JPH09230810A - Outdoor display board and its cleaning method - Google Patents
Outdoor display board and its cleaning methodInfo
- Publication number
- JPH09230810A JPH09230810A JP8275190A JP27519096A JPH09230810A JP H09230810 A JPH09230810 A JP H09230810A JP 8275190 A JP8275190 A JP 8275190A JP 27519096 A JP27519096 A JP 27519096A JP H09230810 A JPH09230810 A JP H09230810A
- Authority
- JP
- Japan
- Prior art keywords
- outdoor display
- display panel
- photocatalyst
- layer
- display board
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Description
【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,
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to outdoor signboards for storefronts, nameplates, etc.
【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 the combustion products in the exhaust gas of automobiles and the accumulation of soot and dust floating in the atmosphere. Furthermore, in rainy weather, suspended dust is carried by the rain,
When the surface of the outdoor display board flows down, contaminants adhere to the surface of the outdoor display board along the path of rainwater, and when the surface dries, stripes of dirt are 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 board makes it difficult to see the displayed contents and disturbs the aesthetic landscape 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-cleaning (self-cleaning) by rainfall and a cleaning method thereof, which does not involve dangerous cleaning work. Another object of the present invention is to provide an outdoor display panel having a surface that can be cleaned by watering or rinsing without dangerous cleaning work, and a method for cleaning the same. Another object of the present invention is to provide an outdoor display panel having a surface on which combustion products and soot and dust are unlikely 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 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.
【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 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 the surface of the outdoor display panel is exposed to rainfall, adhered deposits and / or contaminants are not generated. 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 the rainwater containing the contaminant flows down the surface of the outdoor display panel, the contaminant becomes Is prevented from adhering to.
【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 easily-cleanable outdoor display panel having a surface layer containing photocatalyst particles on the surface of the 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 ability of silica to 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.
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.
【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 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.
【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。BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. On the surface of the outdoor display board 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. By taking 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. As a result, when the surface of the outdoor display board is exposed to rainfall, the adhered deposits and / or contaminants are washed away by raindrops. In addition, when rainwater containing contaminants flows down the surface of the outdoor display board, the contaminants are prevented from adhering to the surface. Further, it becomes easy to wash the surface of the outdoor display board 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 is composed of only the 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 board according to the present invention includes a traffic sign,
Signboards for advertising, electronic bulletin boards, aurora vision, neon signs, signboards for storefronts, nameplates, etc. are shown. Materials are plastic base materials such as polycarbonate, acrylic or its coated plate, hard coat plate; fluorescent display is glass, plastic etc. A plate covered with the transparent body can be preferably used.
【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/
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。The photocatalyst means an electron 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. A substance that is excited (photoexcited) to generate conduction electrons and holes. For example, anatase-type titanium oxide, rutile-type titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, and oxide oxide. Diiron, strontium titanate and the like can be preferably used. Here, as the light source used for the photoexcitation of the photocatalyst, sunlight; a light source in the environment such as a street lamp or a night light; Here, as the electric lamp, a light source such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp can be preferably used. In order to make the surface of the base material highly hydrophilic 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 is less than or equal to μm. Then, white turbidity 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。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、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 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, self-cleanability, easy cleaning with water,
PCT / JP96 / 00 for prevention of dirt adhesion due to rainfall
As disclosed in 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
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, the production method in the case where the surface layer is composed of only the photocatalyst will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. 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 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 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 the sol coating firing method, the other is the organic titanate method, the other is 4
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 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 a photocatalyst 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 a photocatalyst 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. Spray coating method on the surface of the substrate,
It is applied by a method such as a dip coating method, a flow coating method, a spin coating method, a roll coating method, etc., and a hydrolyzate of a silicone precursor is subjected to dehydration polycondensation by a method such as heating to obtain anatase type titanium oxide particles. A surface layer made of silicone is formed. The formed surface layer, by photoexcitation of anatase type titanium oxide by irradiation with light including ultraviolet rays, at least a part of the organic group bonded to the silicon atom in the silicone molecule is substituted with a hydroxyl group, and further on it. A physically adsorbed water layer is formed,
It exhibits a high degree of hydrophilicity. Here, the precursor of silicone includes methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, and 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/cm2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 coating (Toshiba silicone, a coating in which PH93 was diluted 6 times with a toluene solvent) was applied to a 10 cm square PMMA plate surface by a spray coating method, and then dried at room temperature to apply a primer resin to a substrate. Coated with layers. Next, a silicone-based 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. Furthermore, the surface of the hard coat layer was treated with a corona surface treatment device (Kasuga Denki) using a wire electrode as an electrode, the gap between the electrode tip and the sample surface was 2 mm, the voltage was 26 kV, the frequency was 39 kHz, and the sample feed rate was 4.2 m / min. A high frequency corona discharge treatment was performed under the conditions to obtain a # 1 sample. On the other hand, 56 parts by weight of anatase-type titanium oxide sol (TA-15, average particle size 12n
m) and 33 parts by weight of silica sol (Nippon Synthetic Rubber, Glasca A liquid) are mixed and diluted with ethanol, and then 11 parts by weight of methyltrimethoxysilane (Nippon Synthetic Rubber, Grasca B).
Liquid) was added to prepare a titanium oxide-containing coating composition.
The above coating composition was applied to the # 1 sample by the flow coating method, and heat-treated at 90 ° C. for 3 hours to be cured.
A sample was obtained. This # 2 sample was used as an ultraviolet light source (Sankyo Denki,
A # 3 sample was obtained by irradiating the surface of the sample with ultraviolet light at a UV illuminance of 0.6 mW / cm 2 for about 48 hours using a black light blue (BLB) fluorescent lamp. 10c for comparison
An m-square PMMA plate sample was also prepared. First, # 3 sample 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 surface of the three samples from the microsyringe, it was observed that the water droplets spread uniformly on the surface of the sample 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 case of the PMMA plate sample, when water droplets were dropped from the microsyringe on the surface of the sample, the water droplets were somewhat adapted to the surface, but did not form a uniform water film. 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 tilted at 45 degrees
The plate sample was allowed to flow down with 150 ml of the above slurry for 15 minutes and then with 150 ml of distilled water for 15 minutes to dry, and this cycle was repeated 25 times. The color difference change before and after the test was measured using a color difference meter (Tokyo Denshoku).
Color difference is ΔE according to Japanese Industrial Standard (JIS) H0201
* Indication used. As a result, the PMMA plate sample had a large color difference change of 22, while the # 3 sample had a color difference change of only 0.6.
【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, the surface of the outdoor display board substrate is
By providing a surface layer containing photocatalyst particles, the surface of the outdoor display panel exhibits a high degree of hydrophilicity in response to photoexcitation of the photocatalyst, and is self-cleaning (self-cleaning) by rainfall or watering or rinsing with water. It can be cleaned to a certain extent, or combustion products and soot dust caused by rainwater are less likely to adhere.
【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.
Claims (16)
含有する表面層を備え、前記光触媒の光励起に応じて、
前記層の表面は親水性を呈し、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。1. A surface layer containing photocatalyst particles is provided on the surface of an outdoor display board substrate, and in response to photoexcitation of the photocatalyst,
A self-cleaning outdoor display panel, wherein the surface of the layer exhibits hydrophilicity, thus allowing the deposited deposits and / or contaminants to be washed away by raindrops when the layer of the outdoor display panel is exposed to rainfall.
含有する表面層を備え、前記光触媒の光励起に応じて、
前記層の表面は親水性を呈し、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 board substrate, and in response to photoexcitation of the photocatalyst,
The antifouling outdoor display panel, wherein the surface of the layer exhibits hydrophilicity, and thus prevents contaminants from adhering to the surface when rainwater containing the contaminant flows down the surface of the layer of the outdoor display panel.
含有する表面層を備え、前記光触媒の光励起に応じて、
前記層の表面は親水性を呈し、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 an outdoor display board substrate, and in response to photoexcitation of the photocatalyst,
The easily-cleanable outdoor display panel, wherein the surface of the layer exhibits hydrophilicity, and thus the surface of the layer of the outdoor display panel can be easily washed with water.
れていることを特徴とする請求項1〜3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.
有されていることを特徴とする請求項1〜3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 strong acid.
有されていることを特徴とする請求項1〜3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.
起に応じて、水との接触角に換算して10゜以下の親水
性を呈することを特徴とする請求項1〜6に記載の屋外
表示板。7. 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 photocatalyst. Outdoor display board.
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に記載の屋外表
示板。8. The surface of the surface layer exhibits hydrophilicity of 5 ° or less in terms of contact angle with water in response to photoexcitation of the photocatalyst. Outdoor display board.
ることを特徴とする請求項1〜6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 0.4 μm or less.
あることを特徴とする請求項1〜6に記載の屋外表示
板。10. The outdoor display panel according to claim 1, wherein the surface layer has a thickness of 0.2 μm or less.
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に記載の屋外表示板。11. The surface of the surface layer is further provided with a hydrophilic protective layer.
The outdoor display board according to any one of claims 1 to 6.
とを特徴とする請求項1〜11に記載の屋外表示板。12. The outdoor display board according to claim 1, wherein the outdoor display board is a traffic sign.
ことを特徴とする請求項1〜11に記載の屋外表示板。13. The outdoor display board according to claim 1, wherein the outdoor display board is an advertising signboard.
ことを特徴とする請求項1−11に記載の屋外表示板。14. The outdoor display board according to claim 1, wherein the outdoor display board is an electronic bulletin board.
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。15. A step of preparing the outdoor display panel according to claim 1; a step of arranging the outdoor display panel outdoors; and a photocatalyst contained in a surface layer of the outdoor display panel being photoexcited. The step of making the surface of the layer hydrophilic; the step of exposing the outdoor display panel to rainfall to wash away the deposits and / or contaminants adhering to the surface of the layer with raindrops. Cleaning method.
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。16. A step of preparing the outdoor display panel according to claim 1; and a step of making a surface of the layer hydrophilic by photoexciting a photocatalyst contained in a surface layer of the outdoor display panel. A method for cleaning an outdoor display panel, comprising the steps of rinsing the outdoor display panel with water to release deposits and / or contaminants adhering to the surface of the layer from the surface and rinse with water.
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 true JPH09230810A (en) | 1997-09-05 |
JP3277983B2 JP3277983B2 (en) | 2002-04-22 |
Family
ID=18438979
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JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
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JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
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JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
Family Applications After (52)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
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 |
JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
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JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
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JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
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JP28453496A Expired - Lifetime JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
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JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
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JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
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JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
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JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
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JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
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