JP3277983B2 - Outdoor display panel and its cleaning method - Google Patents

Outdoor display panel and its cleaning method

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Publication number
JP3277983B2
JP3277983B2 JP27519096A JP27519096A JP3277983B2 JP 3277983 B2 JP3277983 B2 JP 3277983B2 JP 27519096 A JP27519096 A JP 27519096A JP 27519096 A JP27519096 A JP 27519096A JP 3277983 B2 JP3277983 B2 JP 3277983B2
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JP
Japan
Prior art keywords
display panel
outdoor display
layer
water
photocatalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP27519096A
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Japanese (ja)
Other versions
JPH09230810A (en
Inventor
隆一 古城
信 早川
Original Assignee
東陶機器株式会社
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Classifications

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

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Finishing Walls (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Prevention Of Fouling (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Building Environments (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Refuge Islands, Traffic Blockers, Or Guard Fence (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
  • Road Signs Or Road Markings (AREA)
  • Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
  • Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Greenhouses (AREA)
  • Panels For Use In Building Construction (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Bridges Or Land Bridges (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Elimination Of Static Electricity (AREA)
  • Photometry And Measurement Of Optical Pulse Characteristics (AREA)

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、交通標識、広告用
看板、電光掲示板、オーロラビジョン、ネオンサイン、
店舖用看板、表札等の屋外表示板、及びその清浄化方法
に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a traffic sign, an advertising sign, an electric signboard, an aurora vision, a neon sign,
The present invention relates to an outdoor signboard such as a signboard for a shop, a nameplate, etc., and a method of cleaning the same.

【0002】[0002]

【従来の技術】屋外表示板は、自動車等の排気ガス中の
燃焼生成物や大気中に浮遊する煤塵の堆積により汚れ
る。更に、雨天には浮遊煤塵は雨によって持ち運ばれ、
屋外表示板の表面を流下する際に、表面に雨水の道筋に
沿って汚染物質が付着し、表面が乾燥すると縞状の汚れ
を形成する。
2. Description of the Related Art Outdoor display panels are contaminated by combustion products in exhaust gas from automobiles and the accumulation of dust floating in the atmosphere. Furthermore, in the rain, floating dust is carried by rain,
When flowing down the surface of the outdoor display panel, contaminants adhere to the surface along the path of rainwater, and when the surface is dried, striped dirt is formed.

【0003】[0003]

【発明の解決すべき課題】このような屋外表示板の汚れ
は表示内容を見にくくするとともに、都市の美的景観を
乱す。また、多くの屋外表示板は高所にあるため、清掃
作業は危険であり、かつ時間もかかる。本発明の目的
は、危険な清掃作業を伴わない、降雨により自己清浄化
(セルフクリーニング)される表面を有する屋外表示
板、及びその清浄化方法を提供することにある。本発明
の他の目的は、危険な清掃作業を伴わない、散水や水濯
ぎ程度で清掃可能な表面を有する屋外表示板、及びその
清浄化方法を提供することにある。本発明の他の目的
は、燃焼生成物や煤塵の付着しにくい表面を有する屋外
表示板を提供することにある。
Such dirt on the outdoor display panel makes it difficult to see the display contents and disturbs the aesthetic view of the city. In addition, since many outdoor display boards are located at a high place, cleaning work is dangerous and time-consuming. An object of the present invention is to provide an outdoor display panel having a surface that is self-cleaned (self-cleaned) by rainfall without a dangerous cleaning operation, and a cleaning method thereof. It is another object of the present invention to provide an outdoor display panel having a surface that can be cleaned by watering or rinsing without dangerous cleaning work, and a method of cleaning the same. Another object of the present invention is to provide an outdoor display panel having a surface to which combustion products and dust are less likely to adhere.

【0004】[0004]

【課題を解決するための手段】本発明は、光触媒を含有
する表面層を形成した部材において、光触媒を光励起す
ると、部材の表面が高度に親水化されるという発見に基
づく。この現象は以下に示す機構により進行すると考え
られる。すなわち、光触媒の価電子帯上端と伝導帯下端
とのエネルギ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.

【0005】本発明では、屋外表示板基材の表面に、光
触媒粒子を含有する表面層を備えたセルフクリーニング
性屋外表示板を提供する。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、表面層の表
面は親水性を呈するので、屋外表示板の表面が降雨にさ
らされた時に付着堆積物及び/又は汚染物が雨滴により
洗い流されるのが可能となる。
The present invention provides a self-cleaning outdoor display panel provided with a surface layer containing photocatalyst particles on the surface of the outdoor display panel base material. By providing the surface layer containing the photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to the photoexcitation of the photocatalyst, so that when the surface of the outdoor display panel is exposed to rainfall, deposits and / or contaminants are removed. It can be washed away by raindrops.

【0006】本発明では、屋外表示板基材の表面に、光
触媒粒子を含有する表面層を備えた防汚性屋外表示板を
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、表面層の表面は親水性を
呈するので、汚染物を含んだ雨水が屋外表示板の表面を
流下するときに汚染物が表面に付着するのが防止され
る。
The present invention provides an antifouling outdoor display panel having a surface layer containing photocatalyst particles on the surface of an outdoor display panel substrate. By providing the surface layer containing the photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to the photoexcitation of the photocatalyst, so that when rainwater containing the contaminant flows down the surface of the outdoor display panel, the contaminant is exposed to the surface. Is prevented.

【0007】本発明では、屋外表示板基材の表面に、光
触媒粒子を含有する表面層を備えた易清掃性屋外表示板
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、表面層の表面は親水性を
呈するので、屋外表示板の表面を水で洗浄するのが容易
になる。
The present invention provides an easy-to-clean outdoor display panel having a surface layer containing photocatalyst particles on the surface of an outdoor display panel substrate. By providing the surface layer containing the photocatalyst, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, so that the surface of the outdoor display panel can be easily washed with water.

【0008】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.

【0009】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 superacid.
When the super strong acid is contained, the surface is likely to exhibit a high degree of hydrophilicity near a water wetting angle of 0 °, and the hydrophilicity retention when kept in a dark place is improved. The reason is that when a super-strong acid is contained in the surface layer, the polarity of the surface is extremely large regardless of the presence or absence of light, so water molecules that are polar molecules are selectively adsorbed rather than 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.

【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。本発明における屋外表示板の表面には、
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、屋外表示板の表面は、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、表面の親水性が
親油性より強まる。それにより、屋外表示板の表面が降
雨にさらされた時に付着堆積物及び/又は汚染物が雨滴
により洗い流されるようになる。また、汚染物を含んだ
雨水が屋外表示板の表面を流下するときに汚染物が表面
に付着するのが防止される。さらに、屋外表示板の表面
を水で洗浄するのが容易になる。
Next, a specific configuration of the present invention will be described. On the surface of the outdoor display panel in the present invention,
As shown in FIG. 1 or FIG. 2, a layer containing a photocatalyst is formed on the surface of the substrate. With such a surface structure, the surface of the outdoor display panel is highly hydrophilized in response to photoexcitation of the photocatalyst. Thereby, the hydrophilicity of the surface becomes stronger than the lipophilicity. Thereby, when the surface of the outdoor display panel is exposed to rainfall, attached deposits and / or contaminants are washed away by raindrops. In addition, when rainwater containing the contaminant flows down the surface of the outdoor display panel, the contaminant is prevented from adhering to the surface. Further, it becomes easy to wash the surface of the outdoor display panel with water.

【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 shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, the pollutant is rejected by a photoexcitation effect of a photocatalyst mixed into the surface layer other than the inorganic oxide,
By forming the adsorbed water layer, a uniform water film can be formed.

【0013】本発明における屋外表示板は、交通標識、
広告用看板、電光掲示板、オーロラビジョン、ネオンサ
イン、店舖用看板、表札等を示し、材質としては、ポリ
カーボネート、アクリル等のプラスチック基材又はその
塗装板、ハードコート板;蛍光表示をガラス、プラスチ
ック等の透明体でカバーした板等が好適に利用できる。
The outdoor display panel according to the present invention includes a traffic sign,
Shows advertising billboards, electronic bulletin boards, aurora visions, neon signs, signboards for storefronts, nameplates, etc. The material is plastic base material such as polycarbonate or acrylic, or its painted plate, hard-coated plate; fluorescent display glass, plastic, etc. And the like covered with a transparent body.

【0014】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;街
灯、常夜灯等の環境にある光源;等が利用でき、電光表
示板においては内部にある電灯も利用できる。ここで電
灯としては、蛍光灯、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/
cm以上あればよいが、0.01mW/cm以上だ
と好ましく、0.1mW/cm以上だとより好まし
い。
A photocatalyst is a device that emits 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 when the electrons in the valence band are irradiated. 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, sunlight; a light source in an environment such as a streetlight or a nightlight; or the like can be used. Here, as the electric lamp, a light source such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, a mercury lamp, or a xenon lamp can be suitably used. In order for the substrate surface to be highly hydrophilized by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.001 mW /
cm 2 suffices above, but preferably that it 0.01 mW / cm 2 or more, and more preferably it 0.1 mW / cm 2 or more.

【0015】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.

【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。
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.

【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。
The surface layer includes 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. In addition, when a solid superacid is added in addition to the photocatalyst, the acidity of the solid superacid is improved by the addition of a platinum group metal, so that the hydrophilicity retention property is also improved, and the formation of a film of attached water is further promoted. In addition, the hydrophilicity retention when the photocatalyst is not irradiated with the excitation light for a relatively long period of time is also improved.

【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 an alkali network modifying ion such as sodium (soda lime glass, side-by-side 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、セルフクリーニング性、水による易清掃性、
降雨による汚れ付着防止性にはPCT/JP96/00
734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 is about 10 ° or less. In particular, self-cleaning, easy cleaning with water,
PCT / JP96 / 00 for prevention of dirt adhesion due to rainfall
As disclosed in No. 734, the water wetting angle is preferably 10 ° or less, more preferably 5 ° or less.

【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
、硫酸担持TiO、硫酸担持ZrO、硫酸担
持SnO、硫酸担持Fe、硫酸担持SiO
硫酸担持HfO、TiO/WO、WO/SnO
、WO/ZrO、WO/Fe、SiO
・Al等が好適に利用できる。
In the present invention, the solid superacid is a strong acid containing a solid oxide having a Hammett acidity function Ho ≦ −11.93 as a constituent element.
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。 (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, a production method in the case where the surface layer is composed of only a photocatalyst will be described with reference to an example in which the photocatalyst is an anatase type titanium oxide. In this case, there are roughly three methods. One method is a sol coating and firing method, the other method is an organic titanate method, and the other method is an electron beam evaporation method. (1) Sol-coating and firing method Anatase-type titanium oxide sol is applied to the surface of a substrate by a method such as spray coating, dip coating, flow coating, spin coating, or roll coating, and then fired. (2) Organic titanate method A hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) is added to an organic titanate such as titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, etc. , After diluting with a non-aqueous solvent such as alcohol (ethanol, propanol, butanol, etc.) and then partially or completely allowing hydrolysis to proceed, the mixture is spray-coated, dip-coated, Apply by flow coating, spin coating, roll coating, etc.
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 Deposition Method An amorphous titanium oxide layer is formed on the surface of a base material 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)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 a photocatalyst and silica will be described with reference to the case where the photocatalyst is an anatase type titanium oxide. In this case, for example, there are the following three methods. One method is a sol coating and baking method, the other is an organic titanate method, and the other is a 4 method.
This is a functional silane method. (1) Sol coating and baking method A mixture of anatase-type titanium oxide sol and silica sol is applied to the substrate surface 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 then fired. I do. (2) Organic titanate method A hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol are added to an organic titanate such as titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, etc. 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 an anatase-type titanium oxide sol is spray-coated on the surface of the substrate, and dip-coated. After applying by a method such as a flow coating method, a spin coating method, and a roll coating method, and hydrolyzing as necessary to form a silanol, the silanol is subjected to dehydration condensation polymerization by a method such as heating.

【0023】次に、表面層が光触媒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TiO/WO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 a photocatalyst and a solid superacid is described with reference to 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 with reference to 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.

【0025】[0025]

【実施例】まず、10cm角のPMMA板表面に、プラ
イマー塗料(東芝シリコーン、PH93をトルエン溶媒
で6倍に希釈した塗料)をスプレーコーティング法にて
塗布後室温で乾燥させて、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(東
芝シリコーン、トスガード)をフローコーティング法に
て塗布し、90℃で3時間乾燥し、プライマー樹脂層の
上にハードコート層を形成した。さらに、ハードコート
層表面を、コロナ表面処理装置(春日電機)により、電
極にワイヤー電極を用い、電極先端と試料表面とのギャ
ップ2mm、電圧26kV、周波数39kHz、試料送
り速度4.2m/分の条件で、高周波コロナ放電処理し
て#1試料を得た。一方、アナターゼ型酸化チタンゾル
56重量部(日産化学、TA−15、平均粒径12n
m)とシリカゾル33重量部(日本合成ゴム、グラスカ
A液)を混合し、エタノールで希釈後、更にメチルトリ
メトキシシラン11重量部(日本合成ゴム、グラスカB
液)を添加し、酸化チタン含有塗料組成物を調整した。
上記塗料組成物を、#1試料に、フローコーティング法
にて塗布し、90℃で3時間熱処理して硬化させ、#2
試料を得た。この#2試料を、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0.6mW/cmの紫外線照度で約48時間
紫外線を照射し、#3試料を得た。比較のため、10c
m角のPMMA板試料も準備した。まず、#3試料とP
MMA板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#
3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、PMMA板試料
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、水滴は表面にややなじむものの、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60゜であった。
EXAMPLE First, a primer paint (Toshiba Silicone, a paint obtained by diluting PH93 6 times with a toluene solvent) was applied to the surface of a 10 cm square PMMA plate by a spray coating method, and then dried at room temperature. Layer. Next, a silicone hard coating agent (Toshiba Silicone, Tosgard) was applied by a flow coating method, and dried at 90 ° C. for 3 hours to form a hard coat layer on the primer resin layer. Further, the surface of the hard coat layer was treated with a corona surface treatment device (Kasuga Electric) using a wire electrode as the electrode, a gap of 2 mm between the electrode tip and the sample surface, a voltage of 26 kV, a frequency of 39 kHz, and a sample feed speed of 4.2 m / min. Under the conditions, a high-frequency corona discharge treatment was performed to obtain a # 1 sample. On the other hand, 56 parts by weight of anatase-type titanium oxide sol (Nissan Chemical Co., TA-15, average particle size 12n)
m) and 33 parts by weight of silica sol (Nippon Synthetic Rubber, Glasca A solution), and after dilution with ethanol, 11 parts by weight of methyltrimethoxysilane (Nippon Synthetic Rubber, Glaska B)
Liquid) was added to prepare a coating composition containing titanium oxide.
The above coating composition was applied to a # 1 sample by a flow coating method, and cured by heat treatment at 90 ° C. for 3 hours.
A sample was obtained. This # 2 sample was placed in an ultraviolet light source (Sankyo Electric,
The surface of the sample was irradiated with ultraviolet light at an ultraviolet illuminance of 0.6 mW / cm 2 for about 48 hours using a black light blue (BLB) fluorescent lamp) to obtain a # 3 sample. 10c for comparison
An m square PMMA plate sample was also prepared. First, sample # 3 and P
A water drop was dropped on the MMA plate 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-X150).
Evaluation was made based on the contact angle with water 30 seconds after dropping. as a result#
When water droplets were dropped on the sample surface from the microsyringe of the three samples, it was observed that the water droplets spread uniformly over the sample surface in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the PMMA plate sample, when a water drop was dropped on the sample surface from the microsyringe, the water drop slightly adapted to the surface, but did not reach a uniform water film state. The contact angle with water after 30 seconds was 60 °.

【0026】次に、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#3試料及びPMMA
板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
*表示を用いた。その結果、PMMA板試料では色差変
化22と大きかったのに対し、#3試料では色差変化は
0.6に止まった。
Next, 1 part by weight of hydrophobic carbon black,
A slurry was prepared by suspending a powder mixture consisting of 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. # 3 sample and PMMA inclined at 45 degrees
150 ml of the above slurry was allowed to flow down to the plate sample and dried for 15 minutes, and then 150 ml of distilled water was allowed to flow down and dried for 15 minutes. This cycle was repeated 25 times. The color difference change before and after the test was measured using a color difference meter (Tokyo Denshoku).
The color difference is ΔE according to Japanese Industrial Standards (JIS) H0201.
* Indication was used. As a result, while the color difference change was as large as 22 in the PMMA plate sample, the color difference change was only 0.6 in the # 3 sample.

【0026】[0026]

【発明の効果】本発明では、屋外表示板基材の表面に、
光触媒粒子を含有する表面層を備えるようにすることに
より、屋外表示板表面は、光触媒の光励起に応じて高度
の親水性を呈し、降雨により自己清浄化(セルフクリー
ニング)され、或いは散水や水濯ぎ程度で清掃可能にな
り、若しくは雨水によりもたらされる燃焼生成物や煤塵
が付着しにくくなる。
According to the present invention, on the surface of the outdoor display panel base material,
By providing the surface layer containing the photocatalyst particles, the surface of the outdoor display panel exhibits a high degree of hydrophilicity according to the photoexcitation of the photocatalyst, and is self-cleaned (self-cleaning) by rainfall, or sprayed or rinsed with water. It is possible to clean by a certain degree, or it becomes difficult for combustion products and dust brought by rainwater to adhere.

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

【図1】 本発明に係る屋外表示板の表面構造を示す
図。
FIG. 1 is a diagram showing a surface structure of an outdoor display panel according to the present invention.

【図2】 本発明に係る屋外表示板の他の表面構造を示
す図。
FIG. 2 is a diagram showing another surface structure of the outdoor display panel according to the present invention.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平7−171408(JP,A) 特開 平6−266289(JP,A) 特開 平6−278241(JP,A) 特開 昭62−260717(JP,A) 特開 昭60−151250(JP,A) 特開 平9−90889(JP,A) 特開 平5−302173(JP,A) 特開 平7−113272(JP,A) 特開 平7−171403(JP,A) 特開 昭63−100042(JP,A) 特開 昭63−5301(JP,A) 特開 平4−174679(JP,A) 特開 昭60−210641(JP,A) 特開 平7−88367(JP,A) 特開 平7−100378(JP,A) (58)調査した分野(Int.Cl.7,DB名) G09F 7/00 C09K 3/18 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-7-171408 (JP, A) JP-A-6-266289 (JP, A) JP-A-6-278241 (JP, A) JP-A-62-1987 260717 (JP, A) JP-A-60-151250 (JP, A) JP-A-9-90889 (JP, A) JP-A-5-302173 (JP, A) JP-A-7-113272 (JP, A) JP-A-7-171403 (JP, A) JP-A-63-100042 (JP, A) JP-A-63-5301 (JP, A) JP-A-4-174679 (JP, A) JP-A-60-210641 (JP, A) JP-A-7-88367 (JP, A) JP-A-7-100378 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G09F 7/00 C09K 3 / 18

Claims (15)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 屋外表示板基材の表面に、光触媒粒子を
含有する表面層を備え、前記層の表面が、前記光触媒の
光励起に応じて、水との接触角に換算して10゜以下の
親水性を呈し、以て屋外表示板の前記層が降雨にさらさ
れた時に付着堆積物及び/又は汚染物が雨滴により洗い
流されるのを可能にするセルフクリーニング性屋外表示
板。
A surface layer containing photocatalyst particles is provided on the surface of a substrate of an outdoor display panel, and the surface of said layer has a contact angle with water of 10 ° or less in response to photoexcitation of said photocatalyst. A self-cleaning outdoor display panel which exhibits a hydrophilic nature, thereby enabling attached deposits and / or contaminants to be washed away by raindrops when said layer of the outdoor display panel is exposed to rainfall.
【請求項2】 屋外表示板基材の表面に、光触媒粒子を
含有する表面層を備え、前記層の表面が、前記光触媒の
光励起に応じて、水との接触角に換算して10゜以下の
親水性を呈し、以て汚染物を含んだ雨水が屋外表示板の
前記層表面を流下するときに汚染物が表面に付着するの
を防止する防汚性屋外表示板。
2. A surface layer containing photocatalyst particles is provided on the surface of an outdoor display panel base material, and the surface of the layer has a contact angle with water of 10 ° or less in response to photoexcitation of the photocatalyst. An antifouling outdoor display panel having a hydrophilic property and preventing contaminants from adhering to the surface when rainwater containing the contaminant flows down the layer surface of the outdoor display panel.
【請求項3】 屋外表示板基材の表面に、光触媒粒子を
含有する表面層を備え、前記層の表面が、前記光触媒の
光励起に応じて、水との接触角に換算して10゜以下の
親水性を呈し、以て屋外表示板の前記層表面を水で洗浄
するのが容易になる易清掃性屋外表示板。
3. A surface layer containing photocatalyst particles is provided on the surface of the outdoor display panel base material, and the surface of the layer is 10 ° or less in terms of a contact angle with water according to the photoexcitation of the photocatalyst. An easy-to-clean outdoor display panel having a hydrophilic property, whereby the surface of the layer of the outdoor display panel can be easily washed with water.
【請求項4】 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1〜3のいずれか一項
に記載の屋外表示板。
4. The outdoor display panel according to claim 1, wherein the surface layer further contains silica.
【請求項5】 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1〜3のいずれか
一項に記載の屋外表示板。
5. The outdoor display panel according to claim 1, wherein the surface layer further contains a solid superacid.
【請求項6】 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1〜3のいずれか
一項に記載の屋外表示板。
6. The outdoor display panel according to claim 1, wherein the surface layer further contains silicone.
【請求項7】 前記表面層の表面は、前記光触媒の光励
起に応じて、水との接触角に換算して5゜以下の親水性
を呈することを特徴とする請求項1〜6のいずれか一項
に記載の屋外表示板。
7. A surface according to claim 1, wherein the surface of the surface layer exhibits a hydrophilicity of 5 ° or less in terms of a contact angle with water in response to photoexcitation of the photocatalyst. The outdoor display panel according to claim 1.
【請求項8】 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1〜6のいずれか一項に記載
の屋外表示板。
8. The outdoor display panel according to claim 1, wherein the thickness of the surface layer is 0.4 μm or less.
【請求項9】 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1〜6のいずれか一項に記載
の屋外表示板。
9. The outdoor display panel according to claim 1, wherein the thickness of the surface layer is 0.2 μm or less.
【請求項10】 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
〜6のいずれか一項に記載の屋外表示板。
10. The method according to claim 1, wherein a protective layer capable of being made hydrophilic is further provided on the surface of the surface layer.
An outdoor display panel according to any one of claims 1 to 6.
【請求項11】 前記屋外表示板は、交通標識であるこ
とを特徴とする請求項1〜10のいずれか一項に記載の
屋外表示板。
11. The outdoor display panel according to claim 1, wherein the outdoor display panel is a traffic sign.
【請求項12】 前記屋外表示板は、広告用看板である
ことを特徴とする請求項1〜10のいずれか一項に記載
の屋外表示板。
12. The outdoor display panel according to claim 1, wherein the outdoor display panel is an advertisement signboard.
【請求項13】 前記屋外表示板は、電光掲示板である
ことを特徴とする請求項1〜10のいずれか一項に記載
の屋外表示板。
13. The outdoor display panel according to claim 1, wherein the outdoor display panel is an electronic bulletin board.
【請求項14】 請求項1〜13の屋外表示板を準備す
る工程と;前記屋外表示板を屋外に配置する工程と;前
記屋外表示板の表面層に含有される光触媒を光励起する
ことにより、前記層の表面を水との接触角に換算して1
0゜以下の親水性にする工程と;前記屋外表示板を降雨
にさらして、前記層の表面に付着する堆積物及び/又は
汚染物を雨滴により洗い流させる工程;からなる屋外表
示板のセルフクリーニング方法。
14. A step of preparing the outdoor display panel according to claim 1; arranging the outdoor display panel outdoors; and photo-exciting a photocatalyst contained in a surface layer of the outdoor display panel, The surface of the layer is converted into a contact angle with water to be 1
Self-cleaning of the outdoor display panel, the method comprising: exposing the outdoor display panel to rainfall to wash off deposits and / or contaminants adhering to the surface of the layer by raindrops; Method.
【請求項15】 請求項1〜13の屋外表示板を準備す
る工程と;前記屋外表示板の表面層に含有される光触媒
を光励起することにより、前記層の表面を水との接触角
に換算して10゜以下の親水性にする工程と;前記屋外
表示板を水で濯ぐことにより、前記層の表面に付着する
堆積物及び/又は汚染物を表面から釈放させて水により
洗い流す工程;からなる屋外表示板の清浄化方法。
15. A step of preparing the outdoor display panel according to claim 1, wherein the photocatalyst contained in the surface layer of the outdoor display panel is photo-excited to convert the surface of the layer into a contact angle with water. Rinsing the outdoor display panel with water to release sediment and / or contaminants adhering to the surface of the layer from the surface and to wash it off with water; A method for cleaning an outdoor display panel comprising:
JP27519096A 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method Expired - Lifetime JP3277983B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27519096A JP3277983B2 (en) 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP35464995 1995-12-22
JP7-354649 1995-12-22
JP27519096A JP3277983B2 (en) 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method

Publications (2)

Publication Number Publication Date
JPH09230810A JPH09230810A (en) 1997-09-05
JP3277983B2 true JP3277983B2 (en) 2002-04-22

Family

ID=18438979

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Families Citing this family (197)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6830785B1 (en) * 1995-03-20 2004-12-14 Toto Ltd. Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof
JPH09227779A (en) * 1995-12-22 1997-09-02 Toto Ltd Rubber member for construction and impartment of hydrophilicity to surface thereof
JPH09230105A (en) * 1995-12-22 1997-09-05 Toto Ltd Antifogging method and facility applied with the method
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance
JPH09186949A (en) * 1995-12-27 1997-07-15 Toshiba Lighting & Technol Corp Video equipment
JP3400259B2 (en) * 1996-08-26 2003-04-28 セントラル硝子株式会社 Hydrophilic coating and method for producing the same
JP3949788B2 (en) * 1996-09-17 2007-07-25 大野 隆司 Goods storage container
JP4305001B2 (en) * 1996-09-20 2009-07-29 株式会社日立製作所 Articles with a photocatalytic film
CN1254365C (en) * 1996-09-20 2006-05-03 株式会社日立制作所 Thin photocatalytic film and articles provided with the same
JPH10148705A (en) * 1996-11-21 1998-06-02 Hitachi Chem Co Ltd Antifog treatment
JP3467994B2 (en) * 1996-11-27 2003-11-17 松下電工株式会社 Silicone transfer film and transfer structure thereof
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
JP4672822B2 (en) * 1997-02-24 2011-04-20 株式会社ティオテクノ Hydrophilic coating agent and surface hydrophilic substrate
JP3518251B2 (en) * 1997-05-20 2004-04-12 株式会社日立製作所 Oxide photocatalytic thin film and article provided with the same
JPH1190236A (en) * 1997-09-22 1999-04-06 Ebara Corp Photocatalyst and reaction device using photocatalyst
JPH11100695A (en) * 1997-09-26 1999-04-13 Nippon Alum Co Ltd Production of titanium material having photocatalytic activity
JPH11100526A (en) * 1997-09-29 1999-04-13 Toto Ltd Photocatalytic hydrophilic member and photocatalytic hydrophilic coating composition
JP3996682B2 (en) * 1997-10-20 2007-10-24 日本デコール株式会社 Decorative sheet having organic substance decomposing function and method for producing the same
JPH11152447A (en) * 1997-11-21 1999-06-08 Toto Ltd Surface-treating agent for forming photocatalyzing coating film, and formation of photocatalyzing coating film using the surface-treating agent
KR100740055B1 (en) * 1997-12-25 2007-10-18 산젠 가꼬 가부시키가이샤 Anti-fogging laminates
JPH11197516A (en) * 1998-01-09 1999-07-27 Takenaka Komuten Co Ltd Photocatalyst material and its production
AU2546599A (en) * 1998-02-10 1999-08-30 Toto Ltd. Coating material for forming photocatalytic hydrophilic film, method of forming photocatalytic hydrophilic film, and photocatalytic hydrophilic member
JPH11263950A (en) * 1998-03-16 1999-09-28 Nippon Carbide Ind Co Inc Transparent adhesive sheet for preventing dew condensation and dew condensation-preventing deflective sign
EP0989166A4 (en) * 1998-04-10 2001-11-28 Matsushita Electric Works Ltd Inorganic coating composition and hydrophilic inorganic coating film
JPH11347482A (en) * 1998-06-12 1999-12-21 Dainippon Toryo Co Ltd Production of joint part coated porcelain tile panel
CH693138A5 (en) * 1998-06-19 2003-03-14 Unaxis Trading Ag Laminated glass and method for making a coated plastic film therefor.
KR100290066B1 (en) * 1998-07-13 2001-05-15 김명신 How to fix titanium dioxide, used as an air freshener, on activated carbon
TW473400B (en) 1998-11-20 2002-01-21 Asahi Chemical Ind Modified photocatalyst sol
JP2000226234A (en) * 1998-12-03 2000-08-15 Toto Ltd Hydrophilic member
JP3340688B2 (en) * 1999-01-28 2002-11-05 シャープ株式会社 Air conditioner
EP1023910A1 (en) * 1999-01-29 2000-08-02 Institut Straumann AG Preparation of osteophilic surfaces for metallic prosthetic devices anchorable to bone
EP1182169A4 (en) * 1999-02-04 2004-12-15 Japan Science & Tech Agency Process for producing anatase titania or composite oxide containing anatase titania
JP2000234892A (en) * 1999-02-12 2000-08-29 Zexel Corp Method for reducing heat exchanger and heat exchanger manufactured by that method
AU2940200A (en) 1999-03-09 2000-09-28 Toto Ltd. Hydrophilic member, method for preparation thereof, and coating agent and apparatus for preparation thereof
JP4029516B2 (en) * 1999-03-18 2008-01-09 株式会社Inax Photocatalytic tile
KR100308818B1 (en) * 1999-04-01 2001-09-26 이계안 Hydrophilic coating glass coated with porous thin layer of TiO2
JP4345941B2 (en) * 1999-04-16 2009-10-14 ベック株式会社 Coating method
US6485838B1 (en) 1999-05-21 2002-11-26 Jsr Corporation Coating composition, and a coated film and glass each having a coating layer comprised thereof
JP2000334308A (en) * 1999-05-25 2000-12-05 Shinichi Harigai Cafrrier for photocatalyst and photocatalyst using the same
JP2000334309A (en) * 1999-05-25 2000-12-05 Shinichi Harigai Photocatalyst
FR2794225B3 (en) * 1999-05-25 2001-06-15 Saint Gobain Vitrage REFRIGERATED ENCLOSURE DOOR WITH VACUUM WINDOWS
JP4513141B2 (en) * 1999-06-21 2010-07-28 パナソニック株式会社 air purifier
JP4507302B2 (en) * 1999-08-10 2010-07-21 凸版印刷株式会社 High refractive index composition
DE60008466T2 (en) 1999-09-02 2004-12-23 Central Glass Co., Ltd., Ube Articles with photocatalytic coating
JP2001080974A (en) * 1999-09-08 2001-03-27 Fuji Photo Film Co Ltd Composite base plate material and method for producing the same
WO2001025362A1 (en) * 1999-10-01 2001-04-12 Nippon Soda Co., Ltd. Sheet for transferring photocatalyst
JP2001164117A (en) * 1999-12-07 2001-06-19 Toppan Printing Co Ltd High-refractive-index composition and antireflection laminate
TW468053B (en) * 1999-12-14 2001-12-11 Nissan Chemical Ind Ltd Antireflection film, process for forming the antireflection film, and antireflection glass
US6603320B2 (en) 2000-02-07 2003-08-05 Organo Corporation Electric conductometer, electrode for measuring electric conductivity, and method for producing the same
US8632583B2 (en) 2011-05-09 2014-01-21 Palmaz Scientific, Inc. Implantable medical device having enhanced endothelial migration features and methods of making the same
US6866937B2 (en) 2000-08-22 2005-03-15 Central Glass Company, Limited Glass plate with oxide film and process for producing same
KR100631104B1 (en) * 2000-11-03 2006-10-02 한국유리공업주식회사 Hydrophilic glass coated with metal oxide and method for producing it
JP2002159910A (en) * 2000-11-27 2002-06-04 Cleanup Corp Method for forming photocatalytic coating film on surface of base material
JP4755756B2 (en) * 2000-12-20 2011-08-24 日本テトラパック株式会社 Photocatalytic material
AU2002253882A1 (en) 2001-01-30 2002-08-28 The Procter And Gamble Company Coating compositions for modifying surfaces
TWI232229B (en) * 2001-03-21 2005-05-11 Bridgestone Corp Method of forming an antifouling coating film, and antifouling product with the antifouling coating film
JP2002285036A (en) * 2001-03-23 2002-10-03 Seiichi Rengakuji Photocatalyst supported aluminum material and its manufacturing method
KR100393733B1 (en) * 2001-03-28 2003-08-06 홍국선 Ceramic Compositions for superhydrophilic coating and its manufacturing method
US6827966B2 (en) * 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
CN100366300C (en) * 2001-10-11 2008-02-06 斯特劳曼控股公司 Bone-seeking implant
JP2003135228A (en) * 2001-11-02 2003-05-13 Sanyo Electric Co Ltd Low temperature show case
WO2003069044A1 (en) * 2002-02-14 2003-08-21 Lg Electronics Inc. Door for washing machine and method for manufacturing the same
US6938546B2 (en) 2002-04-26 2005-09-06 Mitsubishi Heavy Industries, Ltd. Printing press, layered formation and making method thereof, and printing plate and making method thereof
JP4282597B2 (en) 2002-06-03 2009-06-24 旭化成ケミカルズ株式会社 Photocatalyst composition
JP4169557B2 (en) * 2002-09-19 2008-10-22 旭化成ケミカルズ株式会社 Photocatalyst
JP4069369B2 (en) 2002-09-25 2008-04-02 信越化学工業株式会社 Antireflection film and method of manufacturing antireflection film
WO2004028347A2 (en) 2002-09-26 2004-04-08 Advanced Bio Prosthetic Surfaces, Ltd. Implantable materials having engineered surfaces and method of making same
US8679517B2 (en) 2002-09-26 2014-03-25 Palmaz Scientific, Inc. Implantable materials having engineered surfaces made by vacuum deposition and method of making same
US8268340B2 (en) 2002-09-26 2012-09-18 Advanced Bio Prosthetic Surfaces, Ltd. Implantable materials having engineered surfaces and method of making same
JP2003231204A (en) * 2002-12-09 2003-08-19 Toto Ltd Functional material and functional coating composition
JP3707737B2 (en) * 2003-03-06 2005-10-19 重岡 誠司 Outdoor heat exchanger
DE10325768A1 (en) * 2003-06-05 2004-12-23 Chemetall Gmbh Coating system for glass surfaces, process for its production and its application
JP4493290B2 (en) * 2003-06-23 2010-06-30 菊治 山下 Artificial biomaterial and method for producing the same
US20050040151A1 (en) 2003-08-20 2005-02-24 Robert Dyrdek Heated side window glass
JP2005096336A (en) * 2003-09-26 2005-04-14 Lintec Corp Process film for ceramic green sheet production and its production method
JP2005186353A (en) * 2003-12-25 2005-07-14 Murakami Corp Anti-fogging element
JP4995428B2 (en) * 2004-03-10 2012-08-08 東海旅客鉄道株式会社 Titanium oxide coating formation method
EP1779155A2 (en) * 2004-08-10 2007-05-02 Cardinal CG Company Lcd mirror system and method
JP4758086B2 (en) * 2004-09-09 2011-08-24 タキロン株式会社 Construction structure using a sealing material used for polycarbonate resin parts with photocatalytic function
AU2005287016B2 (en) 2004-09-20 2012-04-12 Agc Flat Glass North America, Inc. Anti-fog refrigeration door and method of making the same
JP2006091249A (en) 2004-09-22 2006-04-06 Murakami Corp Camera
KR101231894B1 (en) * 2004-12-28 2013-02-08 카운슬 오브 사이언티픽 앤드 인더스트리얼 리서치 Photocatalytic auto-cleaning process of stains
JPWO2006088079A1 (en) * 2005-02-18 2008-07-03 日本曹達株式会社 Organic inorganic composite
WO2006090630A1 (en) 2005-02-24 2006-08-31 Central Research Institute Of Electric Power Industry Process for producing multifunctional material
EP1852183A4 (en) 2005-02-24 2011-06-29 Central Res Inst Elect Multifunctional material
JP4771359B2 (en) * 2005-02-28 2011-09-14 財団法人電力中央研究所 Playground equipment
JP4814534B2 (en) * 2005-02-28 2011-11-16 財団法人電力中央研究所 Manufacturing method of structural materials
JP4995425B2 (en) * 2005-02-28 2012-08-08 一般財団法人電力中央研究所 Irrigation apparatus, irrigation member, manufacturing method thereof, and irrigation system
JP4807725B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method of energy generating equipment
JP4480014B2 (en) * 2005-02-28 2010-06-16 財団法人電力中央研究所 Rocket parts
JP4807723B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method of heat-resistant member
JP4843231B2 (en) * 2005-02-28 2011-12-21 財団法人電力中央研究所 Kitchen products
JP4807724B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Rail vehicle manufacturing method
JP4958029B2 (en) * 2005-02-28 2012-06-20 一般財団法人電力中央研究所 Building materials
JP4807722B2 (en) * 2005-02-28 2011-11-02 財団法人電力中央研究所 Manufacturing method for environmentally resistant equipment
JP4541929B2 (en) * 2005-02-28 2010-09-08 財団法人電力中央研究所 Flying object
JP2006247760A (en) * 2005-03-08 2006-09-21 Disco Abrasive Syst Ltd Machining apparatus
TW200631899A (en) 2005-03-09 2006-09-16 Tokai Ryokaku Tetsudo Kk Titanium oxide-coating agent, and forming method for titanium oxide-coating film
JP4659494B2 (en) * 2005-03-23 2011-03-30 株式会社ミクニ Infrared transmitting window material, infrared sensor unit, and combustion apparatus
US7757629B2 (en) * 2005-04-14 2010-07-20 Transitions Optical, Inc. Method and apparatus for coating an optical article
JP3795515B1 (en) * 2005-08-10 2006-07-12 善典 中川 Manufacturing method of semiconductor photoelectrochemical cell
KR100796718B1 (en) * 2005-08-10 2008-01-21 요시노리 나카가와 Method for manufacturing photoelectro-chemical cell and photoelectro-chemical cell
US8087377B2 (en) 2005-11-04 2012-01-03 Tokuyama Corporation Coating apparatus
JP5004561B2 (en) * 2005-11-30 2012-08-22 株式会社トクヤマ Coating equipment
GB0602933D0 (en) 2006-02-14 2006-03-22 Pilkington Automotive Ltd Vehicle glazing
EP1829991A1 (en) * 2006-03-02 2007-09-05 UGINE & ALZ FRANCE Stainless steel plate coated with self-cleaning coating.
JP2007247166A (en) * 2006-03-14 2007-09-27 Sumitomo Chemical Co Ltd Road mirror
JP2007262498A (en) * 2006-03-28 2007-10-11 National Institute Of Advanced Industrial & Technology Color-controlled titanium alloy bolt and nut
JP4849525B2 (en) * 2006-04-04 2012-01-11 花王株式会社 Resin composition
JP2007277935A (en) * 2006-04-07 2007-10-25 Sekisui Jushi Co Ltd Indicating body for road
JP2008013833A (en) * 2006-07-07 2008-01-24 National Institute Of Advanced Industrial & Technology Titanium alloy member which develops controlled color
JP4966614B2 (en) * 2006-09-14 2012-07-04 Mkvドリーム株式会社 Agricultural film
JP2008114760A (en) * 2006-11-06 2008-05-22 Asahi Glass Co Ltd Vehicle with anti-fogging glass and set of vehicle window glass
JP4823045B2 (en) * 2006-12-12 2011-11-24 旭化成ケミカルズ株式会社 Water-based photocatalytic composition
JP5064817B2 (en) * 2007-01-30 2012-10-31 トヨタ自動車株式会社 Method for preventing contamination of automobile wheel and automobile wheel
JP2008184357A (en) * 2007-01-30 2008-08-14 National Institute Of Advanced Industrial & Technology Method of making surface of oxide amphiphilic
US7659226B2 (en) 2007-02-26 2010-02-09 Envont Llc Process for making photocatalytic materials
JP2008260667A (en) * 2007-04-13 2008-10-30 Univ Of Electro-Communications Method for manufacturing titanium oxide thin film and resin product with titanium oxide thin film
KR100809030B1 (en) * 2007-05-08 2008-03-03 주식회사 에임하이글로벌 Board for road facilities and preparation method thereof
JP2009002979A (en) * 2007-06-19 2009-01-08 Mitsubishi Electric Corp Video display device and its manufacturing method
JP5510911B2 (en) * 2007-08-17 2014-06-04 株式会社伸興サンライズ Composite interior coating material for buildings
JP2007327071A (en) * 2007-08-23 2007-12-20 Kawasaki Heavy Ind Ltd Method for producing hydrophilic coating composition
JP2009090641A (en) 2007-09-20 2009-04-30 Fujifilm Corp Anticlouding cover and cover for meter using it
JP5705398B2 (en) * 2007-12-05 2015-04-22 トヨタ自動車株式会社 Vehicle wheels and wheel caps
JP5145023B2 (en) * 2007-12-19 2013-02-13 住友軽金属工業株式会社 Fin material for heat exchanger and manufacturing method thereof
US7910085B2 (en) 2007-12-28 2011-03-22 Tdk Corporation Process for production of iron oxyhydroxide particles
JP4993745B2 (en) * 2007-12-28 2012-08-08 株式会社アルバック Deposition equipment
JP2009185107A (en) * 2008-02-04 2009-08-20 Pialex Technologies Corp Hydrophilic coating material and hydrophilic coated object
KR101104262B1 (en) * 2008-12-31 2012-01-11 주식회사 노루홀딩스 Article wih self-cleaning effect and method of preparation thereof
JP5267308B2 (en) * 2009-04-28 2013-08-21 信越化学工業株式会社 Photocatalyst coating liquid that provides a photocatalytic thin film excellent in photoresponsiveness and the photocatalytic thin film
US20110008612A1 (en) * 2009-07-10 2011-01-13 Korea University Research And Business Foundation Self-cleaning surfaces
JP5365501B2 (en) * 2009-12-24 2013-12-11 平岡織染株式会社 Non-flammable interior illuminated signboard
JP5365500B2 (en) * 2009-12-24 2013-12-11 平岡織染株式会社 Non-flammable interior illuminated signboard
JP5411791B2 (en) * 2010-04-23 2014-02-12 三菱レイヨン株式会社 Manufacturing method of laminated resin plate
CN101830644B (en) * 2010-05-14 2012-11-14 中国科学院上海技术物理研究所 High-stability car coated glass membrane system
JP5810294B2 (en) * 2010-07-27 2015-11-11 パナソニックIpマネジメント株式会社 Rainwater collecting wall material
WO2012014893A1 (en) 2010-07-29 2012-02-02 Toto株式会社 Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material
CN104759297B (en) 2010-07-29 2018-02-23 Toto株式会社 Object with photo-catalyst coating and photocatalyst coating liquid
EP3009185B1 (en) * 2010-09-28 2017-08-16 Dow Global Technologies LLC Reactive flow static mixer with cross-flow obstructions and mixing method
JP2012086104A (en) * 2010-10-15 2012-05-10 Asahi Kasei Chemicals Corp Photocatalyst composition
JP2012087213A (en) 2010-10-19 2012-05-10 Nippon Parkerizing Co Ltd Hydrophilic film for metal material, hydrophilization-treating agent, and hydrophilization-treating method
US8728563B2 (en) 2011-05-03 2014-05-20 Palmaz Scientific, Inc. Endoluminal implantable surfaces, stents, and grafts and method of making same
WO2013024897A1 (en) * 2011-08-18 2013-02-21 株式会社インパクト Guidance display board
JP2013096959A (en) * 2011-11-04 2013-05-20 Shiyouichi Yoshino Radioactive decontamination method
JP5250685B2 (en) * 2011-11-25 2013-07-31 パナソニック株式会社 Camera cover and camera
KR20130118456A (en) * 2012-04-20 2013-10-30 호서대학교 산학협력단 Ozone contactor with static mixer
JP6171275B2 (en) * 2012-07-02 2017-08-02 大日本印刷株式会社 Transparent film and method for producing the same
JP6028495B2 (en) * 2012-09-27 2016-11-16 Toto株式会社 Photocatalyst member
CN102923836A (en) * 2012-11-15 2013-02-13 常州大学 Method for treating washing wastewater by using composite-film modified sintered gangue ceramsite
JP6105998B2 (en) * 2013-03-26 2017-03-29 パナホーム株式会社 Method for producing photocatalyst composition and method for producing photocatalyst
CN105732125B (en) * 2013-11-30 2018-03-13 国网河南省电力公司平顶山供电公司 A kind of porcelain and glass insulator low-temperature resistance coating
CN105960384B (en) * 2014-02-05 2019-04-02 Agc株式会社 The manufacturing method of laminated glass
CN104047343A (en) * 2014-06-20 2014-09-17 欧士玺 Mobile toilet capable of recycling water
JP5909604B1 (en) 2014-07-30 2016-04-26 三菱マテリアル株式会社 Surface coating material, coating film and hydrophilic oil-repellent material
JP5879014B1 (en) 2014-07-30 2016-03-08 三菱マテリアル株式会社 Hydrophilic oil repellent and production method thereof, surface coating material, coating film, resin composition, oil-water separation filter medium, porous body
EP3175899B1 (en) 2014-07-30 2019-03-13 Mitsubishi Materials Corporation Filter medium, method for producing filter medium, water treatment module, and water treatment device
JP6461573B2 (en) 2014-07-30 2019-01-30 三菱マテリアル株式会社 Oil / water separator / collector
KR101942261B1 (en) * 2014-09-24 2019-01-28 (주)엘지하우시스 Visible light active photocatalyst tile
KR101642870B1 (en) * 2014-10-21 2016-08-29 가천대학교 산학협력단 Endoscope
JP2016104681A (en) * 2014-12-01 2016-06-09 大日本印刷株式会社 Method for producing laminated glass, and laminated glass
WO2016136395A1 (en) 2015-02-27 2016-09-01 富士フイルム株式会社 Gas separation asymmetric membrane, gas separation module, gas separation device, and gas separation method
CN104720649B (en) * 2015-03-18 2017-03-01 杭州桑莱特卫浴有限公司 A kind of bathroom cabinet and its production method
CN104848985B (en) * 2015-06-05 2017-03-08 合肥工业大学 A kind of vacuum detecting method based on infrared laser spectroscopy and system
JPWO2017022075A1 (en) * 2015-08-04 2017-08-03 三菱電機株式会社 Elevator car panels
JP2017090380A (en) * 2015-11-16 2017-05-25 株式会社デンソーウェーブ Laser radar device, window member for laser radar device, and control program for laser radar device
CN105349042A (en) * 2015-11-20 2016-02-24 杨京广 Silicon carbide coating and use method thereof
CN105444486A (en) * 2015-12-31 2016-03-30 广西路桥工程集团有限公司 Multi-way valve circulation system for cooling system
JP6811415B2 (en) * 2016-01-29 2021-01-13 パナソニックIpマネジメント株式会社 urinal
CN105694688B (en) * 2016-03-16 2017-09-26 曲阜师范大学 A kind of fast preparation method of high intensity super-hydrophobic coat
JP2017165612A (en) * 2016-03-16 2017-09-21 Towa株式会社 Translucent material, low adhesion material and molding member
CN107313490A (en) * 2016-04-26 2017-11-03 厦门致杰智能科技有限公司 A kind of Split intelligent toilet seat
CN105860692A (en) * 2016-04-29 2016-08-17 南京晨光艺术工程有限公司 Self-cleaning Buddha statue
CN106242314A (en) * 2016-08-23 2016-12-21 张洪建 A kind of glass copper-plating technique
CN108261086A (en) * 2017-01-03 2018-07-10 佛山市顺德区美的电热电器制造有限公司 The preparation method of Anti-fog mirror, cooking apparatus and Anti-fog mirror
JP6814473B2 (en) * 2017-02-28 2021-01-20 国立大学法人東北大学 Photocatalytic functional member and its manufacturing method
JP6428864B2 (en) * 2017-07-03 2018-11-28 大日本印刷株式会社 Transparent film and method for producing the same
KR102138411B1 (en) * 2017-07-07 2020-07-27 주식회사 엘지화학 Coating composition including the same, organic light emitting device using the same and method of manufacturing the same
JP2019070247A (en) * 2017-10-06 2019-05-09 スリーエム イノベイティブ プロパティズ カンパニー Window film
MX2023000863A (en) * 2018-01-30 2023-03-01 Viavi Solutions Inc Optical device having optical and mechanical properties.
CN108383396A (en) * 2018-02-27 2018-08-10 张家港外星人新材料科技有限公司 The double-deck film glass with anti-reflection film and antistatic automatically cleaning film and its preparation method
CN110157224A (en) * 2018-03-14 2019-08-23 成都今天化工有限公司 A method of preparing nano ceramics anti-pollution flashover coating
JP2019158247A (en) * 2018-03-14 2019-09-19 株式会社デンソー Heat exchanger
PL425045A1 (en) * 2018-03-28 2019-10-07 Uniwersytet Jagielloński Method for producing nanoporous semiconducting layers of metal oxides
KR101917149B1 (en) 2018-05-17 2018-11-09 주식회사 대수하이테크 Anti-fouling coating composition having excellent weatherability
JP7086744B2 (en) * 2018-06-22 2022-06-20 株式会社東芝 Camera system
JP7329909B2 (en) * 2018-06-28 2023-08-21 小林製薬株式会社 Coating agent for toilet bowl
JP2020069684A (en) * 2018-10-30 2020-05-07 三井化学株式会社 Multilayer structure
JP7290938B2 (en) * 2018-12-11 2023-06-14 イビデン株式会社 Manufacturing method of cover for infrared detection element
JP2020106751A (en) * 2018-12-28 2020-07-09 ホヤ レンズ タイランド リミテッドHOYA Lens Thailand Ltd Spectacle lens
CN109667139B (en) * 2018-12-31 2021-06-29 盐城工学院 Anti-ultraviolet self-cleaning composition and preparation method and application thereof
WO2020202593A1 (en) * 2019-04-03 2020-10-08 株式会社ワンアンドオンリー Antistatic agent, antistatic method, antistatic coating film, resin composition for forming antistatic layer and antistatic method
US11747272B2 (en) 2019-06-10 2023-09-05 Analog Devices, Inc. Gas detection using differential path length measurement
US11821836B2 (en) 2020-07-13 2023-11-21 Analog Devices, Inc. Fully compensated optical gas sensing system and apparatus
CN112143299B (en) * 2020-09-24 2022-02-01 南京长江涂料有限公司 Long-acting self-cleaning high-weatherability fluorocarbon coating and preparation method thereof
WO2022085105A1 (en) 2020-10-21 2022-04-28 三菱電機株式会社 Heat exchanger, and method for manufacturing heat exchanger
CN113311444B (en) * 2021-06-22 2022-08-02 山东高速建设管理集团有限公司 Water film identification and treatment device and use method thereof
CN113462273A (en) * 2021-06-29 2021-10-01 广东康伴新材料科技有限公司 High-wear-resistance high-hand-sensitivity rubber coating and preparation method thereof

Family Cites Families (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5211321B2 (en) * 1972-04-11 1977-03-30
JPS49124166A (en) * 1973-02-07 1974-11-27
JPS5826052A (en) * 1981-08-06 1983-02-16 Asahi Glass Co Ltd Glass body provided with alkali diffusion preventing silicon oxide film
JPS59145808A (en) * 1983-02-09 1984-08-21 財団法人鉄道総合技術研究所 Cloudiness-proof road mirror
JPS60151250A (en) * 1984-01-12 1985-08-09 Matsushita Electric Ind Co Ltd Enamel film backed phosphor
JPS60210641A (en) * 1984-02-22 1985-10-23 Unitika Ltd Antifogging plastic molding
JPS6183106A (en) * 1984-10-01 1986-04-26 Giken Kogyo Kk Method of preventing contamination of surface of solid material to be brought into contact with water
JPS6191042A (en) * 1984-10-08 1986-05-09 Toyota Motor Corp Anti-fogging glass and its production
JPS61133125A (en) * 1984-11-29 1986-06-20 Tsutomu Kagitani Denitration process using ultraviolet ray
JPS621750A (en) * 1985-06-27 1987-01-07 Toray Silicone Co Ltd Room temperature curing organopolysiloxane composition
JPH0647668B2 (en) * 1985-12-16 1994-06-22 三菱化成ビニル株式会社 Anti-fog composition
JPH0615407B2 (en) * 1986-05-07 1994-03-02 株式会社資生堂 Optical semiconductor and its manufacturing method
JPS635301A (en) * 1986-06-25 1988-01-11 Matsushita Electric Works Ltd Reflecting mirror
JPS6363726A (en) * 1986-09-05 1988-03-22 Nippon Shokubai Kagaku Kogyo Co Ltd Composition for surface treatment
JPS6381176A (en) * 1986-09-24 1988-04-12 Yoshio Ichikawa Composition for coating
JPS63100042A (en) * 1986-10-14 1988-05-02 Nippon Sheet Glass Co Ltd Glass article difficult-to be dirtied
JPS63246167A (en) * 1987-04-02 1988-10-13 チタン工業株式会社 White deodorant and its production
JPH01169866A (en) * 1987-12-25 1989-07-05 Hitachi Ltd Discharge lamp
JPH06102155B2 (en) * 1988-02-29 1994-12-14 株式会社日立製作所 Deodorant, deodorant manufacturing method, deodorizing method, deodorizing device, and refrigeration cycle device equipped with this deodorizing device
JP2856754B2 (en) * 1989-02-17 1999-02-10 株式会社東芝 Ultraviolet-suppressed luminescence source, coating agent for ultraviolet-suppressed luminescence source, and method for producing ultraviolet-suppressed luminescence source
JPH0787891B2 (en) * 1989-04-14 1995-09-27 日本ゼオン株式会社 Removing agent and method for removing oxidizable harmful substances
JPH0330314U (en) * 1989-07-31 1991-03-26
DE4023267A1 (en) * 1990-07-21 1992-01-23 Hoechst Ag PLATE, FILM OR TAPE-BASED CARRIER MATERIAL FOR OFFSET PRINT PLATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
JP2618287B2 (en) * 1990-11-06 1997-06-11 日本ゼオン株式会社 Photoreactive harmful substance remover and harmful substance removal method using the same
JPH04206201A (en) * 1990-11-29 1992-07-28 Honda Motor Co Ltd Resin lens headlamp for vehicle
JPH04225301A (en) * 1990-12-27 1992-08-14 Seiko Epson Corp Optical product having clouding preventive performance
JP3224865B2 (en) * 1991-08-14 2001-11-05 東レ合成フィルム株式会社 Agricultural coating film and method for producing the same
JP2883761B2 (en) * 1991-12-06 1999-04-19 工業技術院長 Antibacterial growth inhibitor
JP2913966B2 (en) * 1991-12-10 1999-06-28 市光工業株式会社 Vehicle lighting
JPH05209072A (en) * 1992-01-29 1993-08-20 Japan Synthetic Rubber Co Ltd Method for treating substrate surface
JPH05232566A (en) * 1992-02-24 1993-09-10 Olympus Optical Co Ltd Optical member
JP3340149B2 (en) * 1992-04-28 2002-11-05 セントラル硝子株式会社 Hydrophilic coating and method for forming the coating
JPH06293519A (en) * 1992-07-28 1994-10-21 Ishihara Sangyo Kaisha Ltd Production of titanium oxide particles and film
JP3036247B2 (en) * 1992-08-14 2000-04-24 東陶機器株式会社 Lighting equipment
JPH06190340A (en) * 1992-09-11 1994-07-12 Sekisui Jushi Co Ltd Coated metal body
JPH06278241A (en) * 1992-09-22 1994-10-04 Takenaka Komuten Co Ltd Building material
DE4235996A1 (en) * 1992-10-24 1994-04-28 Degussa Titanium dioxide mixed oxide produced by flame hydrolysis, process for its preparation and use
JP3316048B2 (en) * 1992-11-06 2002-08-19 株式会社竹中工務店 Building material and manufacturing method thereof
JP3496229B2 (en) * 1993-02-19 2004-02-09 日本電池株式会社 Method for producing photocatalyst body
JP2878922B2 (en) * 1993-03-04 1999-04-05 シャープ株式会社 In-vehicle camera device
JPH06266289A (en) * 1993-03-10 1994-09-22 Dainippon Ink & Chem Inc Manufacture of durable display body
JPH06315614A (en) * 1993-03-11 1994-11-15 Agency Of Ind Science & Technol Method for removing contaminants and cleaning material
JPH085660B2 (en) * 1993-04-13 1996-01-24 工業技術院長 Method for producing silica gel containing titanium oxide ultrafine particles dispersed therein
AU676299B2 (en) * 1993-06-28 1997-03-06 Akira Fujishima Photocatalyst composite and process for producing the same
JP3115745B2 (en) * 1993-07-12 2000-12-11 富士写真フイルム株式会社 Photosensitive material
JPH0751646A (en) * 1993-08-12 1995-02-28 Ishihara Sangyo Kaisha Ltd Method for cleaning off contaminant on solid matter surface
JP3279755B2 (en) * 1993-08-24 2002-04-30 松下精工株式会社 Photocatalyst and method for supporting photocatalyst
JP3499585B2 (en) * 1993-09-21 2004-02-23 日揮ユニバーサル株式会社 Ethylene decomposition photocatalyst
JP2517874B2 (en) * 1993-09-30 1996-07-24 工業技術院長 Method for producing titanium oxide thin film photocatalyst
JP3334767B2 (en) * 1993-10-20 2002-10-15 日新製鋼株式会社 Building materials with moisture absorption and release functions
JP2602022Y2 (en) * 1993-11-25 1999-12-20 旭光学工業株式会社 Dew condensation removal device in camera
JPH07149520A (en) * 1993-11-29 1995-06-13 Hoya Corp Coating composition
JPH07164607A (en) * 1993-12-13 1995-06-27 Mitsubishi Chem Corp Agricultural film
JPH07168001A (en) * 1993-12-15 1995-07-04 Nikon Corp Mildew-proofing optical equipment
JP3488496B2 (en) * 1993-12-21 2004-01-19 日揮ユニバーサル株式会社 Poison-resistant deodorizing photocatalyst
JP3391543B2 (en) * 1993-12-27 2003-03-31 花王株式会社 Hydrophilizing agent and hydrophilizing method
JP2883000B2 (en) * 1994-03-29 1999-04-19 三菱重工業株式会社 Automobile sound insulation wall cleaning device
JP3693363B2 (en) * 1994-03-30 2005-09-07 松下エコシステムズ株式会社 Supporting method for forming a photocatalyst layer
JPH07331120A (en) * 1994-06-10 1995-12-19 Hitachi Ltd Coating for removing nitrogen oxide and its use
JP2832239B2 (en) * 1994-06-21 1998-12-09 三井金属鉱業株式会社 Lighting equipment with photocatalytic function
JPH0810576A (en) * 1994-07-05 1996-01-16 Ebara Res Co Ltd Removing method of harmful gas and device therefor
JPH08119673A (en) * 1994-10-21 1996-05-14 Kansai Paint Co Ltd Hydrophilization treatment of glass
JPH08277147A (en) * 1995-03-31 1996-10-22 Nippon Muki Co Ltd Plate glass
JPH09129012A (en) * 1995-03-31 1997-05-16 Toshiba Lighting & Technol Corp Photocatalyst, fluorescent lamp and luminaire
JP3101537B2 (en) * 1995-05-10 2000-10-23 ワイケイケイ株式会社 Antifouling building material and exterior building material unit
JPH0929103A (en) * 1995-05-17 1997-02-04 Toshiba Lighting & Technol Corp Photocatalytic body, photocatalytic device, light source and lightening equipment
JPH08313705A (en) * 1995-05-22 1996-11-29 Seiko Epson Corp Anti-clouding article and its production
JP3127827B2 (en) * 1995-06-14 2001-01-29 東陶機器株式会社 Anti-fog seal
EP1955768A1 (en) * 1995-06-19 2008-08-13 Nippon Soda Co., Ltd. Photocatalyst-carrying structure and photocatalyst coating material
JPH0990889A (en) * 1995-09-27 1997-04-04 Toshiba Lighting & Technol Corp Sign body and externally illuminated sign device
JPH09173783A (en) * 1995-10-27 1997-07-08 Matsushita Electric Ind Co Ltd Sheet glass and resin plate and their production and method for removing contaminant
JP4237830B2 (en) * 1995-12-20 2009-03-11 日本曹達株式会社 Photocatalyst-carrying lighting fixture
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance

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JPH09225389A (en) 1997-09-02
JPH09227156A (en) 1997-09-02
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JPH09228134A (en) 1997-09-02
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JPH09228326A (en) 1997-09-02
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JPH09231807A (en) 1997-09-05
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