JPH09231807A - Vehicle headlight cover, vehicle with it, and its defogging method - Google Patents

Vehicle headlight cover, vehicle with it, and its defogging method

Info

Publication number
JPH09231807A
JPH09231807A JP8275189A JP27518996A JPH09231807A JP H09231807 A JPH09231807 A JP H09231807A JP 8275189 A JP8275189 A JP 8275189A JP 27518996 A JP27518996 A JP 27518996A JP H09231807 A JPH09231807 A JP H09231807A
Authority
JP
Japan
Prior art keywords
surface layer
titanium oxide
vehicle
cover according
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.)
Pending
Application number
JP8275189A
Other languages
Japanese (ja)
Inventor
Makoto Hayakawa
信 早川
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=18438979&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPH09231807(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP8275189A priority Critical patent/JPH09231807A/en
Publication of JPH09231807A publication Critical patent/JPH09231807A/en
Pending legal-status Critical Current

Links

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

Abstract

PROBLEM TO BE SOLVED: To provide a headlight cover glass and its defogging method which can achieve a high degree of visibility by equipping the cover at least on its internal surface with a substantially transparent surface layer containing titanium oxide particles to work as photocatalyst. SOLUTION: A layer containing titanium oxide (crystalline) or the like to work as photocatalyst is formed on the surface of a base material. When applied to the internal surface of a cover for the headlight of a vehicle, this surface structure is turned hydrophilic to a high degree in response to photo-excitation of the photocatalyst caused by ultraviolet rays contained in the beams of light emitted by the headlight. Even when the moisture in the atmosphere is condensed to be attached to the surface of the base material, it will not grow to water drops, but a uniform water film is produced. This allows preventing the headlight cover from being foggy by the condensate and/or water drops. The surface layer may consist of particles of titanium oxide solely, or amixture of titanium oxide particles with ordinary inorganic oxides.

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、自動車、オートバ
イや、電車、汽車、気動車、機関車等の鉄道車両の付帯
設備である前照灯の防曇技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifogging technique for a headlight, which is an auxiliary equipment for automobiles, motorcycles, trains, trains, railcars such as trains and locomotives.

【０００２】[0002]

【従来の技術】寒冷時や雨天に自動車、オートバイの前
照灯用カバーガラスが凝縮湿分で曇り、照度が低下する
のはよく経験されることである。それが極端になれば寒
冷時や雨天の夜間走行に支障をきたすことになる。一般
に、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、カバーガラスは見かけ上不透明となり、
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、表面は翳り、ぼやけ、斑模様
になり、或いは曇る。その結果、カバーガラスでは透視
像が歪んで前照灯からの光線の外気への透視性が低下す
る。さらに、カバーガラス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。2. Description of the Related Art It is often experienced that the cover glass for headlights of automobiles and motorcycles becomes cloudy due to condensed moisture and the illuminance decreases when it is cold or rainy. If it becomes extreme, it will hinder nighttime driving in cold weather or in rainy weather. Generally, the surface of an article is fogged because when the surface is placed at a temperature below the dew point of the atmosphere, moisture in the atmosphere condenses and condenses on the surface. If the condensed water droplets are sufficiently fine and their diameter is about 1/2 of the wavelength of visible light, the water droplets scatter light and the cover glass becomes apparently opaque,
Visibility is lost. If the condensation of moisture progresses further, and fine condensed water droplets fuse with each other and grow into larger discrete water droplets, the surface becomes dark due to the refraction of light at the water droplet-surface interface and the water droplet-air interface, Blurred, mottled or cloudy. As a result, the transparent image is distorted on the cover glass, and the transparency of the light rays from the headlight to the outside air is deteriorated. Further, when the cover glass is exposed to rain or splashes and a large number of discrete water droplets adhere to the surface, the surface may be shaded, blurred, mottled, or cloudy, and visibility is also lost. 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.

【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。他方、前照灯カバーガラスの防曇方法として、実開
平５−６８００６号（スタンレー電気）には、親水基を
有するアクリル系モノマーと疎水基を有するモノマーと
のグラフト重合体からなる防曇性被膜を形成された車両
用灯具が開示されている。このグラフト重合体の水との
接触角は５０゜程度であり、この防曇性被膜は充分な防
曇性能を備えていないと考えられる。As is well known, the conventionally used antifogging method is to apply an antifogging 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. On the other hand, as an anti-fog method for a headlight cover glass, Jikkaihei 5-68006 (Stanley Electric Co., Ltd.) discloses an anti-fog coating composed of a graft polymer of an acrylic monomer having a hydrophilic group and a monomer having a hydrophobic group. There is disclosed a vehicular lamp having the above structure. The contact angle of this graft polymer with water is about 50 °, and it is considered that this antifogging film does not have sufficient antifogging performance.

【０００４】[0004]

【発明の解決すべき課題】本発明の目的は、高度な可視
性を実現することの可能な前照灯カバーガラス及びその
防曇方法を提供することにある。本発明の他の目的は、
長期にわたって高度の親水性を維持し、防曇性を示すこ
との可能な前照灯カバーガラス及びその防曇方法を提供
することにある。本発明の他の目的は、ほぼ恒久的に高
度の親水性を維持し、防曇性を示すことの可能な前照灯
カバーガラス及びその防曇方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a headlight cover glass capable of achieving a high degree of visibility and a method for preventing the fog thereof. Another object of the present invention is to
It is an object of the present invention to provide a headlight cover glass capable of maintaining a high degree of hydrophilicity for a long period of time and exhibiting antifogging properties, and a method for preventing the fog. Another object of the present invention is to provide a headlight cover glass capable of maintaining a high degree of hydrophilicity almost permanently and exhibiting an antifogging property, and a method of preventing the same.

【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 the photocatalyst is irradiated with light having an energy larger than the energy gap between the valence band upper end and the conduction band lower end of the photocatalyst, the electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. The action of either or both of them probably imparts polarity to the surface and collects polar components such as water and hydroxyl groups. 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.

【０００６】本発明では、乗物前照灯用カバー基材の少
なくとも内側の表面に、実質的に透明な光触媒性酸化チ
タン粒子を含有する表面層を備えた乗物前照灯用カバー
を提供する。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、前照灯から照射される光線中に含
有される紫外線が、光触媒性酸化チタンに照射されて光
励起されることに応じて、表面層の表面は親水性を呈
し、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。According to the present invention, there is provided a vehicle headlight cover having a surface layer containing substantially transparent photocatalytic titanium oxide particles on at least the inner surface of the vehicle headlight cover base material. By including the surface layer containing the photocatalytic titanium oxide particles, the ultraviolet rays contained in the light beam emitted from the headlight, in response to the photocatalytic titanium oxide being irradiated and photoexcited, the surface layer The surface becomes hydrophilic, so that the condensed water and / or water droplets of the attached moisture are spread evenly on the surface of the layer, so that the condensed water and / or water droplets of the moisture can be prevented from clouding or covering.

【０００７】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 ability of silica to store water in its structure.

【０００８】本発明の好ましい態様においては、表面層
には、さらに固体超強酸が含有されているようにする。
超強酸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。その理由は表面層に
超強酸が含有されると、表面の極性が、光の有無にかか
わらず極端に大きな状態にあるために、疎水性分子より
も極性分子である水分子を選択的に吸着させやすい。そ
のため安定な物理吸着水層が形成されやすく、暗所に保
持しても、表面の親水性をかなり長期にわたり高度に維
持できる。In a preferred embodiment of the present invention, the surface layer further contains a solid super strong acid.
By containing a super strong acid, the surface is likely to exhibit a high degree of hydrophilicity close to a water wetting angle of 0 °, and at the same time, the hydrophilicity maintaining property when kept in a dark place is improved. The reason is that when the surface layer contains a super strong acid, the polarity of the surface is extremely large irrespective of the presence or absence of light, so that water molecules, which are polar molecules, are selectively adsorbed over hydrophobic molecules. Easy to make. Therefore, a stable physically adsorbed water layer is easily formed, and even if the layer is kept in a dark place, the hydrophilicity of the surface can be maintained at a high level for a considerably long period.

【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 silicone, by photoexcitation of the photocatalyst, at least a part of the organic group bonded to the silicon atom in the silicone is replaced with a hydroxyl group, and a physically adsorbed water layer is formed on the organic group, so that the surface is It exhibits a high degree of hydrophilicity close to a water wetting angle of 0 °, and improves the hydrophilicity maintaining ability when kept in a dark place.

【００１０】[0010]

【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。本発明における乗物前照灯用カバーの内
側表面には、図１又は図２に示すように、基材の表面に
光触媒（結晶）性酸化チタン等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、乗物前照灯用カ
バーの内側表面は、前照灯から照射される光線中に含有
される紫外線の照射により、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。BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. As shown in FIG. 1 or 2, on the inner surface of the vehicle headlight cover in the present invention, a layer containing a photocatalytic (crystalline) titanium oxide or the like is formed on the surface of the base material. By taking such a surface structure, the inner surface of the vehicle headlamp cover is highly hydrophilized in response to photoexcitation of the photocatalyst by irradiation of ultraviolet rays contained in the light emitted from the headlight. It is. As a result, even if the moisture in the atmosphere is condensed and adheres, it does not grow in the form of water droplets, and a uniform water film is formed, which prevents the moisture condensed water and / or water droplets from clouding or clinging. It

【００１１】図１においては、表面層が光触媒性酸化チ
タン粒子のみからなる。この場合、光触媒が酸化物から
なることにより、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, the surface layer consists only of photocatalytic titanium oxide particles. In this case, since the photocatalyst is made of an oxide, the oxide shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, so that the photoexcited action is to eliminate the pollutant to form an adsorbed water layer. so,
It easily exhibits hydrophilicity and can form a uniform water film. 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. Also in this case, since the oxide shows hydrophilicity in the state where the pollutant in the environment is not adsorbed, the pollutant is excluded by the photoexcitation action of the photocatalytic titanium oxide mixed in the surface layer other than the above inorganic oxide. By forming the adsorbed water layer, a uniform water film can be formed.

【００１２】本発明における乗物前照灯用カバー基材に
は、ガラス、プラスチック等の透明体からなるカバーが
好適に利用できる。その用途は、特に限定されるもので
はないが、自動車前照灯用カバー、（自動）二輪車前照
灯用カバー、鉄道車両前照灯用カバーに特に好適に利用
できる。A cover made of a transparent material such as glass or plastic can be suitably used as the vehicle headlight cover base material in the present invention. The use is not particularly limited, but it can be particularly suitably used for a vehicle headlight cover, a (motorcycle) motorcycle headlight cover, and a railway vehicle headlight cover.

【００１３】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、光触媒性酸化チタ
ンとは、例えば、アナターゼ型酸化チタン、ルチル型酸
化チタン等の結晶性酸化チタンをいう。ここで光触媒の
光励起に用いる光源としては、前照灯が利用できる。前
照灯としては、白熱電灯、メタルハライドランプ、水銀
ランプ、キセノンランプ等の光源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、０．００１ｍＷ／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。A photocatalyst is a photocatalyst of electrons in the valence band when irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. Excitation (photoexcitation) refers to a substance capable of generating conduction electrons and holes, and the photocatalytic titanium oxide refers to crystalline titanium oxide such as anatase type titanium oxide and rutile type titanium oxide. Here, a headlight can be used as a light source used for photoexcitation of the photocatalyst. As the headlight, a light source such as an incandescent lamp, a metal halide lamp, a mercury lamp, or a xenon lamp can be preferably used.
By photoexcitation of the photocatalyst, because the substrate surface is highly hydrophilized, illuminance of the excitation light, may if 0.001 mW / cm 2 or more, preferably that it 0.01 mW / cm 2 or more, 0. More preferably, it is 1 mW / cm 2 or more.

【００１４】光触媒性酸化チタンを含有する表面層の膜
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、光触媒性酸化チタン
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 photocatalytic titanium oxide is preferably 0.4 μm or less. Then, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, it is more preferable that the thickness of the surface layer containing the photocatalytic titanium oxide 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. 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.

【００１５】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
媒性酸化チタンに、屈折率２以下の他の物質を表面層に
添加する。ここで、屈折率２以下の他の物質としては、
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）等を表面層に添加できる。The surface layer preferably has a refractive index that is not so high as that of 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. To reduce the refractive index of the surface layer to 2 or less, another substance having a refractive index of 2 or less is added to the photocatalytic titanium oxide. Here, as another substance having a refractive index of 2 or less,
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 can be added to the surface layer.

【００１６】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。Metals such as Ag, Cu and 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.

【００１７】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。また、光
触媒以外に固体超強酸を添加した場合には、白金族金属
の添加により固体超強酸の酸度が向上するので、親水維
持性も向上し、付着水の水膜化がより促進されると共
に、ある程度長期間光触媒に励起光が照射されない場合
の親水維持性も向上する。On the surface layer, 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. Further, when a solid superacid other than the photocatalyst is added, since the acidity of the solid superacid is improved by the addition of the platinum group metal, the hydrophilicity maintenance property is also improved and the formation of a water film of the adhered water is further promoted. Also, the hydrophilicity maintaining property is improved when the photocatalyst is not irradiated with the excitation light for a certain period of time.

【００１８】基材がナトリウムのようなアルカリ網目修
飾イオンを含むガラス（ソーダライムガラス、並板ガラ
ス等）の場合には、基材と表面層との間にシリカ等の中
間層を形成してもよい。そうすれば、焼成中にアルカリ
網目修飾イオンが基材から表面層へ拡散するのが防止さ
れ、光触媒機能がよりよく発揮される。When the substrate is a glass containing alkali network modifying ions such as sodium (soda lime glass, parallel plate glass, etc.), an intermediate layer such as silica may be formed between the substrate and the surface layer. Good. Then, the diffusion of the alkali network modifying ions from the base material to the surface layer during the firing is prevented, and the photocatalytic function is more effectively exhibited.

【００１９】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／ＪＰ９６／００７３４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 easily fitting into the surface when water is dropped, and generally means 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 is about 10 ° or less. In particular, as disclosed in PCT / JP96 / 00734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less, as disclosed in PCT / JP96 / 00734.

【００２０】本発明における固体超強酸とは、ハメット
の酸度関数Ｈｏ≦−１１．９３なる固体酸化物を構成要
素に含む強酸をいい、具体的には、硫酸担持Ａｌ
２Ｏ３、硫酸担持ＴｉＯ２、硫酸担持ＺｒＯ２、硫酸担
持ＳｎＯ２、硫酸担持Ｆｅ２Ｏ３、硫酸担持ＳｉＯ２、
硫酸担持ＨｆＯ２、ＴｉＯ２／ＷＯ３、ＷＯ３／ＳｎＯ
２、ＷＯ３／ＺｒＯ２、ＷＯ３／Ｆｅ２Ｏ３、ＳｉＯ２
・Ａｌ２Ｏ３等が好適に利用できる。The solid superacid in the present invention refers to a strong acid containing a solid oxide having a Hammett acidity function Ho ≦ -11.93 as a constituent, and specifically, sulfuric acid-supporting Al.
2 O 3 , sulfuric acid supported TiO 2 , sulfuric acid supported ZrO 2 , sulfuric acid supported SnO 2 , sulfuric acid supported Fe 2 O 3 , sulfuric acid supported SiO 2 ,
Sulfuric acid supporting HfO 2 , TiO 2 / WO 3 , WO 3 / SnO
2 , WO 3 / ZrO 2 , WO 3 / Fe 2 O 3 , SiO 2
-Al 2 O 3 or the like can be suitably used.

【００２１】次に、表面層の形成方法について説明す
る。まず表面層が光触媒性酸化チタンのみからなる場合
の製法について、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、大別して３
つの方法がある。１の方法はゾル塗布焼成法であり、他
の方法は有機チタネート法であり、他の方法は電子ビー
ム蒸着法である。 （１）ゾル塗布焼成法 アナターゼ型酸化チタンゾルを、基材表面に、スプレー
コーティング法、デイ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、焼成する。 （２）有機チタネート法 チタンアルコキシド（テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等）、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤（塩酸、エチルアミン
等）を添加し、アルコール（エタノール、プロパノー
ル、ブタノール等）などの非水溶媒で希釈した後、部分
的に加水分解を進行させながら又は完全に加水分解を進
行させた後、混合物を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、
乾燥させる。乾燥により、有機チタネートの加水分解が
完遂して水酸化チタンが生成し、水酸化チタンの脱水縮
重合により無定型酸化チタンの層が基材表面に形成され
る。その後、アナターゼの結晶化温度以上の温度で焼成
して、無定型酸化チタンをアナターゼ型酸化チタンに相
転移させる。 （３）電子ビーム蒸着法 酸化チタンのターゲットに電子ビームを照射することに
より、基材表面に無定型酸化チタンの層を形成する。そ
の後、アナターゼの結晶化温度以上の温度で焼成して、
無定型酸化チタンをアナターゼ型酸化チタンに相転移さ
せる。Next, a method for forming the surface layer will be described. First, the production method in the case where the surface layer is composed of only photocatalytic titanium oxide will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is roughly divided into 3
There are two ways. The first method is a sol coating firing method, the other method is an organic titanate method, and the other method is an electron beam evaporation method. (1) Sol coating firing method Anatase type titanium oxide sol is coated on the substrate surface by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method and the like, and then baked. (2) Organic titanate method Titanium alkoxide (tetraethoxy titanium, tetramethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, etc.), titanium acetate, titanium chelate, etc. are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.). , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.), while partially or completely proceeding the hydrolysis, the mixture is spray-coated, dip-coated, Apply by methods such as flow coating method, spin coating method, roll coating method,
dry. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Electron beam evaporation method An amorphous titanium oxide layer is formed on the surface of a substrate by irradiating a titanium oxide target with an electron beam. After that, firing at a temperature higher than the crystallization temperature of anatase,
Phase transition of amorphous titanium oxide to anatase titanium oxide.

【００２２】次に、表面層が光触媒性酸化チタンとシリ
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。この場合の方法は、例
えば、以下の３つの方法がある。１つの方法はゾル塗布
焼成法であり、他の方法は有機チタネート法であり、他
の方法は４官能性シラン法である。 （１）ゾル塗布焼成法 アナターゼ型酸化チタンゾルとシリカゾルとの混合液
を、基材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、スピンコーテイン
グ法、ロールコーテイング法等の方法で塗布し、焼成す
る。 （２）有機チタネート法 チタンアルコキシド（テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等）、チタンアセテート、チタンキレート等の
有機チタネートに加水分解抑制剤（塩酸、エチルアミン
等）とシリカゾルを添加し、アルコール（エタノール、
プロパノール、ブタノール等）などの非水溶媒で希釈し
た後、部分的に加水分解を進行させながら又は完全に加
水分解を進行させた後、混合物を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、乾燥させる。乾燥により、有機チタネートの
加水分解が完遂して水酸化チタンが生成し、水酸化チタ
ンの脱水縮重合により無定型酸化チタンの層が基材表面
に形成される。その後、アナターゼの結晶化温度以上の
温度で焼成して、無定型酸化チタンをアナターゼ型酸化
チタンに相転移させる。 （３）４官能性シラン法 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）とアナターゼ型酸化チタンゾルとの混
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、必
要に応じて加水分解させてシラノールを形成した後、加
熱等の方法でシラノールを脱水縮重合に付す。Next, the case where the surface layer is composed of photocatalytic titanium oxide and silica will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, for example, there are the following three methods. One method is a sol coating and firing method, the other is an organic titanate method, and the other is a tetrafunctional silane method. (1) Sol coating firing method A mixture of anatase type titanium oxide sol and silica sol is applied to the surface of the substrate by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method and the like, and firing. To do. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol. Add alcohol (ethanol,
After diluting with a non-aqueous solvent such as propanol, butanol, etc., and then allowing the hydrolysis to proceed partially or completely, the mixture is spray-coated, dip-coated, flow-coated,
It is applied by a method such as spin coating or roll coating and dried. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature equal to or higher than the crystallization temperature of anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Tetrafunctional silane method A mixture of tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.) and anatase type titanium oxide sol is spray-coated or dip-coated on the surface of a substrate. , A flow coating method, a spin coating method, a roll coating method, or the like, and if necessary, hydrolyzing to form silanol, and then silanol is subjected to dehydration condensation polymerization by a method such as heating.

【００２３】次に、表面層が光触媒性酸化チタンと固体
超強酸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、固体超強酸がＴｉＯ２／ＷＯ３の場合を例に
とり説明する。この場合の方法は、タングステン酸のア
ンモニア溶解液とアナターゼ型酸化チタンゾルとを混合
し、必要に応じて希釈液（水、エタノール等）で希釈し
た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、焼成する。Next, the case where the surface layer is composed of photocatalytic titanium oxide and a solid superacid is described by taking as an example the case where the photocatalyst is anatase type titanium oxide and the solid superacid is TiO 2 / WO 3 . In this case, a method of mixing an ammonia solution of tungstic acid and an anatase-type titanium oxide sol and, if necessary, diluting the mixture with a diluting liquid (water, ethanol, etc.) on the surface of the base material by spray coating, dip coating, or the like. It is applied by a method such as a flow coating method, a spin coating method, and a roll coating method, and is baked.

【００２４】次に、表面層が光触媒性酸化チタンとシリ
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 composed of photocatalytic titanium oxide and silicone will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is to mix a coating composed of uncured or partially cured silicone or a precursor of silicone and anatase type titanium oxide sol, and hydrolyze the precursor of silicone as needed, and then mix the mixture. Is applied to the surface of the substrate by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method and a roll coating method, and the hydrolyzate of the silicone precursor is dehydrated and polycondensed by a method such as heating. Then, a surface layer composed of anatase type titanium oxide particles and 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. A physisorbed water layer is formed and exhibits a high degree of hydrophilicity. Here, the silicone precursor includes methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane,
Ethyltripropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldi Ethoxysilane,
Diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldibutoxysilane,
Phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, their hydrolysates, and mixtures thereof can be suitably used.

【００２５】[0025]

【実施例】テトラエトキシシラン（和光純薬）０．６９
ｇとアナターゼ型酸化チタンゾル（日産化学、ＴＡ−１
５、平均粒径１０ｎｍ）１．０７ｇとエタノール２９．
８８ｇと、純水０．３６ｇを混合し、コーティング液を
調製した。このコーティング液をフローコーティング法
により、１０ｃｍ角のガラス基材上に塗布した。このガ
ラス板を約２０分間約１５０℃の温度に保持することに
より、テトラエトキシシランを加水分解と脱水縮重合に
付し、アナターゼ型酸化チタン粒子が無定型シリカで結
着されたコーティングをガラス板表面に形成した。この
コーティング中の、酸化チタンとシリカとの重量比は１
であった。このガラス板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１時間紫外線を照射し、＃１試料を得た。
比較のため、１０ｃｍ角のガラス板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−Ｘ１５０）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
れていた。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、水滴は表面になじ
んでいくものの、一様に水膜状になるまでには至らなか
った。また３０秒後の水との接触角は３０゜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２日間暗所に放置し、＃３試料を得た。そ
して＃３試料について、同様に水との接触角を接触角測
定器により測定した。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。また水との接触角は約３゜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: Tetraethoxysilane (Wako Pure Chemical Industries) 0.69
g and anatase type titanium oxide sol (NISSAN CHEMICAL, TA-1
5, average particle size 10 nm) 1.07 g and ethanol 29.
88 g and 0.36 g of pure water were mixed to prepare a coating liquid. This coating liquid was applied on a 10 cm square glass substrate by a flow coating method. By holding this glass plate at a temperature of about 150 ° C. for about 20 minutes, tetraethoxysilane is subjected to hydrolysis and dehydration polycondensation, and a coating in which anatase-type titanium oxide particles are bound with amorphous silica is applied to the glass plate. Formed on the surface. The weight ratio of titanium oxide to silica in this coating is 1
Met. After leaving this glass plate in the dark for several days, it is then exposed to an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB)).
The surface of the sample was irradiated with ultraviolet rays for about 1 hour using a fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm 2 to obtain a # 1 sample.
For comparison, a # 2 sample in which a 10 cm square glass plate was left in the dark 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 was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) based on the contact angle with water 30 seconds after dropping. 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. Further, 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 droplet adapted to the surface but did not reach a uniform water film state. The contact angle with water after 30 seconds was 30 °.
Next, the # 1 sample and the # 2 sample were blown to examine whether or not clouding 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 two days thereafter, to obtain a # 3 sample. Then, for the # 3 sample, the contact angle with water was similarly measured by a contact angle measuring device. 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. The contact angle with water was maintained at about 3 °.
Next, the presence or absence of fogging after spraying was observed for the # 3 sample. As a result, no fogging was observed.

【００２６】[0026]

【発明の効果】本発明では、乗物前照灯用カバーの少な
くとも内側の表面に、実質的に透明な光触媒性酸化チタ
ン粒子を含有する表面層を備えることにより、前照灯か
ら照射される光線中に含有される紫外線が、光触媒性酸
化チタンに照射されて光励起されることに応じて、表面
層の表面は親水性を呈し、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。According to the present invention, a light beam emitted from a headlight is provided by providing a surface layer containing substantially transparent photocatalytic titanium oxide particles on at least an inner surface of a vehicle headlight cover. When the photocatalytic titanium oxide is irradiated with the ultraviolet rays contained therein to be photoexcited, the surface of the surface layer exhibits hydrophilicity, and condensed water of the attached moisture and / or
Alternatively, the water droplets spread evenly on the surface of the layer, so that the moisture-condensed water and / or the water droplets are prevented from clouding or covering.

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

【図１】 本発明に係る前照灯用カバーの表面構造を示
す図。FIG. 1 is a diagram showing a surface structure of a headlight cover according to the present invention.

【図２】 本発明に係る前照灯用カバーの他の表面構造
を示す図。FIG. 2 is a view showing another surface structure of the headlight cover according to the present invention.

Claims (13)

【特許請求の範囲】[Claims] 【請求項１】 乗物前照灯用カバー基材の少なくとも内
側の表面に、実質的に透明な光触媒性酸化チタン粒子を
含有する表面層を備え、前記光触媒性酸化チタンが、前
照灯から照射される光線中に含有される紫外線の照射に
より光励起されることに応じて、前記層の表面は親水性
を呈し、以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った
乗物前照灯用カバー。1. A vehicle headlamp cover substrate is provided with a surface layer containing substantially transparent photocatalytic titanium oxide particles on at least an inner surface thereof, and the photocatalytic titanium oxide is irradiated from the headlamp. The surface of the layer becomes hydrophilic in response to being photoexcited by irradiation with ultraviolet rays contained in the light rays, and thus the condensed water and / or water droplets of the attached moisture are not absorbed on the surface of the layer. The vehicle headlight cover that spreads out and is prevented from being clouded or covered by moisture condensed water and / or water droplets. 【請求項２】 前記表面層には、さらにシリカが含有さ
れていることを特徴とする請求項１に記載の乗物前照灯
用カバー。2. The vehicle headlamp cover according to claim 1, wherein the surface layer further contains silica. 【請求項３】 前記表面層には、さらに固体超強酸が含
有されていることを特徴とする請求項１に記載の乗物前
照灯用カバー。3. The vehicle headlamp cover according to claim 1, wherein the surface layer further contains a solid superacid. 【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に記載の乗物前
照灯用カバー。4. The vehicle headlamp cover according to claim 1, wherein the surface layer further contains silicone. 【請求項５】 前記表面層の表面は、前記光触媒性酸化
チタンが光励起されることに応じて、水との接触角に換
算して１０゜以下の親水性を呈することを特徴とする請
求項１〜４に記載の乗物前照灯用カバー。5. The surface of the surface layer exhibits hydrophilicity of 10 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalytic titanium oxide. The vehicle headlamp cover according to any one of 1 to 4. 【請求項６】 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１〜４に記載の乗物前照灯用
カバー。6. The vehicle headlamp cover according to claim 1, wherein the surface layer has a thickness of 0.4 μm or less. 【請求項７】 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１〜４に記載の乗物前照灯用
カバー。7. The vehicle headlamp cover according to claim 1, wherein the surface layer has a thickness of 0.2 μm or less. 【請求項８】 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〜
４に記載の乗物前照灯用カバー。8. A hydrophilic protective layer is further provided on the surface of the surface layer.
The vehicle headlight cover according to item 4. 【請求項９】 前記面層の屈折率は２以下であることを
特徴とする請求項１〜４に記載の乗物前照灯用カバー。9. The vehicle headlamp cover according to claim 1, wherein the surface layer has a refractive index of 2 or less. 【請求項１０】 請求項１〜８の乗物前照灯用カバーを
備えた自動車。10. An automobile comprising the vehicle headlight cover according to claim 1. 【請求項１１】 請求項１〜８の乗物前照灯用カバーを
備えた二輪車。11. A motorcycle comprising the vehicle headlight cover according to claim 1. 【請求項１２】 請求項１〜８の乗物前照灯用カバーを
備えた鉄道車両。12. A railway vehicle comprising the vehicle headlight cover according to any one of claims 1 to 8. 【請求項１３】 請求項１〜８の乗物前照灯用カバーを
準備する工程、前記カバーの内側の表面層に前照灯から
照射される光線中に含有される紫外線を照射して、前記
に表面層に含有される光触媒性酸化チタンを光励起する
ことにより、前記層の表面を親水性になし、以て付着し
た湿分の凝縮水及び／又は水滴が前記層の表面に一様に
広がらせる工程；からなる乗物前照灯用カバーの防曇方
法。13. The step of preparing the vehicle headlamp cover according to claim 1, wherein the surface layer on the inside of the cover is irradiated with ultraviolet rays contained in a light beam emitted from the headlight, By photoexciting the photocatalytic titanium oxide contained in the surface layer, the surface of the layer is made hydrophilic, and the condensed water and / or water droplets of the attached moisture are spread evenly on the surface of the layer. A method for defrosting a vehicle headlight cover, which comprises the step of:
JP8275189A 1995-12-22 1996-09-10 Vehicle headlight cover, vehicle with it, and its defogging method Pending JPH09231807A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8275189A JPH09231807A (en) 1995-12-22 1996-09-10 Vehicle headlight cover, vehicle with it, and its defogging method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP35464995 1995-12-22
JP7-354649 1995-12-22
JP8275189A JPH09231807A (en) 1995-12-22 1996-09-10 Vehicle headlight cover, vehicle with it, and its defogging method

Publications (1)

Publication Number Publication Date
JPH09231807A true JPH09231807A (en) 1997-09-05

Family

ID=18438979

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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
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JP8238927A Pending JPH09227159A (en) 1995-12-22 1996-09-10 Front and rear window glass of vehicle

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JP8281224A Pending JPH09228134A (en) 1995-12-22 1996-09-17 Antifogging helmet shield and antifogging method
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
JP8281220A Expired - Lifetime JP3003593B2 (en) 1995-12-22 1996-09-17 Photocatalytic hydrophilic member
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