JP3173391B2 - Hydrophilic film, and method for producing and using the same - Google Patents

Hydrophilic film, and method for producing and using the same

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Publication number
JP3173391B2
JP3173391B2 JP28453496A JP28453496A JP3173391B2 JP 3173391 B2 JP3173391 B2 JP 3173391B2 JP 28453496 A JP28453496 A JP 28453496A JP 28453496 A JP28453496 A JP 28453496A JP 3173391 B2 JP3173391 B2 JP 3173391B2
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JP
Japan
Prior art keywords
film
photocatalyst
water
antifogging
surface layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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JP28453496A
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Japanese (ja)
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JPH09226042A (en
Inventor
隆一 古城
信 早川
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東陶機器株式会社
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
    • F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
    • F24F8/22—Treatment, 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00—Coatings; Surface treatments
    • F28F2245/02—Coatings; Surface treatments hydrophilic

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、基材の表面を高度
の親水性になし、かつ維持するためのフィルムに関す
る。より詳しくは、本発明は、鏡、レンズ、ガラス、プ
リズムその他の透明基材の表面を高度に親水化すること
により、基材の曇りや水滴形成を防止する防曇性フィル
ムに関する。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、又は表面を自己浄化（セルフクリー
ニング）し若しくは容易に清掃することの可能なフィル
ムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for making the surface of a substrate highly hydrophilic and maintaining it. More specifically, the present invention relates to an anti-fogging film that prevents fogging and water droplet formation on a substrate by highly hydrophilizing the surface of a mirror, lens, glass, prism or other transparent substrate. The present invention also provides a highly hydrophilic surface of a building, window glass, mechanical device or article to prevent the surface from being soiled, or to self-clean (self-clean) or easily clean the surface. Related to possible films.

【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、眼鏡やゴーグルのレン
ズ、及び各種計器盤のカバー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。更に、車両の風防ガラスや窓ガラス、建物の窓ガラ
ス、眼鏡やゴーグルのレンズ、マスクやヘルメットのシ
ー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、バックミラーが寒冷時や雨天
に翳り、ぼやけ、斑模様になり、或いは曇ると、視界の
確保が困難となり、交通の安全性が損なわれる。内視鏡
レンズやデンタルミラーが曇ると、的確な診断、手術、
処置の障害となる。計器盤のカバーガラスが曇ると、デ
ータの読みが困難となる。2. Description of the Related Art It is often experienced that in cold weather, windshields and windows of automobiles and other vehicles, window glasses of buildings, lenses of glasses and goggles, and cover glasses of various instrument panels are fogged by condensed moisture. is there. In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. Furthermore, when windshields and windowpanes of vehicles, windowpanes of buildings, lenses of glasses and goggles, shields of masks and helmets receive rain and splashes, and a large number of discrete water droplets adhere to the surface, those surfaces become dark, Blurred, mottled, or cloudy, again losing visibility. 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, window glass, or rearview mirror of a vehicle is exposed to cold or rainy weather, becomes blurred, spotted, or fogged, it becomes difficult to secure a view, and traffic safety is impaired. When endoscope lens and dental mirror become cloudy, accurate diagnosis, surgery,
Obstruct treatment. If the cover glass of the instrument panel becomes cloudy, it will be difficult to read the data.

【０００３】周知のように、従来用いられている防曇方
法は、ポリエチレングリコールのような親水性化合物或
いはシリコーンのような撥水性化合物を含んだ防曇性組
成物を表面に塗布することである。しかし、この種の防
曇性被膜はあくまで一時的なもので、水洗や接触によっ
て容易に取除かれ、早期に効果を失うという難点があ
る。As is well known, a conventionally used anti-fog method is to apply an anti-fog composition containing a hydrophilic compound such as polyethylene glycol or a water-repellent compound such as silicone to the surface. . However, this kind of anti-fog coating is only temporary, and has the drawback that it is easily removed by washing or contact and loses its effect early.

【０００４】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、カー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ている（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．１５−２４）。[0004] On the other hand, in the fields 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. Dirt on building exterior materials and coatings consists of combustion products such as carbon black, and inorganic pollutants such as urban dust and clay particles. It is believed that the diversity of such contaminants complicates antifouling measures (Yoshinori Tachibana,
"Method for Accelerated Testing of Exterior Wall Finishing Material Contamination", Architectural Institute of Japan Structural Transactions, No. 404, October 1989,
p. 15-24).

【０００５】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（ＰＴ
ＦＥ）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、塗膜の表面をできるだけ親水性にするのが望まし
いと考えられている（高分子、４４巻、１９９５年５月
号、ｐ．３０７）。そこで、親水性のグラフトポリマー
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３０〜４０゜のグラフトポリマーに対して親和性
を有しその表面に付着しやすいので、このグラフトポリ
マー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。According to conventional wisdom, in order to prevent dirt on the building exterior and the like, polytetrafluoroethylene (PT) is used.
Water-repellent paints such as FE) have been considered preferable, but recently it has been considered desirable to make the surface of the paint film as hydrophilic as possible for urban dust containing a large amount of hydrophobic components. (Polymer, Vol. 44, May 1995, p. 307). Therefore, it has been proposed to paint the building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily", January 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 from 20 ° to 50 °, and has an affinity for the graft polymer having a contact angle with water of 30 to 40 ° and adheres to the surface. Therefore, it is considered that this graft polymer coating film cannot prevent contamination by inorganic dust.

【０００６】[0006]

【発明の解決すべき課題】上記の如く、基材表面を親水
性にすることにより、基材の曇りや水滴形成を防止した
り、また、建物や窓ガラスや機械装置や物品の表面が汚
れるのを防止し、又は表面を自己浄化（セルフクリーニ
ング）し若しくは容易に清掃することができる提案は存
在するものの、表面を高度の親水性に長期にわたり維持
できないため、その効果は充分でなかった。そこで、本
発明では、上記事情に鑑み、基材表面に貼着させるだけ
で、基材表面を長期にわたり高度の親水性に維持できる
フィルム、及びその製造方法、使用方法を提供すること
を目的とする。As described above, by making the surface of the base material hydrophilic, it is possible to prevent clouding and water droplet formation on the base material, and to stain the surfaces of buildings, window glasses, mechanical devices and articles. Although there are proposals that can prevent the occurrence of blemishes or that the surface can be self-cleaned (self-cleaning) or easily cleaned, the effect is not sufficient because the surface cannot be maintained at a high degree of hydrophilicity for a long time. In view of the above circumstances, it is an object of the present invention to provide a film capable of maintaining a highly hydrophilic surface of a substrate for a long period of time by simply adhering to the surface of the substrate, and a method for producing and using the film. I do.

【０００７】[0007]

【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
とのエネルギーギャップ以上のエネルギーを有する光が
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、おそらく表面に極性が付与され、水
や水酸基等の極性成分が集められる。そして伝導電子と
正孔のいずれかまたは双方と、上記極性成分との協調的
な作用により、表面と前記表面に化学的に吸着した汚染
物質との化学結合を切断すると共に、表面に化学吸着水
が吸着し、さらに物理吸着水層がその上に形成されるの
である。また、一旦部材表面が高度に親水化されたなら
ば、部材を暗所に保持しても、表面の親水性はある程度
の期間持続する。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 greater 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 to generate conduction electrons and holes. By either or both actions, polarities are probably imparted to the surface and polar components such as water and hydroxyl groups are collected. Then, one or both of conduction electrons and holes and the above-mentioned polar component cooperate with each other to cut off a chemical bond between the surface and the contaminant chemically adsorbed on the surface, and to cause a chemical adsorbed water on the surface. Is adsorbed, and a physically adsorbed water layer is formed thereon. Further, once the surface of the member is highly hydrophilized, the hydrophilicity of the surface is maintained for a certain period even if the member is kept in a dark place.

【０００８】本発明では、フィルム基体表面に、光触媒
粒子を含有する表面層を備えた親水性フィルムを提供す
る。光触媒を含有する表面層を備えることにより、光触
媒の光励起に応じて、恒久的に表面層の表面は高度の親
水性を呈するようになる。透明な表面が高度の親水性を
呈するようになると、付着した湿分の凝縮水及び／又は
水滴が前記層の表面に一様に広がり、湿分凝縮水及び／
又は水滴によって曇り若しくは翳るのが防止されるよう
になり、可視性が失われるのが防止される。また、表面
が高度の親水性を呈するようになると、表面が降雨にさ
らされた時に、付着堆積物及び／又は汚染物が雨滴によ
り洗い流せるようになり、降雨によるセルフクリーニン
グが可能となる。さらに、表面が高度の親水性を呈する
ようになると、表面が水濯ぎや簡単な水拭き程度で洗浄
できるようになり、水洗浄が容易になる。The present invention provides a hydrophilic film having a surface layer containing photocatalyst particles on the surface of a film substrate. By providing a surface layer containing a photocatalyst, the surface of the surface layer becomes permanently highly hydrophilic in response to photoexcitation of the photocatalyst. When the transparent surface becomes highly hydrophilic, the condensed water and / or droplets of the attached moisture spread evenly on the surface of the layer, and the moisture condensed water and / or
Alternatively, it is possible to prevent clouding or clouding due to water droplets, thereby preventing loss of visibility. Also, when the surface becomes highly hydrophilic, the deposits and / or contaminants can be washed away by raindrops when the surface is exposed to rainfall, and self-cleaning by rainfall becomes possible. Furthermore, when the surface exhibits a high degree of hydrophilicity, the surface can be washed with water rinsing or simple water wiping, which facilitates water washing.

【０００９】本発明の好ましい態様においては、表面層
には、さらにシリカが含有されているようにする。シリ
カが含有されることにより、表面が水濡れ角０゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由はシリカは構造
中に水を蓄えることができることと関係していると思わ
れる。In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. The reason seems to be related to the fact that silica can store water in its structure.

【００１０】本発明の好ましい態様においては、表面層
には、さらにシリコーンが含有されているようにする。
シリコーンが含有されることにより、光触媒の光励起に
よって、シリコーン中のシリコン原子に結合する有機基
の少なくとも一部が水酸基に置換され、さらにその上に
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゜に近い高度の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。In a preferred embodiment of the present invention, the surface layer further contains silicone.
By containing the silicone, at least a part of the organic group bonded to the silicon atom in the silicone is replaced by a hydroxyl group by photoexcitation of the photocatalyst, and further, a physisorbed water layer is formed thereon, whereby the surface is formed. It exhibits a high degree of hydrophilicity near the water wetting angle of 0 °, and improves the hydrophilicity retention when kept in a dark place.

【００１１】[0011]

【発明の実施の形態】次に、本発明の具体的な構成につ
いて説明する。本発明における親水性フィルム表面に
は、図１又は図２に示すように、基材の表面に光触媒を
含む層が形成されている。このような表面構造をとるこ
とで、親水性フィルム表面は、光触媒の光励起に応じて
高度に親水化されるのである。それにより、雰囲気の湿
分が凝縮して付着しても水滴状には成長せず、一様に水
膜化するようになり、湿分凝縮水及び／又は水滴によっ
て曇り若しくは翳るのが防止される。また、表面が降雨
にさらされた時に、付着堆積物及び／又は汚染物が雨滴
により洗い流せるようになり、降雨によるセルフクリー
ニングが可能となる。さらに、表面が高度の親水性を呈
するようになると、表面が水濯ぎや簡単な水拭き程度で
洗浄できるようになり、水洗浄が容易になる。Next, a specific configuration of the present invention will be described. As shown in FIG. 1 or FIG. 2, a layer containing a photocatalyst is formed on the surface of a substrate on the surface of the hydrophilic film in the present invention. With such a surface structure, the hydrophilic film surface is highly hydrophilized in response to photoexcitation of the photocatalyst. As a result, even if the moisture in the atmosphere condenses and adheres, it does not grow in the form of water droplets, but uniformly forms a water film, and is prevented from being clouded or overshadowed by the moisture condensed water and / or water droplets. You. Also, when the surface is exposed to rainfall, attached deposits and / or contaminants can be washed away by raindrops, and self-cleaning by rainfall becomes possible. Furthermore, when the surface exhibits a high degree of hydrophilicity, the surface can be washed with water rinsing or simple water wiping, which facilitates water washing.

【００１２】図１においては、表面層が光触媒のみから
なる場合には、光触媒は酸化物であることが好ましい。
そうすることにより、酸化物は環境中の汚染物質が吸着
していない状態では親水性を示すので、光励起作用によ
りその汚染物質を排斥させ、吸着水層を形成させること
で、親水性を呈しやすく、一様な水膜が形成できる。図
２において、Ｍは金属元素を示す。従って、図２の場
合、最表面は一般の無機酸化物からなる。この場合も、
酸化物は環境中の汚染物質が吸着していない状態では親
水性を示すので、上記無機酸化物以外に表面層に混入す
る光触媒性酸化チタンの光励起作用によりその汚染物質
を排斥させ、吸着水層を形成させることで、一様な水膜
が形成できる。In FIG. 1, when the surface layer comprises only a photocatalyst, the photocatalyst is preferably an oxide.
By doing so, the oxide shows hydrophilicity in the state where the pollutants in the environment are not adsorbed, so that the pollutants are rejected by the photoexcitation action and the adsorbed water layer is formed, so that the oxides easily exhibit hydrophilicity. A uniform water film can be formed. In FIG. 2, M represents a metal element. Therefore, in the case of FIG. 2, the outermost surface is made of a general inorganic oxide. Again,
Since the oxide is hydrophilic when the pollutants in the environment are not adsorbed, the photocatalytic titanium oxide mixed into the surface layer other than the inorganic oxide removes the contaminants by the photoexciting action, and the adsorbed water layer Is formed, a uniform water film can be formed.

【００１３】本発明におけるフィルム基体には、ポリエ
チレンテレフタレート、塩化ビニル、ポリエチレン等の
プラスチック、プラスチック基材の上に透明なハードコ
ートを設けたプラスチック等が好適に利用できる。ま
た、場合によって、これらの基体は飛散防止、意匠付
与、耐蝕等の他の機能を兼備えることもできる。As the film substrate in the present invention, plastics such as polyethylene terephthalate, vinyl chloride, and polyethylene, and plastics provided with a transparent hard coat on a plastic substrate can be suitably used. In some cases, these substrates may also have other functions such as scattering prevention, design provision, and corrosion resistance.

【００１４】また、本発明におけるフィルムは種々の基
材に適用できる。本発明におけるフィルムが適用可能な
基材としては、上記防曇効果を期待する場合には透明な
基材であり、その材質はガラス、透明プラスチック等の
基材に好適に利用できる。適用可能な基材を用途でいえ
ば、車両用バックミラー、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、写
真機レンズ、照明用レンズ、レーザー光集束レンズ、半
導体用レンズ、複写機用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、ロー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、鉄道車両、オートバイ、航空機、船舶、潜水艇、
雪上車、ロー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；防護用ゴーグル、ス
ポーツ用ゴーグル、防護用マスクのシールド、スポーツ
用マスクのシールド、ヘルメットのシールド、冷凍食品
陳列ケースのガラス；計測機器のカバーガラスなどに好
適に利用できる。本発明におけるフィルムが適用可能な
基材としては、上記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、セラミックス、ガラ
ス、プラスチック、木、石、セメント、コンクリート、
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、防塵カバー及び
塗装、交通標識、各種表示装置、広告塔、道路用防音
壁、鉄道用防音壁、橋梁、ガードレールの外装及び塗
装、トンネル内装及び塗装、碍子、太陽電池カバー、太
陽熱温水器集熱カバー、ビニールハウス、車両用照明灯
のカバー、住宅設備、便器、浴槽、洗面台、照明器具、
照明カバー、台所用品、食器、食器洗浄器、食器乾燥
器、流し、調理レンジ、キッチンフード、換気扇などに
好適に利用できる。本発明におけるフィルムは、長期に
わたり高度の親水性を維持することができるので、帯電
防止機能も期待できる。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、セラミックス、ガラ
ス、プラスチック、木、石、セメント、コンクリート、
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、オーディオテープ、ビデオテープ、アナログレ
コード、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
塵カバー及び塗装などに好適に利用できる。The film of the present invention can be applied to various substrates. The substrate to which the film according to the present invention can be applied is a transparent substrate when the above antifogging effect is expected, and the material thereof can be suitably used for a substrate such as glass or transparent plastic. Applicable substrates include mirrors such as vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors; spectacle lenses, optical lenses, camera lenses, illumination lenses, lasers. Lenses such as light focusing lenses, semiconductor lenses, and copier lenses; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, ropeway gondolas,
Amusement park gondola, window glass for vehicles like spaceships; cars, railcars, motorcycles, aircraft, ships, submarines,
Snow car, ropeway gondola, amusement park gondola,
Windshield glass for vehicles such as spaceships; protective goggles, sports goggles, shields for protective masks, shields for sports masks, shields for helmets, glass for frozen food display cases; suitable for cover glass for measuring instruments, etc. Available. As a substrate to which the film of the present invention can be applied, when the above surface cleaning effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete,
Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used. Applicable base materials include 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 types of Display devices, advertising towers, noise barriers for roads, noise barriers for railways, bridges, guardrail exteriors and coatings, tunnel interiors and coatings, insulators, solar cell covers, solar water heater collector covers, plastic greenhouses, vehicle lighting Covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures,
It can be suitably used for lighting covers, kitchenware, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and the like. Since the film in the present invention can maintain a high degree of hydrophilicity for a long period of time, an antistatic function can also be expected. When antistatic effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete,
Fibers, fabrics, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housing and parts for household electrical appliances, exterior and coating, OA equipment It can be suitably used for housing, parts, exterior and coating of products, building materials, building exterior, building interior, window frames, window glass, structural members, exterior and coating of vehicles, exterior of machinery and articles, dustproof cover and coating, etc. .

【００１５】光触媒とは、その結晶の伝導帯と価電子帯
との間のエネルギーギャップよりも大きなエネルギー
（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物質をいい、例えば、アナター
ゼ型酸化チタン、ルチル型酸化チタン、酸化錫、酸化亜
鉛、三酸化二ビスマス、三酸化タングステン、酸化第二
鉄、チタン酸ストロンチウム等が好適に利用できる。こ
こで光触媒の光励起に用いる光源としては、太陽光、一
般室内照明等の環境にある光源を利用してもよいし、付
属設備や携帯設備として励起光を照射しうる光源を使用
してもよい。さらに、本発明のプラスチックレンズ又は
プラスチックレンズを備えた眼鏡或いはプラスチックレ
ンズを備えたゴーグル専用の保管容器を設け、そこに励
起光を照射しうる光源を設置してもよい。その場合使用
する光源には、例えば、白熱電灯、メタルハライドラン
プ、水銀ランプ、キセノンランプ、殺菌灯、蛍光灯等が
好適に利用できる。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。A photocatalyst is a device that, when irradiated with light (excitation light) having an energy (that is, a shorter wavelength) larger than the energy gap between the conduction band and the valence band of the crystal, emits electrons in the valence band. A substance that can generate conduction electrons and holes by excitation (photoexcitation). Examples thereof include anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, bismuth trioxide, tungsten trioxide, and tungsten oxide. Ferrous iron, strontium titanate and the like can be suitably used. Here, as a light source used for photoexcitation of the photocatalyst, a light source in an environment such as sunlight or general indoor lighting may be used, or a light source capable of irradiating excitation light as accessory equipment or portable equipment may be used. . Further, the plastic lens of the present invention, or a spectacle provided with the plastic lens or a storage container dedicated to goggles provided with the plastic lens, may be provided with a light source capable of irradiating excitation light. As the light source used in this case, for example, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, a germicidal lamp, a fluorescent lamp and the like can be suitably used. 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 / cm 2 or more.
m 2 or more, more preferably 0.1 mW / cm 2 or more.

【００１６】光触媒を含有する表面層の膜厚は、０．４
μｍ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、光触媒を含有する表面層の膜厚を
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。上記表面層の表面に、更に、親水化可能な耐摩耗性
又は耐食性の保護層や他の機能膜を設けても良い。The thickness of the surface layer containing the photocatalyst is 0.4
It is preferable that the thickness be not more than μm. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. More preferably, the thickness of the surface layer containing the photocatalyst is 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. The surface of the surface layer may be further provided with a wear-resistant or corrosion-resistant protective layer capable of being made hydrophilic and other functional films.

【００１７】上記表面層は、基材と比較して屈折率があ
まり高くないのが好ましい。好ましくは表面層の屈折率
は２以下であるのがよい。そうすれば、基材と表面層と
の界面、及び表面層と空気との界面における光の反射を
抑制できる。表面層の屈折率を２以下にするには、光触
媒に２以下の屈折率を有する物質を用いるか、或いは光
触媒が屈折率２以上の場合には、屈折率２以下の他の物
質を表面層に添加する。２以下の屈折率を有する光触媒
としては、酸化錫（屈折率１．９）等が利用できる。２
以上の屈折率を有する光触媒には、アナターゼ型酸化チ
タン（屈折率２．５）やルチル型酸化チタン（屈折率
２．７）があるが、この場合には屈折率２以下の他の物
質、例えば、炭酸カルシウム（屈折率１．６）、水酸化
カルシウム（屈折率１．６）、炭酸マグネシウム（屈折
率１．５）、炭酸ストロンチウム（屈折率１．５）、ド
ロマイト（屈折率１．７）、フッ化カルシウム（屈折率
１．４）、フッ化マグネシウム（屈折率１．４）、シリ
カ（屈折率１．５）、アルミナ（屈折率１．６）、ケイ
砂（屈折率１．６）、モンモリロナイト（屈折率１．
５）、カオリン（屈折率１．６）、セリサイト（屈折率
１．６）、ゼオライト（屈折率１．５）、酸化錫（屈折
率１．９）等を表面層に添加すればよい。The surface layer preferably has a refractive index not so high as compared with the substrate. Preferably, the refractive index of the surface layer is 2 or less. Then, light reflection at the interface between the substrate and the surface layer and the interface between the surface layer and air can be suppressed. In order to reduce the refractive index of the surface layer to 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst, or if the photocatalyst has a refractive index of 2 or more, another substance having a refractive index of 2 or less is used for the surface layer. To be added. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index: 1.9) or the like can be used. 2
Photocatalysts having the above refractive index include anatase-type titanium oxide (refractive index: 2.5) and rutile-type titanium oxide (refractive index: 2.7). For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7) ), Calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica sand (refractive index 1.6) ), Montmorillonite (refractive index 1.
5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9) and the like may be added to the surface layer.

【００１８】上記表面層には、Ａｇ、Ｃｕ、Ｚｎ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。A metal such as Ag, Cu, or Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.

【００１９】上記表面層には、Ｐｔ、Ｐｄ、Ｒｕ、Ｒ
ｈ、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表面層は、光触媒の酸化還元
活性を増強でき、脱臭浄化作用等が向上する。Pt, Pd, Ru, R
A platinum group metal such as h, Ir, Os can be added. The surface layer to which the metal is added can enhance the oxidation-reduction activity of the photocatalyst and improve the deodorizing and purifying action and the like.

【００２０】親水性とは、表面に水を滴下したときにな
じみやすい性質をいい、一般に水濡れ角が９０゜未満の
状態をいう。本発明における高度の親水性とは、表面に
水を滴下したときに非常になじみやすい性質をいい、よ
り具体的には平滑表面における水濡れ角が１０゜以下程
度になる状態をいう。特に、防曇性にはＰＣＴ／ＪＰ９
６／００７３４に開示したように、水濡れ角が１０゜以
下であると好ましく、５゜以下ではより好ましい。The term "hydrophilic" refers to the property of being easily conformed when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The term “high hydrophilicity” in the present invention refers to a property that is highly compatible when water is dropped on the surface, and more specifically, a state where the water wetting angle on a smooth surface is about 10 ° or less. In particular, PCT / JP9
As disclosed in 6/00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less.

【００２１】次に、フィルム上への光触媒含有表面層の
形成方法について、表面層が光触媒とシリカからなる場
合、表面層が光触媒とシリコーンからなる場合を例にと
り説明する。まず、表面層が光触媒とシリカからなる場
合について、光触媒がアナターゼ型酸化チタンの場合を
例にとり説明する。この場合は、基本的には、無定型シ
リカの前駆体を塗膜形成要素とし、塗膜形成要素をアナ
ターゼ型酸化チタン粒子とともにフィルム基材上にスプ
レーコーティング法、ディップコーティング法、フロー
コーティング法、スピンコーティング法、ロールコーテ
ィング法等の方法で塗布後、塗膜形成要素の硬化反応に
より、無定型シリカを生成するとともに、アナターゼ型
酸化チタン粒子を無定型シリカを結着剤として固着させ
る。ここで、塗膜形成要素をアナターゼ型酸化チタン粒
子とともに塗布する前に、フィルム基材上にプライマー
層やハードコート層、或いはその双方といった中間層を
形成するようにしてもよい。このようにすることで、フ
ィルム基材と表面層との密着性を向上させることができ
る。また、ここで無定型シリカの前駆体には、テトラア
ルコキシシラン（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、テトラメトキシシ
ラン等）、その部分加水分解、脱水縮重合物である平均
組成式（ＯＲ）ｘＳｉＯｙ（０＜ｘ≦４、０≦ｙ＜２）
（Ｒはアルキル基）からなる４官能性シロキサン樹脂、
シラノール、その脱水縮重合物であるシラノール樹脂等
の塗膜形成要素が好適に利用できる。このうち、保管安
定性が良く、常温で硬化反応を生じさせることが容易で
あることから、平均組成式（ＯＲ）ｘＳｉＯｙ（０＜ｘ
≦４、０≦ｙ＜２）（Ｒはアルキル基）からなる４官能
性シロキサン樹脂を使用するのが最も好ましい。上記と
同様の理由で、中間層を形成する場合にも、中間層の成
分に平均組成式（ＯＲ）ｘＳｉＯｙ（０＜ｘ≦４、０≦
ｙ＜２）（Ｒはアルキル基）からなる４官能性シロキサ
ン樹脂を使用すると、保管安定性が良く、常温で硬化反
応を生じさせることが容易であることから好ましい。特
に常温で硬化反応を生じさせることができると、例えば
基材が塩化ビニルフィルムのように耐熱性のない場合に
都合がよい。塗膜形成要素の硬化反応は、例えば、無定
型シリカの前駆体を水又は空気中の湿分と接触させるこ
とにより加水分解反応させた後、加熱、紫外線照射、室
温放置等の方法により脱水縮重合反応させることにより
行う。Next, a method for forming a photocatalyst-containing surface layer on a film will be described by taking as an example a case where the surface layer is composed of a photocatalyst and silica, and a case where the surface layer is composed of a photocatalyst and silicone. First, the case where the surface layer is made of a photocatalyst and silica will be described by taking the case where the photocatalyst is an anatase type titanium oxide as an example. In this case, basically, a precursor of amorphous silica is used as a film forming element, and the film forming element is spray-coated on a film substrate together with anatase-type titanium oxide particles, a dip coating method, a flow coating method, After application by a method such as a spin coating method or a roll coating method, an amorphous silica is generated by a curing reaction of a coating film forming element, and anatase type titanium oxide particles are fixed using the amorphous silica as a binder. Here, an intermediate layer such as a primer layer, a hard coat layer, or both may be formed on the film substrate before applying the coating film forming element together with the anatase type titanium oxide particles. By doing so, the adhesion between the film substrate and the surface layer can be improved. Here, the precursor of the amorphous silica includes tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.), and an average composition formula (partial hydrolysis, dehydration condensation polymer) OR) xSiOy (0 <x ≦ 4, 0 ≦ y <2)
(R is an alkyl group) a tetrafunctional siloxane resin,
Film forming elements such as silanol and silanol resin which is a dehydration-condensation polymer thereof can be suitably used. Of these, the average composition formula (OR) x SiOy (0 <x
It is most preferable to use a tetrafunctional siloxane resin consisting of ≦ 4, 0 ≦ y <2) (R is an alkyl group). For the same reason as described above, even when the intermediate layer is formed, the components of the intermediate layer include the average composition formula (OR) x SiOy (0 <x ≦ 4, 0 ≦
It is preferable to use a tetrafunctional siloxane resin composed of y <2) (R is an alkyl group) because storage stability is good and a curing reaction can easily be caused at room temperature. In particular, if the curing reaction can be caused at room temperature, it is convenient when the substrate does not have heat resistance such as a vinyl chloride film. The curing reaction of the coating film forming element is performed, for example, by subjecting an amorphous silica precursor to a hydrolysis reaction by contacting the precursor with water or moisture in the air, followed by dehydration and shrinkage by a method such as heating, ultraviolet irradiation, or standing at room temperature. This is performed by a polymerization reaction.

【００２２】次に、表面層が光触媒とシリコーンからな
る場合について、光触媒がアナターゼ型酸化チタンの場
合を例にとり説明する。この場合の方法は、未硬化の若
しくは部分的に硬化したシリコーン又はシリコーンの前
駆体からなる塗料とアナターゼ型酸化チタンゾルとを混
合し、シリコーンの前駆体を必要に応じて加水分解させ
た後、混合物を基材の表面にスプレーコーティング法、
ディップコーティング法、フローコーティング法、スピ
ンコーティング法、ロールコーティング法等の方法で塗
布し、加熱等の方法でシリコーンの前駆体の加水分解物
を脱水縮重合に付して、アナターゼ型酸化チタン粒子と
シリコーンからなる表面層を形成する。形成された表面
層は、紫外線を含む光の照射によりアナターゼ型酸化チ
タンが光励起されることにより、シリコーン分子中のケ
イ素原子に結合した有機基の少なくとも一部を水酸基に
置換され、さらにその上に物理吸着水層が形成されて、
高度の親水性を呈する。ここでシリコーンの前駆体に
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、メチルトリブトキシシラン、メチルトリプロポキ
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、エチルトリブトキシシラン、エチルトリプ
ロポキシシラン、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、フェニルトリブトキシシラン、
フェニルトリプロポキシシラン、ジメチルジメトキシシ
ラン、ジメチルジエトキシシラン、ジメチルジブトキシ
シラン、ジメチルジプロポキシシラン、ジエチルジメト
キシシラン、ジエチルジエトキシシラン、ジエチルジブ
トキシシラン、ジエチルジプロポキシシラン、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、フェニルメチルジブトキシシラン、フェニルメチ
ルジプロポキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、及びそれらの加水分解物、それらの混
合物が好適に利用できる。Next, the case where the surface layer is made of a photocatalyst and silicone will be described by taking as an example the case where the photocatalyst is anatase type titanium oxide. The method in this case is to mix a coating of uncured or partially cured silicone or a silicone precursor with an anatase-type titanium oxide sol, hydrolyze the silicone precursor if necessary, and then mix the mixture. Spray coating method on the surface of the substrate,
Dip coating method, flow coating method, spin coating method, applied by a method such as roll coating method, by subjecting the hydrolyzate of the silicone precursor to dehydration polycondensation by a method such as heating, anatase type titanium oxide particles and A surface layer made of silicone is formed. In the formed surface layer, at least a part of the organic group bonded to the silicon atom in the silicone molecule is replaced with a hydroxyl group by photoexcitation of the anatase type titanium oxide by irradiation with light including ultraviolet rays, and further thereon. The physical adsorption water layer is formed,
It exhibits a high degree of hydrophilicity. Here, silicone precursors include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate thereof, and a mixture thereof can be suitably used.

【００２３】[0023]

【実施例】【Example】

実施例１．１０ｃｍ角のポリエチレンテレフタレートフ
ィルム上にプライマー塗料（信越シリコーン、ＰＣ−７
Ａ）をフローコーティング法にて塗布後、１２０℃で２
０分乾燥させて、基板をプライマー樹脂層で被覆した。
次に、シリコーン系ハードコーティング剤（信越シリコ
ーン、ＫＰ−８５）をフローコーティング法にて塗布
後、１２０℃で６０分乾燥させて、ハードコート層を形
成した。次に、ハードコート層をコロナ放電処理した
後、酸化チタン含有塗料組成物（アナターゼ型酸化チタ
ンゾル（日産化学、ＴＡ−１５、固形分１５重量％）１
６重量部とシリカゾル（日本合成ゴム、グラスカＡ液、
固形分１３重量％）９重量部を混合し、エタノール希釈
後、更にトリメトキシシラン３重量部（日本合成ゴム、
グラスカＢ液）を添加したもの）をフローコーティング
法にて塗布後、１２０℃で３０分熱処理して硬化させ、
試料を得た。この試料を数日間暗所に放置した後、紫外
線光源（三共電気、ブラックライトブルー（ＢＬＢ）蛍
光灯）を用いて試料の表面に０．５ｍＷ／ｃｍ２の紫外
線照度で約２日紫外線を照射し、＃１試料を得た。比較
のため、１０ｃｍ角のポリエチレンテレフタレートフィ
ルムを数日間暗所に放置した＃２試料も準備した。ま
ず、＃１試料と＃２試料に水滴を滴下し、滴下後の様子
の観察及び水との接触角の測定を行った。ここで水との
接触角は接触角測定器（協和界面科学、ＣＡ−Ｘ１５
０）を用い、滴下後３０秒後の水との接触角で評価し
た。その結果＃１試料はマイクロシリンジから試料表面
に水滴を滴下されると、水滴が一様に水膜状に試料表面
を拡がる様子が観察された。また、３０秒後の水との接
触角は約０゜まで高度に親水化された。それに対し、＃
２試料ではマイクロシリンジから試料表面に水滴を滴下
されると、水滴は表面にほとんどなじまず、一様に水膜
状になるまでには至らなかった。３０秒後の水との接触
角は約７０゜であった。次に、＃１試料と＃２試料に息
を吹きかけ曇り発生の有無を調べた。その結果＃２試料
では曇りが生じたのに対し、＃１試料では曇りは生じな
かった。さらに、＃１試料を、その後１週間暗所に放置
し、＃３試料を得た。そして＃３試料について、同様に
水滴を滴下し、滴下後の様子の観察及び水との接触角の
測定を行った。その結果、＃３試料にマイクロシリンジ
から試料表面に水滴を滴下されると、＃１試料と同様
に、水滴が一様に水膜状に試料表面を拡がる様子が観察
された。３０秒後の水との接触角は約２゜に維持され
た。次に＃３試料について息を吹きかけた後の曇り発生
の有無を観察した。その結果、曇りは観察されなかっ
た。Example 1. Primer paint (Shin-Etsu Silicone, PC-7) on a 10 cm square polyethylene terephthalate film
A) is applied at 120 ° C.
After drying for 0 minutes, the substrate was covered with a primer resin layer.
Next, a silicone hard coating agent (Shin-Etsu Silicone, KP-85) was applied by a flow coating method, and then dried at 120 ° C. for 60 minutes to form a hard coat layer. Next, after the hard coat layer was subjected to corona discharge treatment, a titanium oxide-containing coating composition (anatase type titanium oxide sol (Nissan Chemical, TA-15, solid content 15% by weight)) 1
6 parts by weight and silica sol (Nippon Synthetic Rubber, Glasca A solution,
9 parts by weight (solid content 13% by weight) were mixed, diluted with ethanol, and then 3 parts by weight of trimethoxysilane (Nippon Synthetic Rubber,
After the addition of Glasca B solution) by a flow coating method, it is cured by heat treatment at 120 ° C. for 30 minutes.
A sample was obtained. After leaving the sample in a dark place for several days, the surface of the sample is irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 2 days using an ultraviolet light source (Sankyo Electric, black light blue (BLB) fluorescent lamp). Then, a # 1 sample was obtained. For comparison, a # 2 sample in which a 10 cm square polyethylene terephthalate film was left in a dark place for several days was also prepared. First, a water drop was dropped on the # 1 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water is measured using a contact angle measuring device (Kyowa Interface Science, CA-X15).
Using 0), the contact angle with water 30 seconds after dropping was evaluated. As a result, when a water drop was dropped from the micro syringe onto the sample surface, it was observed that the water droplet spread uniformly on the sample surface in a water film shape. The contact angle with water after 30 seconds was highly hydrophilized to about 0 °. For it,#
In two samples, when a water drop was dropped on the sample surface from the microsyringe, the water drop hardly conformed to the surface and did not reach a uniform water film state. The contact angle with water after 30 seconds was about 70 °. Next, the samples # 1 and # 2 were blown to examine whether or not fogging occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 1 sample. Further, the # 1 sample was left in a dark place for one week thereafter to obtain a # 3 sample. A water drop was similarly dropped on the # 3 sample, and the state after the drop was observed and the contact angle with water was measured. As a result, when a water drop was dropped on the sample surface from the microsyringe on the # 3 sample, it was observed that the water droplet spread uniformly on the sample surface like a # 1 sample. After 30 seconds, the contact angle with water was maintained at about 2 °. Next, the presence or absence of fogging after spraying was observed for the # 3 sample. As a result, no fogging was observed.

【００２４】次に、＃３試料の裏側にセッケン水を塗布
し、１０ｃｍ角のガラス基材に貼着した。次いで、ＢＬ
Ｂ蛍光灯を用いて試料の表面に０．５ｍＷ／ｃｍ２の紫
外線照度で約１時間紫外線を照射し、＃４試料を得た。
比較のため、＃２試料の裏側にセッケン水を塗布し、１
０ｃｍ角のガラス基材に貼着した。次いで、ＢＬＢ蛍光
灯を用いて試料の表面に０．５ｍＷ／ｃｍ２の紫外線照
度で約１時間紫外線を照射し、＃５試料を得た。＃４試
料、＃５試料の夫々の表面にオレイン酸を塗布し、試料
表面を水平姿勢に保持しながら夫々の試料を水槽に満た
した水の中に浸漬した。その結果、＃５試料では、オレ
イン酸は表面に付着したままであり、軽くこすってもオ
レイン酸は試料表面を伸びるだけであった。それに対
し、＃４試料では、オレイン酸は丸くなり、軽くこする
と表面から離脱した。従って、＃４試料では、＃５試料
に比較して水洗浄が容易であると考えられる。疎水性カ
ーボンブラック１重量部、親水性カーボンブラック１重
量部からなる粉体混合物を１．０５ｇ／リッターの濃度
で水に懸濁させたスラリーを調製した。４５度に傾斜さ
せた＃４試料、＃５試料に上記スラリー１５０ｍｌを流
下させて１５分間乾燥させ、次いで蒸留水１５０ｍｌを
流下させて１５分間乾燥させ、このサイクルを２５回反
復した。試験前後の色差変化を、色差計（東京電色）を
用いて計測した。色差は日本工業規格（ＪＩＳ）Ｈ０２
０１に従い、ΔＥ＊表示を用いて評価した。その結果、
＃５試料では色差変化が２０と大きかったのに対し、＃
４試料では色差変化は０．４と非常に小さかった。Next, soap water was applied to the back side of the # 3 sample, and the sample was stuck to a 10 cm square glass substrate. Then, BL
Using a B fluorescent lamp, the surface of the sample was irradiated with ultraviolet light at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 4 sample.
For comparison, apply soap water to the back side of # 2 sample,
Affixed to a 0 cm square glass substrate. Next, using a BLB fluorescent lamp, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 5 sample. Oleic acid was applied to the surface of each of the # 4 sample and the # 5 sample, and each sample was immersed in water filled in a water tank while keeping the sample surface in a horizontal posture. As a result, in the # 5 sample, oleic acid remained adhered to the surface, and oleic acid only extended on the sample surface even when rubbed lightly. On the other hand, in the # 4 sample, oleic acid was rounded and detached from the surface when lightly rubbed. Therefore, it is considered that the # 4 sample is easier to wash with water than the # 5 sample. A slurry was prepared by suspending a powder mixture consisting of 1 part by weight of hydrophobic carbon black and 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. The # 4 sample and the # 5 sample inclined at 45 degrees were allowed to flow down 150 ml of the above slurry and dried for 15 minutes, and then flow down 150 ml of distilled water and dried for 15 minutes. This cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). Color difference is Japanese Industrial Standard (JIS) H02
In accordance with No. 01, evaluation was made using ΔE * notation. as a result,
In the # 5 sample, the color difference change was as large as 20,
In the four samples, the change in color difference was as small as 0.4.

【００２５】実施例２．（常温硬化法） １０ｃｍ角のポリエチレンテレフタレートフィルムをコ
ロナ放電処理した後、エチルシリケート５量体相当品
（コルコート、エチルシリケート４０）３０重量部とメ
チルアルコール２３．５重量部を、３０℃の恒温槽に入
れたビーカー中で混合した。これにイオン交換水４５重
量部と６０％硝酸１．５重量部の混合液を添加し、３０
℃に保持したまま５時間加水分解させて、中間コーティ
ング液を調製した。この中間コーティング液をコロナ放
電処理したプライマー樹脂上にフローコーティング法に
て塗布し、常温で１０分乾燥させて、中間層を形成し
た。次に、中間層をコロナ放電処理した後、光触媒コー
ティング液（石原産業のＳＴ−Ｋ０１とＳＴ−Ｋ０３を
１：１で混合後、アルコールで希釈することにより作製
した、アナターゼ型酸化チタン粒子とテトラアルコキシ
シランの部分加水分解物であるアルキルシリケートを１
３：７で含むコーティング液）をフローコーティング法
にて塗布し、常温で１０分乾燥させて、光触媒含有表面
層を形成した。形成面の水との接触角は５゜であった。
また、形成面についてテープ剥離試験（セロファンテー
プを塗膜表面の片端から他端にわたって貼着した後、素
早く剥したときに、塗膜が剥れるか否かを評価する試
験）を調べた。その結果、外観に変化はなかった。また
試験後の水との接触角も５゜であった。この試料を数日
間暗所に放置した後、ＢＬＢ蛍光灯を用いて試料の表面
に０．５ｍＷ／ｃｍ２の紫外線照度で約２日紫外線を照
射し、＃６試料を得た。比較のため、１０ｃｍ角のポリ
エチレンテレフタレートフィルムを数日間暗所に放置し
た実施例１と同様の＃２試料も準備した。まず、＃６試
料と＃２試料に水滴を滴下し、滴下後の様子の観察及び
水との接触角の測定を行った。その結果＃６試料はマイ
クロシリンジから試料表面に水滴を滴下されると、水滴
が一様に水膜状に試料表面を拡がる様子が観察された。
また、３０秒後の水との接触角は約０゜まで高度に親水
化された。それに対し、＃２試料ではマイクロシリンジ
から試料表面に水滴を滴下されると、水滴は表面にほと
んどなじまず、一様に水膜状になるまでには至らなかっ
た。３０秒後の水との接触角は約７０゜であった。次
に、＃６試料と＃２試料に息を吹きかけ曇り発生の有無
を調べた。その結果＃２試料では曇りが生じたのに対
し、＃６試料では曇りは生じなかった。Embodiment 2 FIG. (Cold curing method) After subjecting a 10 cm square polyethylene terephthalate film to a corona discharge treatment, 30 parts by weight of ethyl silicate pentamer equivalent product (colcoat, ethyl silicate 40) and 23.5 parts by weight of methyl alcohol were placed in a thermostat at 30 ° C. In a beaker. To this, a mixed solution of 45 parts by weight of ion-exchanged water and 1.5 parts by weight of 60% nitric acid was added.
The mixture was hydrolyzed for 5 hours while maintaining the temperature at 0 ° C to prepare an intermediate coating solution. This intermediate coating solution was applied on a primer resin subjected to corona discharge treatment by a flow coating method, and dried at room temperature for 10 minutes to form an intermediate layer. Next, after the intermediate layer was subjected to a corona discharge treatment, a photocatalyst coating solution (anatase-type titanium oxide particles and tetratetraoxide prepared by mixing 1: 1 of ST-K01 and ST-K03 of Ishihara Sangyo and diluting with alcohol). Alkyl silicate which is a partial hydrolyzate of alkoxysilane
3: 7) was applied by a flow coating method and dried at room temperature for 10 minutes to form a photocatalyst-containing surface layer. The contact angle of the formed surface with water was 5 °.
In addition, a tape peeling test (a test for evaluating whether or not the coating film peels off when the cellophane tape was quickly peeled off after being adhered from one end to the other end of the coating film surface) was examined for the formed surface. As a result, there was no change in appearance. The contact angle with water after the test was 5 °. After leaving the sample in a dark place for several days, the surface of the sample was irradiated with ultraviolet rays for about two days at a UV illuminance of 0.5 mW / cm 2 using a BLB fluorescent lamp to obtain a # 6 sample. For comparison, a # 2 sample similar to that of Example 1 in which a 10 cm square polyethylene terephthalate film was left in a dark place for several days was also prepared. First, a water drop was dropped on the # 6 sample and the # 2 sample, and the state after the drop was observed and the contact angle with water was measured. As a result, when a water drop was dropped on the sample surface from the microsyringe of the # 6 sample, it was observed that the water droplet spread uniformly on the sample surface in the form of a water film.
The contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the case of the # 2 sample, when a water drop was dropped on the sample surface from the microsyringe, the water drop hardly applied to the surface and did not reach a uniform water film state. The contact angle with water after 30 seconds was about 70 °. Next, the samples # 6 and # 2 were blown to examine whether or not fogging occurred. As a result, fogging occurred in the # 2 sample, but no fogging occurred in the # 6 sample.

【００２６】次に、＃６試料の裏側にセッケン水を塗布
し、１０ｃｍ角のガラス基材に貼着した。次いで、ＢＬ
Ｂ蛍光灯を用いて試料の表面に０．５ｍＷ／ｃｍ２の紫
外線照度で約１時間紫外線を照射し、＃７試料を得た。
比較のため、実施例１と同様に、＃２試料の裏側にセッ
ケン水を塗布し、１０ｃｍ角のガラス基材に貼着し、次
いで、ＢＬＢ蛍光灯を用いて試料の表面に０．５ｍＷ／
ｃｍ２の紫外線照度で約１時間紫外線を照射し、＃５試
料を得た。＃７試料、＃５試料の夫々の表面にオレイン
酸を塗布し、試料表面を水平姿勢に保持しながら夫々の
試料を水槽に満たした水の中に浸漬した。その結果、＃
５試料では、オレイン酸は表面に付着したままであり、
軽くこすってもオレイン酸は試料表面を伸びるだけであ
った。それに対し、＃７試料では、オレイン酸は丸くな
り、軽くこすると表面から離脱した。従って、＃７試料
では、＃５試料に比較して水洗浄が容易であると考えら
れる。疎水性カーボンブラック１重量部、親水性カーボ
ンブラック１重量部からなる粉体混合物を１．０５ｇ／
リッターの濃度で水に懸濁させたスラリーを調製した。
４５度に傾斜させた＃７試料、＃５試料に上記スラリー
１５０ｍｌを流下させて１５分間乾燥させ、次いで蒸留
水１５０ｍｌを流下させて１５分間乾燥させ、このサイ
クルを２５回反復した。試験前後の色差変化を、色差計
（東京電色）を用いて計測した。色差は日本工業規格
（ＪＩＳ）Ｈ０２０１に従い、ΔＥ＊表示を用いて評価
した。その結果、＃５試料では色差変化が２０と大きか
ったのに対し、＃７試料では色差変化は０．４と非常に
小さかった。Next, soap water was applied to the back side of the # 6 sample, and the sample was attached to a 10 cm square glass substrate. Then, BL
Using a B fluorescent lamp, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 7 sample.
For comparison, in the same manner as in Example 1, soap water was applied to the back side of the # 2 sample, adhered to a glass substrate of 10 cm square, and then 0.5 mW /
Ultraviolet light was irradiated for about 1 hour at an ultraviolet illuminance of cm 2 to obtain a # 5 sample. Oleic acid was applied to each surface of the # 7 sample and the # 5 sample, and each sample was immersed in water filled in a water tank while keeping the sample surface in a horizontal posture. as a result,#
In five samples, oleic acid remains attached to the surface,
Oleic acid only extended the sample surface when rubbed lightly. On the other hand, in the sample # 7, oleic acid was rounded and detached from the surface when lightly rubbed. Therefore, it is considered that the # 7 sample is easier to wash with water than the # 5 sample. 1.05 g / powder mixture consisting of 1 part by weight of hydrophobic carbon black and 1 part by weight of hydrophilic carbon black
A slurry suspended in water at the concentration of liter was prepared.
The # 7 sample and the # 5 sample inclined at 45 degrees were allowed to flow 150 ml of the above slurry and dried for 15 minutes, and then were dried for 15 minutes by flowing 150 ml of distilled water, and this cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standards (JIS) H0201 using ΔE * notation. As a result, the color difference change was as large as 20 in the # 5 sample, while the color difference change was as small as 0.4 in the # 7 sample.

【００２７】[0027]

【発明の効果】本発明では、フィルム基体表面に、光触
媒性酸化チタン粒子を含有する表面層を備えることによ
り、光触媒の光励起に応じて、表面層の表面は親水性を
呈する。それにより、このフィルムを貼着するだけで、
透明基材表面の曇り等が防止されて視界確保性が向上す
る。また、降雨により基材表面がセルフクリーニングさ
れるようになる。さらに、基材表面が水により容易に洗
浄されるようになる。According to the present invention, by providing a surface layer containing photocatalytic titanium oxide particles on the surface of the film substrate, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst. By simply sticking this film,
Fogging and the like on the surface of the transparent substrate are prevented, and visibility is improved. In addition, the surface of the base material is self-cleaned by the rainfall. Further, the surface of the base material can be easily washed with water.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明に係るフィルムの表面構造を示す図。FIG. 1 is a view showing a surface structure of a film according to the present invention.

【図２】 本発明に係るフィルムの他の表面構造を示す
図。FIG. 2 is a view showing another surface structure of the film according to the present invention.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−246984（ＪＰ，Ａ) 特開 昭61−91042（ＪＰ，Ａ) 特開 昭63−100042（ＪＰ，Ａ) 特開 平９−57911（ＪＰ，Ａ) 特開 平９−227161（ＪＰ，Ａ) 特開 平９−225387（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 1/00 - 35/00 B05D 5/00 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-246984 (JP, A) JP-A-61-191042 (JP, A) JP-A-63-100042 (JP, A) JP-A-9-92 57911 (JP, A) JP-A-9-227161 (JP, A) JP-A-9-225587 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 1/00-35 / 00 B05D 5/00

Claims (16)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 フィルム基体表面に、光触媒粒子を含有
する表面層を備えてなり、基材表面に貼着すると、表面
が前記光触媒の光励起に応じて親水性を呈することを特
徴とする防曇用フィルム。1. An anti-fogging method comprising: providing a surface layer containing photocatalyst particles on the surface of a film substrate, wherein the surface exhibits hydrophilicity in response to photoexcitation of the photocatalyst when adhered to the substrate surface. For film. 【請求項２】 フィルム基体表面に、実質的に透明な、
光触媒粒子を含有する表面層を備えてなり、基材表面に
貼着すると、表面が前記光触媒の光励起に応じて親水性
を呈し、以って付着した湿分の凝縮水及び／又は水滴が
前記層の表面に一様に広がり、湿分凝縮水及び／又は水
滴によって曇り若しくは翳るのが防止されるようになる
ことを特徴とする防曇用フィルム。2. The method according to claim 1, wherein the substantially transparent,
It is provided with a surface layer containing photocatalyst particles, and when adhered to the substrate surface, the surface exhibits hydrophilicity in response to the photoexcitation of the photocatalyst, and condensed water and / or water droplets of the adhering moisture are thus removed. An anti-fogging film characterized by being uniformly spread on the surface of a layer and being prevented from being clouded or shaded by moisture condensed water and / or water droplets. 【請求項３】 前記表面層には、さらに無定型シリカが
含有されていることを特徴とする請求項１又は２記載の
防曇用フィルム。3. The antifogging film according to claim 1, wherein the surface layer further contains amorphous silica. 【請求項４】 前記表面層には、さらにシリコーンが含
有されていることを特徴とする請求項１又は２記載の防
曇用フィルム。4. The antifogging film according to claim 1, wherein the surface layer further contains silicone. 【請求項５】 前記表面層の膜厚は０．４μｍ以下であ
ることを特徴とする請求項１乃至４いずれか１項記載の
防曇用フィルム。5. The antifogging film according to claim 1, wherein the thickness of the surface layer is 0.4 μm or less. 【請求項６】 前記表面層の膜厚は０．２μｍ以下であ
ることを特徴とする請求項１乃至４いずれか１項記載の
防曇用フィルム。6. The antifogging film according to claim 1, wherein the thickness of the surface layer is 0.2 μm or less. 【請求項７】 前記表面層の表面に、さらに親水化可能
な保護層が設けられていることを特徴とする請求項１乃
至４いずれか１項記載の防曇用フィルム。7. The antifogging film according to claim 1, wherein a protective layer capable of being made hydrophilic is further provided on the surface of the surface layer. 【請求項８】 前記表面層の屈折率は２以下であること
を特徴とする請求項１乃至７いずれか１項記載の防曇用
フィルム。8. The anti-fogging film according to claim 1, wherein the refractive index of the surface layer is 2 or less. 【請求項９】 前記光触媒の光励起に応じて呈する親水
性は、水との接触角に換算して１０°以下であることを
特徴とする請求項１乃至８いずれか１項記載の防曇用フ
ィルム。9. The antifogging agent according to claim 1, wherein the hydrophilicity of the photocatalyst in response to photoexcitation is 10 ° or less in terms of a contact angle with water. the film. 【請求項１０】 前記光触媒の光励起に応じて呈する親
水性は、水との接触角に換算して５°以下であることを
特徴とする請求項１乃至８いずれか１項記載の防曇用フ
ィルム。10. The antifogging agent according to claim 1, wherein the hydrophilicity of the photocatalyst in response to photoexcitation is 5 ° or less in terms of a contact angle with water. the film. 【請求項１１】 フィルム基体を準備する工程、その上
を光触媒粒子と無定型シリカの前駆体で被覆する工程、
無定型シリカの前駆体を硬化反応により無定型シリカに
変換する工程；を含む光励起に応じて親水性を呈する防
曇用フィルムの製造方法。11. A step of preparing a film substrate, and coating the film substrate with photocatalyst particles and a precursor of amorphous silica.
Converting a precursor of amorphous silica into amorphous silica by a curing reaction, the method comprising the steps of: 【請求項１２】 フィルム基体を準備する工程、フィル
ム基体表面にベースコート層を形成する工程、さらにそ
の上を光触媒粒子と無定型シリカの前駆体で被覆する工
程、無定型シリカの前駆体を硬化反応により無定型シリ
カに変換する工程；を含む光励起に応じて親水性を呈す
る防曇用フィルムの製造方法。12. A step of preparing a film base, a step of forming a base coat layer on the surface of the film base, a step of coating the base with a photocatalyst particle and a precursor of amorphous silica, and a curing reaction of the precursor of amorphous silica. A method for producing an antifogging film exhibiting hydrophilicity in response to photoexcitation. 【請求項１３】 前記無定型シリカの前駆体は平均組成
式（ＯＲ）ｘＳｉＯｙ（０＜ｘ≦４、０≦ｙ＜２）（Ｒ
はアルキル基）からなる塗膜形成要素であり、前記無定
型シリカの前駆体を硬化反応により無定型シリカに変換
する工程は、常温で乾燥させる工程である請求項１１又
は１２に記載の光励起に応じて親水性を呈する防曇用フ
ィルムの製造方法。13. The precursor of the amorphous silica has an average composition formula (OR) xSiOy (0 <x ≦ 4, 0 ≦ y <2) (R
Is an alkyl group), and the step of converting the precursor of amorphous silica to amorphous silica by a curing reaction is a step of drying at room temperature. A method for producing a film for antifogging, which exhibits hydrophilicity in response. 【請求項１４】 前記ベースコート層を形成する工程
は、平均組成式（ＯＲ）ｘＳｉＯｙ（０＜ｘ≦４、０≦
ｙ＜２）（Ｒはアルキル基）からなる塗膜形成要素でフ
ィルム基体を被覆する工程と、常温で乾燥させることに
より前記塗膜形成要素を硬化させる工程であることを特
徴とする請求項１２又は１３記載の光励起に応じて親水
性を呈する防曇用フィルムの製造方法。14. The step of forming the base coat layer comprises the step of forming an average composition formula (OR) xSiOy (0 <x ≦ 4, 0 ≦
13. The method according to claim 12, wherein y <2) a step of coating the film substrate with a film-forming element composed of (R is an alkyl group), and a step of curing the film-forming element by drying at room temperature. Or the method for producing an anti-fogging film exhibiting hydrophilicity in response to light excitation according to item 13. 【請求項１５】 フィルム基体を準備する工程、その上
を光触媒粒子とシリコーンの前駆体で被覆する工程、シ
リコーンの前駆体を硬化反応により硬化させて、シリコ
ーン樹脂中に光触媒が分散された塗膜を形成する工程、
前記光触媒を光励起させて、シリコーン樹脂中のシリコ
ーン原子に結合する有機基を水酸基に置換させる工程；
を含む光励起に応じて親水性を呈する防曇用フィルムの
製造方法。15. A step of preparing a film substrate, a step of coating the film substrate with photocatalyst particles and a silicone precursor, and a step of curing the silicone precursor by a curing reaction to disperse a photocatalyst in a silicone resin. Forming a,
A step of photo-exciting the photocatalyst to replace an organic group bonded to a silicone atom in the silicone resin with a hydroxyl group;
A method for producing an antifogging film exhibiting hydrophilicity in response to photoexcitation. 【請求項１６】 請求項１乃至１０いずれか１項記載の
防曇用フィルムを準備する工程、前記親水性フィルムを
基材表面に貼着する工程、前記防曇用フィルム表面層に
含有される光触媒を光励起することにより、前記層の表
面を親水性になす工程；からなる基材表面の防曇化方
法。16. A step of preparing the antifogging film according to claim 1, a step of attaching the hydrophilic film to a substrate surface, and a step of adhering to the surface layer of the antifogging film. Making the surface of the layer hydrophilic by photo-exciting the photocatalyst.
JP28453496A 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same Expired - Lifetime JP3173391B2 (en)

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JP7-354649 1995-12-22
JP35464995 1995-12-22
JP28453496A JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same

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Publications (2)

Publication Number Publication Date
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JP3173391B2 true JP3173391B2 (en) 2001-06-04

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JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP08344585A Expired - Lifetime JP3141802B2 (en) 1995-12-22 1996-12-09 Hydrophilic member and method for maintaining hydrophilicity
JP23956899A Expired - Lifetime JP3613085B2 (en) 1995-12-22 1999-08-26 Photocatalytic hydrophilic member
JP23956799A Expired - Lifetime JP3613084B2 (en) 1995-12-22 1999-08-26 A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor
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
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
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
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
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

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