般式SiX4(式中、Rは一価の有機
基の1種若しくは2種以上からなる官能基、又は、一価
の有機基と水素基から選ばれた2種以上からなる官能基
であり、Xはアルコキシ基、又は、ハロゲン原子であ
る)で表される4官能加水分解性シラン誘導体である。
The tetrafunctional hydrolyzable silane derivative which coats the titanium oxide is represented by the general formula SiX 4 (where R is a functional group comprising one or more monovalent organic groups, or a monovalent organic group) And X is a functional group consisting of two or more selected from hydrogen groups, and X is an alkoxy group or a halogen atom).

【0022】ここで上記4官能加水分解性シラン誘導体
としては、テトラメトキシシラン、テトラエトキシシラ
ン、テトラプロポキシシラン、テトラブトキシシラン、
ジエトキシジメトキシシラン等が好適に利用できる。
Here, the tetrafunctional hydrolyzable silane derivative includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
Diethoxydimethoxysilane and the like can be suitably used.

【0023】酸化チタンを被覆するシリケ−トオリゴマ
−は、平均組成式SiXqO(4-q)/2(式中、Xはアルコ
キシ基、又は、ハロゲン原子であり、qは0<q<4を
満足する数である)で表されるシリケ−トオリゴマ−で
あり、上記4官能加水分解性シラン誘導体の部分加水分
解及び脱水縮重合等で作製することができる4官能加水
分解性シランの2〜10量体をいう。
The silicate oligomer covering the titanium oxide has an average composition of SiXqO (4-q) / 2 (where X is an alkoxy group or a halogen atom, and q satisfies 0 <q <4). 2 to 10 parts of a tetrafunctional hydrolyzable silane which can be prepared by partial hydrolysis, dehydration polycondensation, or the like of the above tetrafunctional hydrolyzable silane derivative. Refers to the body.

【0024】酸化チタン粒子への上記被覆物の固定方法
は、例えば、スプレ−コ−ティング法、ディップコ−テ
ィング法、フロ−コ−ティング法、スピンコ−ティング
法、ロ−ルコ−ティング法、刷毛塗り、スポンジ塗り等
の方法で被覆後、熱処理等の方法で固定する。
Examples of the method of fixing the above-mentioned coating on the titanium oxide particles include a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, and a brush. After coating with a method such as coating or sponge coating, the coating is fixed by a method such as heat treatment.

【0025】コ−ティング組成物には、Ag、Cu、Z
nのような金属を添加することができる。前記金属を添
加した場合、塗膜により形成される表面層は、表面に付
着した細菌や黴を暗所でも死滅させることができる。
The coating composition includes Ag, Cu, Z
A metal such as n can be added. When the metal is added, the surface layer formed by the coating film can kill bacteria and fungi attached to the surface even in a dark place.

【0026】コ−ティング組成物には、Pt、Pd、R
u、Rh、Ir、Osのような白金族金属を添加するこ
とができる。前記金属を添加した場合、塗膜により形成
される表面層は、光触媒の酸化還元活性を増強でき、有
機物汚れの分解性、有害気体や悪臭の分解性を向上させ
ることができる。
The coating composition contains Pt, Pd, R
A platinum group metal such as u, Rh, Ir, Os can be added. When the metal is added, the surface layer formed by the coating film can enhance the oxidation-reduction activity of the photocatalyst, and can improve the decomposability of organic contaminants and harmful gases and odors.

【0027】コ−ティング組成物は、その他に水、エタ
ノ−ル、プロパノ−ル等の溶媒や、塩酸、硝酸、硫酸、
酢酸、マレイン酸等のシリコ−ンの前駆体の加水分解を
促進する触媒や、トリブチルアミン、ヘキシルアミンな
どの塩基性化合物類、アルミニウムトリイソプロポキシ
ド、テトライソプロピルチタネ−トなどの酸性化合物類
等のシリコ−ンの前駆体を硬化させる触媒や、シランカ
ップリング剤等のコ−ティング液の分散性を向上させる
界面活性剤などを添加してもよい。
The coating composition may further contain a solvent such as water, ethanol, propanol, hydrochloric acid, nitric acid, sulfuric acid, or the like.
Catalysts that promote hydrolysis of silicone precursors such as acetic acid and maleic acid, basic compounds such as tributylamine and hexylamine, and acidic compounds such as aluminum triisopropoxide and tetraisopropyl titanate For example, a catalyst for curing the precursor of the silicone such as silane coupling agent or a surfactant for improving the dispersibility of the coating liquid such as a silane coupling agent may be added.

【0028】上記コ−ティング組成物の利用方法は、基
本的には、道路又は鉄道の遮音壁の壁面表面にコ−ティ
ング組成物を塗布し、硬化させて塗膜を形成する。
The method of using the above-mentioned coating composition is basically to apply the coating composition to the wall surface of a sound insulation wall of a road or a railway and to cure the coating composition to form a coating film.

【0029】上記コ−ティング組成物の塗布方法として
は、スプレ−コ−ティング法、ディップコ−ティング
法、フロ−コ−ティング法、スピンコ−ティング法、ロ
−ルコ−ティング法、刷毛塗り、スポンジ塗り等の方法
が好適に利用できる。硬化方法としては、熱処理、室温
放置、紫外線照射等により重合させて行うことができ
る。
The coating method of the above coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.

【0030】上記方法で遮音壁表面に塗膜を形成する
と、壁面表面は光触媒の光励起に応じて親水性を呈する
ようになる。ここで、光触媒の光励起により、基材表面
が高度に親水化されるためには、励起光の照度は0.0
01mW/cm2以上あればよいが、0.01mW/c
m2以上だと好ましく、0.1mW/cm2以上だとより
好ましい。光触媒の光励起に用いる光源としては、太陽
光、室内照明、蛍光灯、水銀灯、白熱電灯、キセノンラ
ンプ、高圧ナトリウムランプ、メタルハライドランプ、
BLBランプ等が好適に利用できる。
When a coating film is formed on the surface of the sound insulating wall by the above method, the surface of the wall surface becomes hydrophilic in response to photoexcitation of the photocatalyst. Here, in order for the substrate surface to be highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.0
0.01 mW / cm 2 or more, but 0.01 mW / c
m2 or more, more preferably 0.1 mW / cm2 or more. Light sources used for photoexcitation of the photocatalyst include sunlight, indoor lighting, fluorescent lamps, mercury lamps, incandescent lamps, xenon lamps, high-pressure sodium lamps, metal halide lamps,
A BLB lamp or the like can be suitably used.

【0031】遮音壁表面に塗膜により形成される表面層
の膜厚は、0.4μm以下にするのが好ましい。そうす
れば、光の乱反射による白濁を防止することができ、表
面層は実質的に透明となる。さらに、表面層の膜厚を、
0.2μm以下にすると一層好ましい。そうすれば、光
の干渉による表面層の発色を防止することができる。ま
た、表面層が薄ければ薄いほどその透明度は向上する。
更に、膜厚を薄くすれば、表面層の耐摩耗性が向上す
る。
The thickness of the surface layer formed of the coating film on the surface of the sound insulating wall is preferably 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, the thickness of the surface layer is
It is more preferable that the thickness be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.

【0032】[0032]

【発明の効果】本発明に係る道路又は鉄道の遮音壁によ
れば、遮音壁表面が水との接触角に換算して10゜以下
の状態になることで、空気中の湿分や湯気が結露して
も、凝縮水が個々の水滴を形成せずに一様な水膜になる
傾向が顕著になる。従って、表面に光散乱性の曇りを生
じない傾向が顕著になる。また、同様に、遮音壁表面が
水との接触角に換算して10゜以下、好ましくは5゜以
下の状態であれば、都市煤塵、自動車等の排気ガスに含
有されるカ−ボンブラック等の燃焼生成物、油脂、シ−
ラント溶出成分等の疎水性汚染物質、及び無機粘土質汚
染物質双方が付着しにくく、付着しても降雨や水洗によ
り簡単に落せる状態になる。
According to the sound insulating wall of a road or a railway according to the present invention, the surface of the sound insulating wall becomes 10 ° or less in terms of a contact angle with water, so that moisture and steam in the air condense. However, condensed water tends to form a uniform water film without forming individual water droplets. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly, if the sound insulation wall surface is in a state of being 10 ° or less, preferably 5 ° or less in terms of a contact angle with water, carbon black contained in exhaust gas from city dust, automobiles, etc. Combustion products, fats and oils, seeds
Both a hydrophobic contaminant such as a runt-eluting component and an inorganic clay contaminant hardly adhere, and even if it adheres, it can be easily dropped by rainfall or washing with water.

【0027】更に、壁面表面が上記高度の親水性を呈
し、かつその状態を維持することで、防曇効果、表面清
浄化効果の他、帯電防止効果(ほこり付着防止効果)、
断熱効果、水中での気泡付着防止効果、熱交換器におけ
る効率向上効果、生体親和性向上効果等が発揮されるよ
うになる。
Further, the surface of the wall surface exhibits the above-mentioned high hydrophilicity, and by maintaining the state, the anti-fogging effect, the surface cleaning effect, the antistatic effect (dust adhesion preventing effect),
The heat insulating effect, the effect of preventing air bubbles from adhering in water, the effect of improving efficiency in a heat exchanger, the effect of improving biocompatibility, and the like are exhibited.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) // C03C 17/30 C03C 17/30 A B Fターム(参考) 4G059 AA01 AA11 AC21 AC22 AC30 EA04 EA18 EB09 FA05 FA22 FA28 FB08 4J038 DL051 DL052 DL071 DL072 HA216 JC31 JC32 KA04 KA15 LA03 MA08 MA10 NA05 NA06 NA26 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // C03C 17/30 C03C 17/30 AB F term (Reference) 4G059 AA01 AA11 AC21 AC22 AC30 EA04 EA18 EB09 FA05 FA22 FA28 FB08 4J038 DL051 DL052 DL071 DL072 HA216 JC31 JC32 KA04 KA15 LA03 MA08 MA10 NA05 NA06 NA26

Claims (9)

【特許請求の範囲】[Claims] 【請求項1】(a)平均組成式RpSiXqO(4-p-q)/2
(式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素であって、硬化させるとシリコ−ン樹
脂の被膜を形成するもの、(b)一般式RpSiX4-p
(式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、pは1または2である)で表
される加水分解性シラン誘導体で表面を被覆した酸化チ
タン粒子であって、前記塗膜形成要素中に分散され、光
励起によって前記被膜の表面のシリコ−ン分子中のケイ
素原子に結合した有機基を光触媒作用により少なくとも
部分的に水酸基に置換させ、さらに光励起に応じて被膜
の表面を親水化するための光触媒性酸化チタン粒子、を
含有することを特徴とする光触媒性親水性コ−ティング
組成物。
(1) An average composition formula RpSiXqO (4-pq) / 2
(In the formula, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is an alkoxy group. And p and q are 0 <p <2, 0 <
q is a number that satisfies q <4), and which forms a silicone resin film when cured, and (b) a siloxane compound represented by the general formula RpSiX4-p
(In the formula, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is an alkoxy group. A titanium oxide particle whose surface is coated with a hydrolyzable silane derivative represented by the following formula: or a halogen atom, and p is 1 or 2. Photocatalytic titanium oxide particles for at least partially replacing an organic group bonded to a silicon atom in a silicon molecule on the surface of the coating with a hydroxyl group by photocatalysis, and further hydrophilizing the surface of the coating in response to photoexcitation. A photocatalytic hydrophilic coating composition comprising:
【請求項2】(a)平均組成式RpSiXqO(4-p-q)/2
(式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素であって、硬化させるとシリコ−ン樹
脂の被膜を形成するもの、(b)平均組成式RpSiXq
O(4-p-q)/2(式中、Rは一価の有機基の1種若しくは
2種以上からなる官能基、又は、一価の有機基と水素基
から選ばれた2種以上からなる官能基であり、Xはアル
コキシ基、又は、ハロゲン原子であり、p及びqは0<
p<2、0<q<4を満足する数である)で表されるシ
ロキサンオリゴマ−で表面を被覆した酸化チタン粒子で
あって、前記塗膜形成要素中に分散され、光励起によっ
て前記被膜の表面のシリコ−ン分子中のケイ素原子に結
合した有機基を光触媒作用により少なくとも部分的に水
酸基に置換させ、さらに光励起に応じて被膜の表面を親
水化するための光触媒性酸化チタン粒子、を含有するこ
とを特徴とする光触媒性親水性コ−ティング組成物。
2. (a) Average composition formula RpSiXqO (4-pq) / 2
(In the formula, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is an alkoxy group. And p and q are 0 <p <2, 0 <
q is a number that satisfies q <4), which forms a silicone resin film when cured, and (b) an average composition formula RpSiXq
O (4-pq) / 2 (wherein, R is a functional group composed of one or more monovalent organic groups, or two or more selected from monovalent organic groups and hydrogen groups) X is an alkoxy group or a halogen atom, and p and q are 0 <
p <2, 0 <q <4) titanium oxide particles whose surface is coated with a siloxane oligomer represented by the following formula: Photocatalytic titanium oxide particles for at least partially replacing an organic group bonded to a silicon atom in a silicon molecule on the surface with a hydroxyl group by photocatalysis and further hydrophilizing the surface of the film in response to photoexcitation. A photocatalytic hydrophilic coating composition comprising:
【請求項3】(a)平均組成式RpSiXqO(4-p-q)/2
(式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素であって、硬化させるとシリコ−ン樹
脂の被膜を形成するもの、(b)一般式SiX4(式
中、Rは一価の有機基の1種若しくは2種以上からなる
官能基、又は、一価の有機基と水素基から選ばれた2種
以上からなる官能基であり、Xはアルコキシ基、又は、
ハロゲン原子である)で表される4官能加水分解性シラ
ン誘導体で表面を被覆した酸化チタン粒子であって、前
記塗膜形成要素中に分散され、光励起によって前記被膜
の表面のシリコ−ン分子中のケイ素原子に結合した有機
基を光触媒作用により少なくとも部分的に水酸基に置換
させ、さらに光励起に応じて被膜の表面を親水化するた
めの光触媒性酸化チタン粒子、を含有することを特徴と
する光触媒性親水性コ−ティング組成物。
3. (a) Average composition formula RpSiXqO (4-pq) / 2
(In the formula, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is an alkoxy group. And p and q are 0 <p <2, 0 <
a film-forming element composed of a siloxane represented by the following formula: q <4, which forms a silicone resin film when cured; (b) a general formula SiX4 (wherein R Is a functional group consisting of one or more monovalent organic groups, or a functional group consisting of two or more selected from monovalent organic groups and hydrogen groups, and X is an alkoxy group, or
Titanium oxide particles whose surface is coated with a tetrafunctional hydrolyzable silane derivative represented by the following formula: A photocatalytic titanium oxide particle for at least partially substituting an organic group bonded to a silicon atom with a hydroxyl group by photocatalysis and further hydrophilizing the surface of the coating in response to photoexcitation. Hydrophilic hydrophilic coating composition.
【請求項4】(a)平均組成式RpSiXqO(4-p-q)/2
(式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素であって、硬化させるとシリコ−ン樹
脂の被膜を形成するもの、(b)平均組成式SiXqO
(4-q)/2(式中、Xはアルコキシ基、又は、ハロゲン原
子であり、qは0<q<4を満足する数である)で表さ
れるシリケ−トオリゴマ−で表面を被覆した酸化チタン
粒子であって、前記塗膜形成要素中に分散され、光励起
によって前記被膜の表面のシリコ−ン分子中のケイ素原
子に結合した有機基を光触媒作用により少なくとも部分
的に水酸基に置換させ、さらに光励起に応じて被膜の表
面を親水化するための光触媒性酸化チタン粒子、を含有
することを特徴とする光触媒性親水性コ−ティング組成
物。
4. An average compositional formula RpSiXqO (4-pq) / 2.
(In the formula, R is a functional group composed of one or more monovalent organic groups, or a functional group composed of two or more monovalent organic groups and hydrogen groups, and X is an alkoxy group. And p and q are 0 <p <2, 0 <
q <4 that satisfies q <4), which forms a silicone resin film when cured, and (b) an average compositional formula SiXqO
The surface was coated with a silicate oligomer represented by (4-q) / 2 (wherein X is an alkoxy group or a halogen atom, and q is a number satisfying 0 <q <4). Titanium oxide particles, wherein the organic groups dispersed in the coating film forming element and bonded to silicon atoms in silicon molecules on the surface of the coating film by photoexcitation are at least partially replaced with hydroxyl groups by photocatalysis, A photocatalytic hydrophilic coating composition, which further comprises photocatalytic titanium oxide particles for hydrophilizing the surface of the coating in response to photoexcitation.
【請求項5】 光励起に応じて表面が斯く親水化された
前記被膜は、その表面に付着した湿分の凝縮水及び/又
は水滴が被膜の表面に広がるのを可能にし、以て、該被
膜によって被覆された基材が湿分の凝縮水及び/又は水
滴によって曇り若しくは翳るのを防止することを特徴と
する請求項1〜4に記載の光触媒性親水性コ−ティング
組成物。
5. The coating, the surface of which has been hydrophilized in response to photoexcitation, allowing the condensed water and / or water droplets of moisture adhering to the surface to spread on the surface of the coating, whereby the coating The photocatalytic hydrophilic coating composition according to any one of claims 1 to 4, wherein the substrate coated with is prevented from being clouded or overcast by condensed water and / or water droplets of moisture.
【請求項6】 光励起に応じて表面が斯く親水化された
前記被膜は、降雨にさらされた時に付着堆積物及び/又
は汚染物が雨水により洗い流されるのを可能にし、以
て、表面の自己浄化を可能にすることを特徴とする請求
項1〜4に記載の光触媒性親水性コ−ティング組成物。
6. The coating, the surface of which has been hydrophilized in response to photo-excitation, allows for deposits and / or contaminants to be washed away by rainwater when exposed to rainfall, whereby the surface self The photocatalytic hydrophilic coating composition according to any one of claims 1 to 4, which enables purification.
【請求項7】 光励起に応じて表面が斯く親水化された
前記被膜は、汚染物を含んだ雨水が接触したときに汚染
物が表面に付着するのを防止することを特徴とする請求
項1〜4に記載の光触媒性親水性コ−ティング組成物。
7. The coating whose surface has been hydrophilized in response to photoexcitation prevents contamination from adhering to the surface when rainwater containing the contamination comes into contact. 5. The photocatalytic hydrophilic coating composition according to any one of items 1 to 4.
【請求項8】 光励起に応じて表面が斯く親水化された
前記被膜は、水に浸漬したとき又は水で濡らしたときに
付着堆積物及び/又は汚染物を釈放し、以て、表面を水
で洗浄するのを容易にすることを特徴とする請求項1〜
4に記載の光触媒性親水性コ−ティング組成物。
8. The coating, the surface of which has been hydrophilized in response to photoexcitation, releases adhering deposits and / or contaminants when immersed in or wetted with water, thereby causing the surface to become hydrated. 3. The method according to claim 1, wherein the cleaning is facilitated.
5. The photocatalytic hydrophilic coating composition according to item 4.
【請求項9】 請求項1〜8に記載のコ−ティング組成
物をpH3〜8の溶媒に分散させてなる組成物。
9. A composition obtained by dispersing the coating composition according to claim 1 in a solvent having a pH of 3 to 8.
JP2002020533A 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall Expired - Fee Related JP3882625B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002020533A JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP7-354649 1995-12-22
JP35464995 1995-12-22
JP2002020533A JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP34047196A Division JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition

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Publication Number Publication Date
JP2002302646A true JP2002302646A (en) 2002-10-18
JP3882625B2 JP3882625B2 (en) 2007-02-21

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ID=18438979

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JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
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JP28895496A Expired - Fee Related JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
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JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8323516A Pending JPH09241038A (en) 1995-12-22 1996-11-19 Photocatalytic hydrophilic member and its production
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
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JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

Family Applications Before (69)

Application Number Title Priority Date Filing Date
JP8083499A Pending JPH09231821A (en) 1995-12-22 1996-04-05 Luminaire and method for maintaining illuminance
JP13408196A Expired - Lifetime JP3385850B2 (en) 1995-12-22 1996-04-19 Composite material with hydrophilicity
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JP15017196A Expired - Lifetime JP3760509B2 (en) 1995-12-22 1996-05-22 Greenhouse ceiling and its condensation prevention method
JP8150410A Pending JPH09225263A (en) 1995-12-22 1996-05-23 Air pollutant removing filter, air pollutant removing fan and ventilator using the fan
JP8156383A Pending JPH09231849A (en) 1995-12-22 1996-05-29 Insulator and dirt preventing method therefore
JP13653596A Expired - Lifetime JP3339304B2 (en) 1995-12-22 1996-05-30 Painted object and painting method
JP8136777A Pending JPH09227178A (en) 1995-12-22 1996-05-30 Laminated glass and its production
JP13782996A Ceased JP3189682B2 (en) 1995-12-22 1996-05-31 Antifouling material
JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
JP8145265A Pending JPH09225276A (en) 1995-12-22 1996-06-07 Separating membrane and formation of surface layer to separating membrane
JP8168662A Pending JPH09225389A (en) 1995-12-22 1996-06-10 Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture
JP8158518A Pending JPH09225021A (en) 1995-12-22 1996-06-19 Medical material
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JP8272814A Pending JPH09226041A (en) 1995-12-22 1996-09-06 Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member
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JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
JP8275189A Pending JPH09231807A (en) 1995-12-22 1996-09-10 Vehicle headlight cover, vehicle with it, and its defogging method
JP8238927A Pending JPH09227159A (en) 1995-12-22 1996-09-10 Front and rear window glass of vehicle
JP27519096A Expired - Lifetime JP3277983B2 (en) 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method
JP28122196A Expired - Lifetime JP3743075B2 (en) 1995-12-22 1996-09-17 Antifogging dental mirror and antifogging method
JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
JP8281223A Expired - Lifetime JP3063968B2 (en) 1995-12-22 1996-09-17 Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror
JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
JP8281225A Pending JPH09230107A (en) 1995-12-22 1996-09-17 Anti-fogging glass lens and its anti-fogging method
JP8281222A Pending JPH09230106A (en) 1995-12-22 1996-09-17 Anti-fogging camera filter and its anti-fogging method
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
JP08282811A Expired - Fee Related JP3075195B2 (en) 1995-12-22 1996-09-18 Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror
JP8282808A Pending JPH09228765A (en) 1995-12-22 1996-09-18 Blind and manufacture thereof
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
JP8282810A Pending JPH09228545A (en) 1995-12-22 1996-09-18 Glass block and its cleaning method
JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
JP8282805A Pending JPH09231499A (en) 1995-12-22 1996-09-18 Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal
JP8282806A Pending JPH09228057A (en) 1995-12-22 1996-09-18 Wheel and its cleaning method
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP8284532A Pending JPH09227805A (en) 1995-12-22 1996-09-19 Photocatalytic hydrophilic coating composition
JP28453496A Expired - Lifetime JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
JP28895696A Expired - Fee Related JP3588206B2 (en) 1995-12-22 1996-09-25 Self-cleaning road decorative panel, and method of cleaning road decorative panel
JP28895496A Expired - Fee Related JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8323516A Pending JPH09241038A (en) 1995-12-22 1996-11-19 Photocatalytic hydrophilic member and its production
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP34300999A Expired - Fee Related JP3844182B2 (en) 1995-12-22 1999-12-02 Hydrophilic film and method for producing and using the same
JP2000180301A Expired - Lifetime JP3414365B2 (en) 1995-12-22 2000-06-15 Building materials for exterior walls
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000181287A Expired - Fee Related JP3465664B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating

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JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10325768A1 (en) * 2003-06-05 2004-12-23 Chemetall Gmbh Coating system for glass surfaces, process for its production and its application

Families Citing this family (196)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JPH09227779A (en) * 1995-12-22 1997-09-02 Toto Ltd Rubber member for construction and impartment of hydrophilicity to surface thereof
JPH09230105A (en) * 1995-12-22 1997-09-05 Toto Ltd Antifogging method and facility applied with the method
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance
JPH09186949A (en) * 1995-12-27 1997-07-15 Toshiba Lighting & Technol Corp Video equipment
JP3400259B2 (en) * 1996-08-26 2003-04-28 セントラル硝子株式会社 Hydrophilic coating and method for producing the same
JP3949788B2 (en) * 1996-09-17 2007-07-25 大野 隆司 Goods storage container
JP4305001B2 (en) * 1996-09-20 2009-07-29 株式会社日立製作所 Articles with a photocatalytic film
CN1254365C (en) * 1996-09-20 2006-05-03 株式会社日立制作所 Thin photocatalytic film and articles provided with the same
JPH10148705A (en) * 1996-11-21 1998-06-02 Hitachi Chem Co Ltd Antifog treatment
JP3467994B2 (en) * 1996-11-27 2003-11-17 松下電工株式会社 Silicone transfer film and transfer structure thereof
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
JP4672822B2 (en) * 1997-02-24 2011-04-20 株式会社ティオテクノ Hydrophilic coating agent and surface hydrophilic substrate
JP3518251B2 (en) * 1997-05-20 2004-04-12 株式会社日立製作所 Oxide photocatalytic thin film and article provided with the same
JPH1190236A (en) * 1997-09-22 1999-04-06 Ebara Corp Photocatalyst and reaction device using photocatalyst
JPH11100695A (en) * 1997-09-26 1999-04-13 Nippon Alum Co Ltd Production of titanium material having photocatalytic activity
JPH11100526A (en) * 1997-09-29 1999-04-13 Toto Ltd Photocatalytic hydrophilic member and photocatalytic hydrophilic coating composition
JP3996682B2 (en) * 1997-10-20 2007-10-24 日本デコール株式会社 Decorative sheet having organic substance decomposing function and method for producing the same
JPH11152447A (en) * 1997-11-21 1999-06-08 Toto Ltd Surface-treating agent for forming photocatalyzing coating film, and formation of photocatalyzing coating film using the surface-treating agent
KR100740055B1 (en) * 1997-12-25 2007-10-18 산젠 가꼬 가부시키가이샤 Anti-fogging laminates
JPH11197516A (en) * 1998-01-09 1999-07-27 Takenaka Komuten Co Ltd Photocatalyst material and its production
WO1999041322A1 (en) * 1998-02-10 1999-08-19 Toto Ltd. Coating material for forming photocatalytic hydrophilic film, method of forming photocatalytic hydrophilic film, and photocatalytic hydrophilic member
JPH11263950A (en) * 1998-03-16 1999-09-28 Nippon Carbide Ind Co Inc Transparent adhesive sheet for preventing dew condensation and dew condensation-preventing deflective sign
CN1263544A (en) * 1998-04-10 2000-08-16 松下电工株式会社 Inorganic coating composition and hydrophilic inorganic coating film
JPH11347482A (en) * 1998-06-12 1999-12-21 Dainippon Toryo Co Ltd Production of joint part coated porcelain tile panel
CH693138A5 (en) * 1998-06-19 2003-03-14 Unaxis Trading Ag Laminated glass and method for making a coated plastic film therefor.
KR100290066B1 (en) * 1998-07-13 2001-05-15 김명신 How to fix titanium dioxide, used as an air freshener, on activated carbon
TW473400B (en) 1998-11-20 2002-01-21 Asahi Chemical Ind Modified photocatalyst sol
JP2000226234A (en) * 1998-12-03 2000-08-15 Toto Ltd Hydrophilic member
JP3340688B2 (en) * 1999-01-28 2002-11-05 シャープ株式会社 Air conditioner
EP1023910A1 (en) * 1999-01-29 2000-08-02 Institut Straumann AG Preparation of osteophilic surfaces for metallic prosthetic devices anchorable to bone
WO2000046154A1 (en) * 1999-02-04 2000-08-10 Japan Science And Technology Corporation Process for producing anatase titania or composite oxide containing anatase titania
JP2000234892A (en) * 1999-02-12 2000-08-29 Zexel Corp Method for reducing heat exchanger and heat exchanger manufactured by that method
JP4165014B2 (en) 1999-03-09 2008-10-15 Toto株式会社 Hydrophilic member, method for producing the same, coating agent and apparatus for the production
JP4029516B2 (en) * 1999-03-18 2008-01-09 株式会社Inax Photocatalytic tile
KR100308818B1 (en) * 1999-04-01 2001-09-26 이계안 Hydrophilic coating glass coated with porous thin layer of TiO2
JP4345941B2 (en) * 1999-04-16 2009-10-14 ベック株式会社 Coating method
US6485838B1 (en) 1999-05-21 2002-11-26 Jsr Corporation Coating composition, and a coated film and glass each having a coating layer comprised thereof
JP2000334308A (en) * 1999-05-25 2000-12-05 Shinichi Harigai Cafrrier for photocatalyst and photocatalyst using the same
FR2794225B3 (en) * 1999-05-25 2001-06-15 Saint Gobain Vitrage REFRIGERATED ENCLOSURE DOOR WITH VACUUM WINDOWS
JP2000334309A (en) * 1999-05-25 2000-12-05 Shinichi Harigai Photocatalyst
JP4513141B2 (en) * 1999-06-21 2010-07-28 パナソニック株式会社 air purifier
JP4507302B2 (en) * 1999-08-10 2010-07-21 凸版印刷株式会社 High refractive index composition
EP1081108B1 (en) 1999-09-02 2004-02-25 Central Glass Company, Limited Article with photocatalytic film
JP2001080974A (en) * 1999-09-08 2001-03-27 Fuji Photo Film Co Ltd Composite base plate material and method for producing the same
WO2001025362A1 (en) * 1999-10-01 2001-04-12 Nippon Soda Co., Ltd. Sheet for transferring photocatalyst
JP2001164117A (en) * 1999-12-07 2001-06-19 Toppan Printing Co Ltd High-refractive-index composition and antireflection laminate
TW468053B (en) * 1999-12-14 2001-12-11 Nissan Chemical Ind Ltd Antireflection film, process for forming the antireflection film, and antireflection glass
US6603320B2 (en) 2000-02-07 2003-08-05 Organo Corporation Electric conductometer, electrode for measuring electric conductivity, and method for producing the same
US8632583B2 (en) 2011-05-09 2014-01-21 Palmaz Scientific, Inc. Implantable medical device having enhanced endothelial migration features and methods of making the same
US6866937B2 (en) 2000-08-22 2005-03-15 Central Glass Company, Limited Glass plate with oxide film and process for producing same
KR100631104B1 (en) * 2000-11-03 2006-10-02 한국유리공업주식회사 Hydrophilic glass coated with metal oxide and method for producing it
JP2002159910A (en) * 2000-11-27 2002-06-04 Cleanup Corp Method for forming photocatalytic coating film on surface of base material
JP4755756B2 (en) * 2000-12-20 2011-08-24 日本テトラパック株式会社 Photocatalytic material
AR032424A1 (en) 2001-01-30 2003-11-05 Procter & Gamble COATING COMPOSITIONS TO MODIFY SURFACES.
KR20030085017A (en) * 2001-03-21 2003-11-01 가부시키가이샤 브리지스톤 Method for forming antifouling coating and antifouling material having antifouling coating
JP2002285036A (en) * 2001-03-23 2002-10-03 Seiichi Rengakuji Photocatalyst supported aluminum material and its manufacturing method
KR100393733B1 (en) * 2001-03-28 2003-08-06 홍국선 Ceramic Compositions for superhydrophilic coating and its manufacturing method
US6827966B2 (en) * 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
EP1434607A1 (en) * 2001-10-11 2004-07-07 Straumann Holding AG Osteophilic implants
JP2003135228A (en) * 2001-11-02 2003-05-13 Sanyo Electric Co Ltd Low temperature show case
JP2005517477A (en) * 2002-02-14 2005-06-16 エルジー エレクトロニクス インコーポレーテッド Washing machine door and manufacturing method thereof
US6938546B2 (en) 2002-04-26 2005-09-06 Mitsubishi Heavy Industries, Ltd. Printing press, layered formation and making method thereof, and printing plate and making method thereof
CN1301795C (en) 2002-06-03 2007-02-28 旭化成株式会社 Photocatalyst composition
JP4169557B2 (en) * 2002-09-19 2008-10-22 旭化成ケミカルズ株式会社 Photocatalyst
JP4069369B2 (en) 2002-09-25 2008-04-02 信越化学工業株式会社 Antireflection film and method of manufacturing antireflection film
US8679517B2 (en) 2002-09-26 2014-03-25 Palmaz Scientific, Inc. Implantable materials having engineered surfaces made by vacuum deposition and method of making same
AU2003272710B2 (en) 2002-09-26 2008-05-15 Vactronix Scientific, Llc Implantable materials having engineered surfaces and method of making same
US8268340B2 (en) 2002-09-26 2012-09-18 Advanced Bio Prosthetic Surfaces, Ltd. Implantable materials having engineered surfaces and method of making same
JP2003231204A (en) * 2002-12-09 2003-08-19 Toto Ltd Functional material and functional coating composition
JP3707737B2 (en) * 2003-03-06 2005-10-19 重岡 誠司 Outdoor heat exchanger
JP4493290B2 (en) * 2003-06-23 2010-06-30 菊治 山下 Artificial biomaterial and method for producing the same
US20050040151A1 (en) 2003-08-20 2005-02-24 Robert Dyrdek Heated side window glass
JP2005096336A (en) * 2003-09-26 2005-04-14 Lintec Corp Process film for ceramic green sheet production and its production method
JP2005186353A (en) * 2003-12-25 2005-07-14 Murakami Corp Anti-fogging element
JP4995428B2 (en) * 2004-03-10 2012-08-08 東海旅客鉄道株式会社 Titanium oxide coating formation method
JP2008510186A (en) * 2004-08-10 2008-04-03 日本板硝子株式会社 LCD mirror system and method
JP4758086B2 (en) * 2004-09-09 2011-08-24 タキロン株式会社 Construction structure using a sealing material used for polycarbonate resin parts with photocatalytic function
NZ554581A (en) 2004-09-20 2011-03-31 Agc Flat Glass Na Inc Anti-fog refrigeration door and method of making the same
JP2006091249A (en) 2004-09-22 2006-04-06 Murakami Corp Camera
KR101231894B1 (en) * 2004-12-28 2013-02-08 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 Photocatalytic auto-cleaning process of stains
JPWO2006088079A1 (en) * 2005-02-18 2008-07-03 日本曹達株式会社 Organic inorganic composite
CN101171357B (en) 2005-02-24 2010-05-19 财团法人电力中央研究所 Process for producing multifunctional material
EP1852183A4 (en) 2005-02-24 2011-06-29 Central Res Inst Elect Multifunctional material
JP4814534B2 (en) * 2005-02-28 2011-11-16 財団法人電力中央研究所 Manufacturing method of structural materials
JP4771359B2 (en) * 2005-02-28 2011-09-14 財団法人電力中央研究所 Playground equipment
JP4995425B2 (en) * 2005-02-28 2012-08-08 一般財団法人電力中央研究所 Irrigation apparatus, irrigation member, manufacturing method thereof, and irrigation system
JP4958029B2 (en) * 2005-02-28 2012-06-20 一般財団法人電力中央研究所 Building materials
JP4807724B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Rail vehicle manufacturing method
JP4807723B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method of heat-resistant member
JP4480014B2 (en) * 2005-02-28 2010-06-16 財団法人電力中央研究所 Rocket parts
JP4807725B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method of energy generating equipment
JP4807722B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method for environmentally resistant equipment
JP4843231B2 (en) * 2005-02-28 2011-12-21 財団法人電力中央研究所 Kitchen products
JP4541929B2 (en) * 2005-02-28 2010-09-08 財団法人電力中央研究所 Flying object
JP2006247760A (en) * 2005-03-08 2006-09-21 Disco Abrasive Syst Ltd Machining apparatus
TW200631899A (en) 2005-03-09 2006-09-16 Tokai Ryokaku Tetsudo Kk Titanium oxide-coating agent, and forming method for titanium oxide-coating film
JP4659494B2 (en) * 2005-03-23 2011-03-30 株式会社ミクニ Infrared transmitting window material, infrared sensor unit, and combustion apparatus
US7757629B2 (en) * 2005-04-14 2010-07-20 Transitions Optical, Inc. Method and apparatus for coating an optical article
KR100796718B1 (en) * 2005-08-10 2008-01-21 요시노리 나카가와 Method for manufacturing photoelectro-chemical cell and photoelectro-chemical cell
JP3795515B1 (en) * 2005-08-10 2006-07-12 善典 中川 Manufacturing method of semiconductor photoelectrochemical cell
WO2007052815A1 (en) * 2005-11-04 2007-05-10 Tokuyama Corporation Coater
JP5004561B2 (en) * 2005-11-30 2012-08-22 株式会社トクヤマ Coating equipment
GB0602933D0 (en) 2006-02-14 2006-03-22 Pilkington Automotive Ltd Vehicle glazing
EP1829991A1 (en) * 2006-03-02 2007-09-05 UGINE &amp; ALZ FRANCE Stainless steel plate coated with self-cleaning coating.
JP2007247166A (en) * 2006-03-14 2007-09-27 Sumitomo Chemical Co Ltd Road mirror
JP2007262498A (en) * 2006-03-28 2007-10-11 National Institute Of Advanced Industrial & Technology Color-controlled titanium alloy bolt and nut
JP4849525B2 (en) * 2006-04-04 2012-01-11 花王株式会社 Resin composition
JP2007277935A (en) * 2006-04-07 2007-10-25 Sekisui Jushi Co Ltd Indicating body for road
JP2008013833A (en) * 2006-07-07 2008-01-24 National Institute Of Advanced Industrial & Technology Titanium alloy member which develops controlled color
JP4966614B2 (en) * 2006-09-14 2012-07-04 Mkvドリーム株式会社 Agricultural film
JP2008114760A (en) * 2006-11-06 2008-05-22 Asahi Glass Co Ltd Vehicle with anti-fogging glass and set of vehicle window glass
JP4823045B2 (en) * 2006-12-12 2011-11-24 旭化成ケミカルズ株式会社 Water-based photocatalytic composition
JP5064817B2 (en) * 2007-01-30 2012-10-31 トヨタ自動車株式会社 Method for preventing contamination of automobile wheel and automobile wheel
JP2008184357A (en) * 2007-01-30 2008-08-14 National Institute Of Advanced Industrial & Technology Method of making surface of oxide amphiphilic
US7659226B2 (en) 2007-02-26 2010-02-09 Envont Llc Process for making photocatalytic materials
JP2008260667A (en) * 2007-04-13 2008-10-30 Univ Of Electro-Communications Method for manufacturing titanium oxide thin film and resin product with titanium oxide thin film
KR100809030B1 (en) * 2007-05-08 2008-03-03 주식회사 에임하이글로벌 Board for road facilities and preparation method thereof
JP2009002979A (en) * 2007-06-19 2009-01-08 Mitsubishi Electric Corp Video display device and its manufacturing method
JP5510911B2 (en) * 2007-08-17 2014-06-04 株式会社伸興サンライズ Composite interior coating material for buildings
JP2007327071A (en) * 2007-08-23 2007-12-20 Kawasaki Heavy Ind Ltd Method for producing hydrophilic coating composition
JP2009090641A (en) 2007-09-20 2009-04-30 Fujifilm Corp Anticlouding cover and cover for meter using it
JP5705398B2 (en) * 2007-12-05 2015-04-22 トヨタ自動車株式会社 Vehicle wheels and wheel caps
JP5145023B2 (en) * 2007-12-19 2013-02-13 住友軽金属工業株式会社 Fin material for heat exchanger and manufacturing method thereof
US7910085B2 (en) 2007-12-28 2011-03-22 Tdk Corporation Process for production of iron oxyhydroxide particles
JP4993745B2 (en) * 2007-12-28 2012-08-08 株式会社アルバック Deposition equipment
JP2009185107A (en) * 2008-02-04 2009-08-20 Pialex Technologies Corp Hydrophilic coating material and hydrophilic coated object
KR101104262B1 (en) * 2008-12-31 2012-01-11 주식회사 노루홀딩스 Article wih self-cleaning effect and method of preparation thereof
JP5267308B2 (en) * 2009-04-28 2013-08-21 信越化学工業株式会社 Photocatalyst coating liquid that provides a photocatalytic thin film excellent in photoresponsiveness and the photocatalytic thin film
US20110008612A1 (en) * 2009-07-10 2011-01-13 Korea University Research And Business Foundation Self-cleaning surfaces
JP5365500B2 (en) * 2009-12-24 2013-12-11 平岡織染株式会社 Non-flammable interior illuminated signboard
JP5365501B2 (en) * 2009-12-24 2013-12-11 平岡織染株式会社 Non-flammable interior illuminated signboard
JP5411791B2 (en) * 2010-04-23 2014-02-12 三菱レイヨン株式会社 Manufacturing method of laminated resin plate
CN101830644B (en) * 2010-05-14 2012-11-14 中国科学院上海技术物理研究所 High-stability car coated glass membrane system
JP5810294B2 (en) * 2010-07-27 2015-11-11 パナソニックIpマネジメント株式会社 Rainwater collecting wall material
US9221031B2 (en) 2010-07-29 2015-12-29 Toto Ltd. Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material
WO2012014877A1 (en) 2010-07-29 2012-02-02 Toto株式会社 Photocatalyst coated body and photocatalyst coating liquid
HUE036624T2 (en) * 2010-09-28 2018-07-30 Dow Global Technologies Llc Reactive flow static mixer with cross-flow obstructions and mixing method
JP2012086104A (en) * 2010-10-15 2012-05-10 Asahi Kasei Chemicals Corp Photocatalyst composition
JP2012087213A (en) * 2010-10-19 2012-05-10 Nippon Parkerizing Co Ltd Hydrophilic film for metal material, hydrophilization-treating agent, and hydrophilization-treating method
US8728563B2 (en) 2011-05-03 2014-05-20 Palmaz Scientific, Inc. Endoluminal implantable surfaces, stents, and grafts and method of making same
WO2013024897A1 (en) * 2011-08-18 2013-02-21 株式会社インパクト Guidance display board
JP2013096959A (en) * 2011-11-04 2013-05-20 Shiyouichi Yoshino Radioactive decontamination method
JP5250685B2 (en) * 2011-11-25 2013-07-31 パナソニック株式会社 Camera cover and camera
KR20130118456A (en) * 2012-04-20 2013-10-30 호서대학교 산학협력단 Ozone contactor with static mixer
JP6171275B2 (en) * 2012-07-02 2017-08-02 大日本印刷株式会社 Transparent film and method for producing the same
JP6028495B2 (en) * 2012-09-27 2016-11-16 Toto株式会社 Photocatalyst member
CN102923836A (en) * 2012-11-15 2013-02-13 常州大学 Method for treating washing wastewater by using composite-film modified sintered gangue ceramsite
JP6105998B2 (en) * 2013-03-26 2017-03-29 パナホーム株式会社 Method for producing photocatalyst composition and method for producing photocatalyst
CN105732125B (en) * 2013-11-30 2018-03-13 国网河南省电力公司平顶山供电公司 A kind of porcelain and glass insulator low-temperature resistance coating
CN105960384B (en) * 2014-02-05 2019-04-02 Agc株式会社 The manufacturing method of laminated glass
CN104047343A (en) * 2014-06-20 2014-09-17 欧士玺 Mobile toilet capable of recycling water
EP3175899B1 (en) 2014-07-30 2019-03-13 Mitsubishi Materials Corporation Filter medium, method for producing filter medium, water treatment module, and water treatment device
US10208210B2 (en) 2014-07-30 2019-02-19 Mitsubishi Materials Corporation Hydrophilic oil repellent and production method of same, surface coating material, coating film, resin composition, oil-water separation filter material, and porous body
JP5909604B1 (en) 2014-07-30 2016-04-26 三菱マテリアル株式会社 Surface coating material, coating film and hydrophilic oil-repellent material
JP6461573B2 (en) 2014-07-30 2019-01-30 三菱マテリアル株式会社 Oil / water separator / collector
KR101942261B1 (en) * 2014-09-24 2019-01-28 (주)엘지하우시스 Visible light active photocatalyst tile
KR101642870B1 (en) * 2014-10-21 2016-08-29 가천대학교 산학협력단 Endoscope
JP2016104681A (en) * 2014-12-01 2016-06-09 大日本印刷株式会社 Method for producing laminated glass, and laminated glass
WO2016136395A1 (en) * 2015-02-27 2016-09-01 富士フイルム株式会社 Gas separation asymmetric membrane, gas separation module, gas separation device, and gas separation method
CN104720649B (en) * 2015-03-18 2017-03-01 杭州桑莱特卫浴有限公司 A kind of bathroom cabinet and its production method
CN104848985B (en) * 2015-06-05 2017-03-08 合肥工业大学 A kind of vacuum detecting method based on infrared laser spectroscopy and system
WO2017022075A1 (en) * 2015-08-04 2017-02-09 三菱電機株式会社 Elevator car panel
JP2017090380A (en) * 2015-11-16 2017-05-25 株式会社デンソーウェーブ Laser radar device, window member for laser radar device, and control program for laser radar device
CN105349042A (en) * 2015-11-20 2016-02-24 杨京广 Silicon carbide coating and use method thereof
CN105444486A (en) * 2015-12-31 2016-03-30 广西路桥工程集团有限公司 Multi-way valve circulation system for cooling system
JP6811415B2 (en) * 2016-01-29 2021-01-13 パナソニックIpマネジメント株式会社 urinal
JP2017165612A (en) * 2016-03-16 2017-09-21 Towa株式会社 Translucent material, low adhesion material and molding member
CN105694688B (en) * 2016-03-16 2017-09-26 曲阜师范大学 A kind of fast preparation method of high intensity super-hydrophobic coat
CN107313490A (en) * 2016-04-26 2017-11-03 厦门致杰智能科技有限公司 A kind of Split intelligent toilet seat
CN105860692A (en) * 2016-04-29 2016-08-17 南京晨光艺术工程有限公司 Self-cleaning Buddha statue
CN106242314A (en) * 2016-08-23 2016-12-21 张洪建 A kind of glass copper-plating technique
CN108261086A (en) * 2017-01-03 2018-07-10 佛山市顺德区美的电热电器制造有限公司 The preparation method of Anti-fog mirror, cooking apparatus and Anti-fog mirror
JP6814473B2 (en) * 2017-02-28 2021-01-20 国立大学法人東北大学 Photocatalytic functional member and its manufacturing method
JP6428864B2 (en) * 2017-07-03 2018-11-28 大日本印刷株式会社 Transparent film and method for producing the same
KR102138411B1 (en) * 2017-07-07 2020-07-27 주식회사 엘지화학 Coating composition including the same, organic light emitting device using the same and method of manufacturing the same
JP2019070247A (en) * 2017-10-06 2019-05-09 スリーエム イノベイティブ プロパティズ カンパニー Window film
TW202307471A (en) * 2018-01-30 2023-02-16 美商菲爾薇解析公司 Optical device having optical and mechanical properties
CN108383396A (en) * 2018-02-27 2018-08-10 张家港外星人新材料科技有限公司 The double-deck film glass with anti-reflection film and antistatic automatically cleaning film and its preparation method
JP2019158247A (en) * 2018-03-14 2019-09-19 株式会社デンソー Heat exchanger
CN110157224A (en) * 2018-03-14 2019-08-23 成都今天化工有限公司 A method of preparing nano ceramics anti-pollution flashover coating
PL425045A1 (en) * 2018-03-28 2019-10-07 Uniwersytet Jagielloński Method for producing nanoporous semiconducting layers of metal oxides
KR101917149B1 (en) 2018-05-17 2018-11-09 주식회사 대수하이테크 Anti-fouling coating composition having excellent weatherability
JP7086744B2 (en) * 2018-06-22 2022-06-20 株式会社東芝 Camera system
JP7329909B2 (en) * 2018-06-28 2023-08-21 小林製薬株式会社 Coating agent for toilet bowl
JP2020069684A (en) * 2018-10-30 2020-05-07 三井化学株式会社 Multilayer structure
JP7290938B2 (en) * 2018-12-11 2023-06-14 イビデン株式会社 Manufacturing method of cover for infrared detection element
JP2020106751A (en) * 2018-12-28 2020-07-09 ホヤ レンズ タイランド リミテッドHOYA Lens Thailand Ltd Spectacle lens
CN109667139B (en) * 2018-12-31 2021-06-29 盐城工学院 Anti-ultraviolet self-cleaning composition and preparation method and application thereof
JP6901186B2 (en) * 2019-04-03 2021-07-14 株式会社ワンアンドオンリー Antistatic agent / antistatic method / antistatic coating film and antistatic layer forming resin composition / antistatic method
US11747272B2 (en) 2019-06-10 2023-09-05 Analog Devices, Inc. Gas detection using differential path length measurement
US11821836B2 (en) 2020-07-13 2023-11-21 Analog Devices, Inc. Fully compensated optical gas sensing system and apparatus
CN112143299B (en) * 2020-09-24 2022-02-01 南京长江涂料有限公司 Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof
WO2022085105A1 (en) 2020-10-21 2022-04-28 三菱電機株式会社 Heat exchanger, and method for manufacturing heat exchanger
CN113311444B (en) * 2021-06-22 2022-08-02 山东高速建设管理集团有限公司 Water film identification and treatment device and use method thereof
CN113462273A (en) * 2021-06-29 2021-10-01 广东康伴新材料科技有限公司 High-wear-resistance high-hand-sensitivity rubber coating and preparation method thereof

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5211321B2 (en) * 1972-04-11 1977-03-30
JPS63100042A (en) * 1986-10-14 1988-05-02 Nippon Sheet Glass Co Ltd Glass article difficult-to be dirtied
JPH04225301A (en) * 1990-12-27 1992-08-14 Seiko Epson Corp Optical product having clouding preventive performance
JPH05209072A (en) * 1992-01-29 1993-08-20 Japan Synthetic Rubber Co Ltd Method for treating substrate surface
JPH06191848A (en) * 1992-10-24 1994-07-12 Degussa Ag Titanium dioxide-mixed oxide, production thereof and method for production of catalyst, catalyst carrier, photocatalyst, ceramic, autolacquer and cosmetics
JPH06246165A (en) * 1993-02-19 1994-09-06 Japan Storage Battery Co Ltd Production of photocatalyst
JPH06278241A (en) * 1992-09-22 1994-10-04 Takenaka Komuten Co Ltd Building material
JPH06315614A (en) * 1993-03-11 1994-11-15 Agency Of Ind Science & Technol Method for removing contaminants and cleaning material
JPH0760132A (en) * 1993-08-24 1995-03-07 Matsushita Seiko Co Ltd Photocatalyst and method for carrying the same
JPH07268823A (en) * 1994-03-29 1995-10-17 Mitsubishi Heavy Ind Ltd Car road soundproofing wall cleaning device
JPH07265714A (en) * 1994-03-30 1995-10-17 Matsushita Seiko Co Ltd Supporting method for forming photocatalyst bed
JPH07331120A (en) * 1994-06-10 1995-12-19 Hitachi Ltd Coating for removing nitrogen oxide and its use

Family Cites Families (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49124166A (en) * 1973-02-07 1974-11-27
JPS5826052A (en) * 1981-08-06 1983-02-16 Asahi Glass Co Ltd Glass body provided with alkali diffusion preventing silicon oxide film
JPS59145808A (en) * 1983-02-09 1984-08-21 財団法人鉄道総合技術研究所 Cloudiness-proof road mirror
JPS60151250A (en) * 1984-01-12 1985-08-09 Matsushita Electric Ind Co Ltd Enamel film backed phosphor
JPS60210641A (en) * 1984-02-22 1985-10-23 Unitika Ltd Antifogging plastic molding
JPS6183106A (en) * 1984-10-01 1986-04-26 Giken Kogyo Kk Method of preventing contamination of surface of solid material to be brought into contact with water
JPS6191042A (en) * 1984-10-08 1986-05-09 Toyota Motor Corp Anti-fogging glass and its production
JPS61133125A (en) * 1984-11-29 1986-06-20 Tsutomu Kagitani Denitration process using ultraviolet ray
JPS621750A (en) * 1985-06-27 1987-01-07 Toray Silicone Co Ltd Room temperature curing organopolysiloxane composition
JPH0647668B2 (en) * 1985-12-16 1994-06-22 三菱化成ビニル株式会社 Anti-fog composition
JPH0615407B2 (en) * 1986-05-07 1994-03-02 株式会社資生堂 Optical semiconductor and its manufacturing method
JPS635301A (en) * 1986-06-25 1988-01-11 Matsushita Electric Works Ltd Reflecting mirror
JPS6363726A (en) * 1986-09-05 1988-03-22 Nippon Shokubai Kagaku Kogyo Co Ltd Composition for surface treatment
JPS6381176A (en) * 1986-09-24 1988-04-12 Yoshio Ichikawa Composition for coating
JPS63246167A (en) * 1987-04-02 1988-10-13 チタン工業株式会社 White deodorant and its production
JPH01169866A (en) * 1987-12-25 1989-07-05 Hitachi Ltd Discharge lamp
JPH06102155B2 (en) * 1988-02-29 1994-12-14 株式会社日立製作所 Deodorant, deodorant manufacturing method, deodorizing method, deodorizing device, and refrigeration cycle device equipped with this deodorizing device
JP2856754B2 (en) * 1989-02-17 1999-02-10 株式会社東芝 Ultraviolet-suppressed luminescence source, coating agent for ultraviolet-suppressed luminescence source, and method for producing ultraviolet-suppressed luminescence source
JPH0787891B2 (en) * 1989-04-14 1995-09-27 日本ゼオン株式会社 Removing agent and method for removing oxidizable harmful substances
JPH0330314U (en) * 1989-07-31 1991-03-26
DE4023267A1 (en) * 1990-07-21 1992-01-23 Hoechst Ag PLATE, FILM OR TAPE-BASED CARRIER MATERIAL FOR OFFSET PRINT PLATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
JP2618287B2 (en) * 1990-11-06 1997-06-11 日本ゼオン株式会社 Photoreactive harmful substance remover and harmful substance removal method using the same
JPH04206201A (en) * 1990-11-29 1992-07-28 Honda Motor Co Ltd Resin lens headlamp for vehicle
JP3224865B2 (en) * 1991-08-14 2001-11-05 東レ合成フィルム株式会社 Agricultural coating film and method for producing the same
JP2883761B2 (en) * 1991-12-06 1999-04-19 工業技術院長 Antibacterial growth inhibitor
JP2913966B2 (en) * 1991-12-10 1999-06-28 市光工業株式会社 Vehicle lighting
JPH05232566A (en) * 1992-02-24 1993-09-10 Olympus Optical Co Ltd Optical member
JP3340149B2 (en) * 1992-04-28 2002-11-05 セントラル硝子株式会社 Hydrophilic coating and method for forming the coating
JPH06293519A (en) * 1992-07-28 1994-10-21 Ishihara Sangyo Kaisha Ltd Production of titanium oxide particles and film
JP3036247B2 (en) * 1992-08-14 2000-04-24 東陶機器株式会社 Lighting equipment
JPH06190340A (en) * 1992-09-11 1994-07-12 Sekisui Jushi Co Ltd Coated metal body
JP3316048B2 (en) * 1992-11-06 2002-08-19 株式会社竹中工務店 Building material and manufacturing method thereof
JP2878922B2 (en) * 1993-03-04 1999-04-05 シャープ株式会社 In-vehicle camera device
JPH06266289A (en) * 1993-03-10 1994-09-22 Dainippon Ink & Chem Inc Manufacture of durable display body
JPH085660B2 (en) * 1993-04-13 1996-01-24 工業技術院長 Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein
AU676299B2 (en) * 1993-06-28 1997-03-06 Akira Fujishima Photocatalyst composite and process for producing the same
JP3115745B2 (en) * 1993-07-12 2000-12-11 富士写真フイルム株式会社 Photosensitive material
JPH0751646A (en) * 1993-08-12 1995-02-28 Ishihara Sangyo Kaisha Ltd Method for cleaning off contaminant on solid matter surface
JP3499585B2 (en) * 1993-09-21 2004-02-23 日揮ユニバーサル株式会社 Ethylene decomposition photocatalyst
JP2517874B2 (en) * 1993-09-30 1996-07-24 工業技術院長 Method for producing titanium oxide thin film photocatalyst
JP3334767B2 (en) * 1993-10-20 2002-10-15 日新製鋼株式会社 Building materials with moisture absorption and release functions
JP2602022Y2 (en) * 1993-11-25 1999-12-20 旭光学工業株式会社 Dew condensation removal device in camera
JPH07149520A (en) * 1993-11-29 1995-06-13 Hoya Corp Coating composition
JPH07164607A (en) * 1993-12-13 1995-06-27 Mitsubishi Chem Corp Agricultural film
JPH07168001A (en) * 1993-12-15 1995-07-04 Nikon Corp Mildew-proofing optical equipment
JP3488496B2 (en) * 1993-12-21 2004-01-19 日揮ユニバーサル株式会社 Poison-resistant deodorizing photocatalyst
JP3391543B2 (en) * 1993-12-27 2003-03-31 花王株式会社 Hydrophilizing agent and hydrophilizing method
JP2832239B2 (en) * 1994-06-21 1998-12-09 三井金属鉱業株式会社 Lighting equipment with photocatalytic function
JPH0810576A (en) * 1994-07-05 1996-01-16 Ebara Res Co Ltd Removing method of harmful gas and device therefor
JPH08119673A (en) * 1994-10-21 1996-05-14 Kansai Paint Co Ltd Hydrophilization treatment of glass
JPH09129012A (en) * 1995-03-31 1997-05-16 Toshiba Lighting & Technol Corp Photocatalyst, fluorescent lamp and luminaire
JPH08277147A (en) * 1995-03-31 1996-10-22 Nippon Muki Co Ltd Plate glass
JP3101537B2 (en) * 1995-05-10 2000-10-23 ワイケイケイ株式会社 Antifouling building material and exterior building material unit
JPH0929103A (en) * 1995-05-17 1997-02-04 Toshiba Lighting & Technol Corp Photocatalytic body, photocatalytic device, light source and lightening equipment
JPH08313705A (en) * 1995-05-22 1996-11-29 Seiko Epson Corp Anti-clouding article and its production
JP3127827B2 (en) * 1995-06-14 2001-01-29 東陶機器株式会社 Anti-fog seal
CN1081490C (en) * 1995-06-19 2002-03-27 日本曹达株式会社 Photocatalyst-carrying structure and photocatalyst coating material
JPH0990889A (en) * 1995-09-27 1997-04-04 Toshiba Lighting & Technol Corp Sign body and externally illuminated sign device
JPH09173783A (en) * 1995-10-27 1997-07-08 Matsushita Electric Ind Co Ltd Sheet glass and resin plate and their production and method for removing contaminant
JP4237830B2 (en) * 1995-12-20 2009-03-11 日本曹達株式会社 Photocatalyst-carrying lighting fixture
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5211321B2 (en) * 1972-04-11 1977-03-30
JPS63100042A (en) * 1986-10-14 1988-05-02 Nippon Sheet Glass Co Ltd Glass article difficult-to be dirtied
JPH04225301A (en) * 1990-12-27 1992-08-14 Seiko Epson Corp Optical product having clouding preventive performance
JPH05209072A (en) * 1992-01-29 1993-08-20 Japan Synthetic Rubber Co Ltd Method for treating substrate surface
JPH06278241A (en) * 1992-09-22 1994-10-04 Takenaka Komuten Co Ltd Building material
JPH06191848A (en) * 1992-10-24 1994-07-12 Degussa Ag Titanium dioxide-mixed oxide, production thereof and method for production of catalyst, catalyst carrier, photocatalyst, ceramic, autolacquer and cosmetics
JPH06246165A (en) * 1993-02-19 1994-09-06 Japan Storage Battery Co Ltd Production of photocatalyst
JPH06315614A (en) * 1993-03-11 1994-11-15 Agency Of Ind Science & Technol Method for removing contaminants and cleaning material
JPH0760132A (en) * 1993-08-24 1995-03-07 Matsushita Seiko Co Ltd Photocatalyst and method for carrying the same
JPH07268823A (en) * 1994-03-29 1995-10-17 Mitsubishi Heavy Ind Ltd Car road soundproofing wall cleaning device
JPH07265714A (en) * 1994-03-30 1995-10-17 Matsushita Seiko Co Ltd Supporting method for forming photocatalyst bed
JPH07331120A (en) * 1994-06-10 1995-12-19 Hitachi Ltd Coating for removing nitrogen oxide and its use

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10325768A1 (en) * 2003-06-05 2004-12-23 Chemetall Gmbh Coating system for glass surfaces, process for its production and its application

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