JP3414365B2 - Building materials for exterior walls - Google Patents

Building materials for exterior walls

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Publication number
JP3414365B2
JP3414365B2 JP2000180301A JP2000180301A JP3414365B2 JP 3414365 B2 JP3414365 B2 JP 3414365B2 JP 2000180301 A JP2000180301 A JP 2000180301A JP 2000180301 A JP2000180301 A JP 2000180301A JP 3414365 B2 JP3414365 B2 JP 3414365B2
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JP
Japan
Prior art keywords
water
surface layer
sample
building material
titanium oxide
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
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JP2000180301A
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Japanese (ja)
Other versions
JP2001049828A (en
Inventor
信 早川
真 千國
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

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (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)
  • Rear-View Mirror Devices That Are Mounted On The Exterior Of The Vehicle (AREA)
  • Dental Tools And Instruments Or Auxiliary Dental Instruments (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Road Signs Or Road Markings (AREA)
  • Bridges Or Land Bridges (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Detergent Compositions (AREA)
  • Panels For Use In Building Construction (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
  • Greenhouses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laser Surgery Devices (AREA)
  • Materials For Medical Uses (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、降雨により自己浄
化(セルフクリーニング)可能な外壁用建材、また、水
洗浄により容易に清浄化される外壁用建材に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an outer wall building material that can be self-cleaned (self-cleaning) by rainfall, and an outer wall building material that can be easily cleaned by washing with water.

【0002】[0002]

【従来の技術】高層ビル等の外壁は、空気中に含まれる
煤塵や排気ガスなどの燃焼生成物や、上方にあるシーラ
ントから溶出する汚れや、建物の排気口から排出される
汚染物質等の疎水性汚れにより汚れる。これらの疎水性
汚れはうす黒く、建物の美観を著しく損ねる。さらに、
高層ビル外壁を清掃しようとすれば、その清掃は、高所
作業であり、重労働であると同時に危険を伴う。
2. Description of the Related Art The outer wall of a high-rise building, for example, contains combustion products such as dust and exhaust gas contained in the air, dirt eluted from an upper sealant, and pollutants discharged from the exhaust port of the building. Stain with hydrophobic stains. These hydrophobic stains are dark black and significantly impair the aesthetics of the building. further,
If the outer wall of a high-rise building is to be cleaned, the cleaning is a work at a high place, is a heavy labor, and is dangerous at the same time.

【0003】[0003]

【発明が解決しようとする課題】本発明の目的は、降雨
や水洗浄により清浄化可能な外壁用建材を提供すること
にある。
SUMMARY OF THE INVENTION An object of the present invention is to provide a building material for outer wall which can be cleaned by rainfall or washing with water.

【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。
The present invention is based on the finding that in a member having a surface layer containing a photocatalyst, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the mechanism shown below. 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. And, by the cooperative action of one or both of conduction electrons and holes and the polar component, the chemical bond between the surface and the contaminant chemically adsorbed on the surface is cut off, and the chemisorbed water is adsorbed on the surface. Are adsorbed, and a physically adsorbed water layer is further formed thereon. Further, once the surface of the member has been made highly hydrophilic, the hydrophilicity of the surface continues for a certain period even if the member is kept in a dark place.

【0005】本発明では、外壁用建材基体の表面に、実
質的に透明な光触媒性酸化物粒子を含有する表面層を備
えたセルフクリーニング性外壁用建材を提供する。光触
媒性酸化物粒子を含有する表面層を備えることにより、
光触媒の光励起に応じて、表面層の表面は親水性を呈
し、外壁用建材表面が、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。
The present invention provides a self-cleaning outer wall building material comprising a surface layer containing substantially transparent photocatalytic oxide particles on the surface of the outer wall building material substrate. By providing a surface layer containing photocatalytic oxide particles,
In response to the photoexcitation of the photocatalyst, the surface of the surface layer becomes hydrophilic, and when the outer wall building material surface is exposed to rainfall, the adhered deposits and / or contaminants are washed away by raindrops.

【0006】本発明では、外壁用建材基体の表面に、実
質的に透明な光触媒性酸化物粒子を含有する表面層を備
えた易清掃性外壁用建材を提供する。光触媒性酸化物粒
子を含有する表面層を備えることにより、光触媒の光励
起に応じて、表面層の表面は親水性を呈し、外壁用建材
表面は、水で洗浄するのが容易になり、水濯ぎや簡単な
水拭き程度で清浄化される。
The present invention provides an easily-cleanable outer wall building material, which comprises a surface layer containing substantially transparent photocatalytic oxide particles on the surface of the outer wall building material substrate. By providing a surface layer containing photocatalytic oxide particles, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst, and the surface of the building material for outer walls becomes easy to wash with water and rinsed with water. It can be cleaned with a simple water wipe.

【0007】本発明の好ましい態様においては、表面層
には、さらにシリカが含有されているようにする。シリ
カが含有されることにより、表面が水濡れ角0゜に近い
高度の親水性を呈しやすくなると共に、暗所に保持した
ときの親水維持性が向上する。その理由はシリカは構造
中に水を蓄えることができることと関係していると思わ
れる。
In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface tends 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 seems to be related to the ability of silica to store water in its structure.

【0008】本発明の好ましい態様においては、表面層
には、さらに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.

【0009】[0009]

【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。本発明における外壁用建材表面には、図
1又は図2に示すように、基材の表面に光触媒(結晶)
性酸化物等を含む層が形成されている。このような表面
構造をとることで、外壁用建材の表面は、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、
降雨により前記表面層の表面に付着する堆積物及び/又
は汚染物が雨滴により洗い流されるようになる。さら
に、外壁用建材の表面に、上記表面構造を設けた場合
に、前記表面層の表面に付着する堆積物及び/又は汚染
物が水で洗浄するのが容易になり、晴天の日が続く場合
でも、水濯ぎや散水程度で清浄化されるようになる。
BEST MODE FOR CARRYING OUT THE INVENTION Next, a specific structure of the present invention will be described. As shown in FIG. 1 or FIG. 2, on the surface of the building material for outer wall in the present invention, a photocatalyst (crystal) is formed on the surface of the base material.
A layer containing a conductive oxide or the like is formed. By taking such a surface structure, the surface of the building material for outer walls is highly hydrophilized according to the photoexcitation of a photocatalyst. Thereby,
The rain drops wash away the deposits and / or contaminants adhering to the surface of the surface layer. Furthermore, when the surface structure is provided on the surface of the building material for outer walls, the deposits and / or contaminants adhering to the surface of the surface layer can be easily washed with water, and if the sunny day continues. However, it can be cleaned by rinsing with water or sprinkling water.

【0010】図1においては、表面層が光触媒性酸化物
粒子のみからなる。この場合、光触媒が酸化物からなる
ことにより、酸化物は環境中の汚染物質が吸着していな
い状態では親水性を示すので、光励起作用によりその汚
染物質を排斥させ、吸着水層を形成させることで、親水
性を呈しやすく、一様な水膜が形成できる。図2におい
て、Mは金属元素を示す。従って、図2の場合、最表面
は一般の無機酸化物からなる。この場合も、酸化物は環
境中の汚染物質が吸着していない状態では親水性を示す
ので、上記無機酸化物以外に表面層に混入する光触媒性
酸化物の光励起作用によりその汚染物質を排斥させ、吸
着水層を形成させることで、一様な水膜が形成できる。
In FIG. 1, the surface layer consists only of photocatalytic oxide particles. In this case, since the photocatalyst is made of an oxide, the oxide shows hydrophilicity in a state where the pollutant in the environment is not adsorbed, so that the photoexcited action is to eliminate the pollutant to form an adsorbed water layer. Thus, it is easy to exhibit hydrophilicity and 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. Also in this case, since the oxide shows hydrophilicity in the state where the pollutant in the environment is not adsorbed, the pollutant is excluded by the photoexcitation action of the photocatalytic oxide mixed in the surface layer in addition to the above inorganic oxide. By forming the adsorbed water layer, a uniform water film can be formed.

【0011】本発明が利用できる外壁用建材基体には、
施釉タイル、無釉タイル、レンガ、結晶化ガラス、ガラ
スブロック、コンクリート、石材、木材;軽量気泡コン
クリート板、石綿セメントケイ酸カルシウム板、プレキ
ャスト鉄筋コンクリート板、石綿スレート板、パルプセ
メント板、石膏ボード板などの無機基材の表層に、アク
リル樹脂、ウレタン樹脂、ポリエステル、シリコーン、
フッ素樹脂、アクリルシリコン樹脂などの樹脂塗料を塗
装した化粧無機建材;アルミニウム、ステンレス、鉄鋼
等の金属基材の表層に、アクリル樹脂、ウレタン樹脂、
ポリエステル、シリコーン、フッ素樹脂、アクリルシリ
コン樹脂などの樹脂塗料を塗装した塗装鋼板;アクリル
板、ポリカーボネート板等のプラスチック板又はその塗
装物等が好適に利用できる。
The building material substrate for outer wall to which the present invention can be applied includes
Glazed tile, unglaze tile, brick, crystallized glass, glass block, concrete, stone, wood; lightweight cellular concrete board, asbestos cement calcium silicate board, precast reinforced concrete board, asbestos slate board, pulp cement board, gypsum board board, etc. Acrylic resin, urethane resin, polyester, silicone,
Decorative inorganic building materials coated with resin paints such as fluororesin and acrylic silicone resin; acrylic resin, urethane resin, on the surface layer of metal base materials such as aluminum, stainless steel, and steel.
A coated steel plate coated with a resin paint such as polyester, silicone, fluororesin, and acrylic silicone resin; a plastic plate such as an acrylic plate or a polycarbonate plate, or a coated product thereof can be preferably used.

【0012】光触媒とは、その結晶の伝導帯と価電子帯
との間のエネルギーギャップよりも大きなエネルギー
(すなわち短い波長)の光(励起光)を照射したとき
に、価電子帯中の電子の励起(光励起)が生じて、伝導
電子と正孔を生成しうる物質をいい、光触媒性酸化チタ
ンとは、例えば、アナターゼ型酸化チタン、ルチル型酸
化チタン等の結晶性酸化チタンをいう。ここで光触媒の
光励起に用いる光源としては、太陽光が好適に利用でき
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
2以上あればよいが、0.01mW/cm2以上だと好ま
しく、0.1mW/cm2以上だとより好ましい。
A photocatalyst is a photocatalyst of an electron in the valence band when it is irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. Excitation (photoexcitation) refers to a substance capable of generating conduction electrons and holes, and the photocatalytic titanium oxide refers to crystalline titanium oxide such as anatase type titanium oxide and rutile type titanium oxide. Here, sunlight can be preferably used as a light source used for photoexcitation of the photocatalyst. 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.
It may be 2 or more, but 0.01 mW / cm 2 or more is preferable, and 0.1 mW / cm 2 or more is more preferable.

【0013】光触媒性酸化チタンを含有する表面層の膜
厚は、0.4μm以下にするのが好ましい。そうすれ
ば、光の乱反射による白濁を防止することができ、表面
層は実質的に透明となる。さらに、光触媒性酸化チタン
を含有する表面層の膜厚を0.2μm以下にすると一層
好ましい。そうすれば、光の干渉による表面層の発色を
防止することができる。また、表面層が薄ければ薄いほ
どその透明度は向上する。更に、膜厚を薄くすれば、表
面層の耐摩耗性が向上する。上記表面層の表面に、更
に、親水化可能な耐摩耗性又は耐食性の保護層や他の機
能膜を設けても良い。
The thickness of the surface layer containing the photocatalytic titanium oxide is preferably 0.4 μm or less. Then, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, it is more preferable that the thickness of the surface layer containing the photocatalytic titanium oxide be 0.2 μm or less. By doing so, it is possible to prevent coloration of the surface layer due to light interference. Also, the thinner the surface layer, the higher its transparency. Furthermore, if 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 which can be made hydrophilic and other functional films.

【0014】上記表面層は、基材と比較して屈折率があ
まり高くないのが好ましい。好ましくは表面層の屈折率
は2以下であるのがよい。そうすれば、基材と表面層と
の界面、及び表面層と空気との界面における光の反射を
抑制できる。表面層の屈折率を2以下にするには、光触
媒性酸化チタンに、屈折率2以下の他の物質を表面層に
添加する。ここで、屈折率2以下の他の物質としては、
例えば、炭酸カルシウム(屈折率1.6)、水酸化カル
シウム(屈折率1.6)、炭酸マグネシウム(屈折率
1.5)、炭酸ストロンチウム(屈折率1.5)、ドロ
マイト(屈折率1.7)、フッ化カルシウム(屈折率
1.4)、フッ化マグネシウム(屈折率1.4)、シリ
カ(屈折率1.5)、アルミナ(屈折率1.6)、ケイ
砂(屈折率1.6)、モンモリロナイト(屈折率1.
5)、カオリン(屈折率1.6)、セリサイト(屈折率
1.6)、ゼオライト(屈折率1.5)、酸化錫(屈折
率1.9)等を表面層に添加できる。
The surface layer preferably has a refractive index that is not so high as that of the substrate. The refractive index of the surface layer is preferably 2 or less. Then, reflection of light at the interface between the substrate and the surface layer and the interface between the surface layer and the air can be suppressed. To reduce the refractive index of the surface layer to 2 or less, another substance having a refractive index of 2 or less is added to the photocatalytic titanium oxide. Here, as another substance having a refractive index of 2 or less,
For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1.7). ), Calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica sand (refractive index 1.6). ), Montmorillonite (refractive index 1.
5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9) and the like can be added to the surface layer.

【0015】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 metal-added surface layer can kill bacteria and mold attached to the surface even in a dark place.

【0016】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
触媒以外に固体酸を添加した場合には、白金族金属の添
加により固体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。上記表面層には、Moが添加されていて
もよい。この場合にも添加により固体酸の酸度が向上す
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
Platinum group metals such as h, Ir, Os can be added. The surface layer to which the metal is added can enhance the redox activity of the photocatalyst and improve the deodorizing purification action and the like. Further, when a solid acid other than the photocatalyst is added, the acidity of the solid acid is improved by the addition of the platinum group metal, so that the hydrophilicity maintenance property is also improved, and the water film of the adhered water is further promoted to some extent. The hydrophilicity maintaining property when the photocatalyst is not irradiated with the excitation light for a long time is also improved. Mo may be added to the surface layer. Also in this case, since the acidity of the solid acid is improved by the addition, the hydrophilicity-maintaining property is also improved, and the formation of a water film of the attached water is further promoted, and the hydrophilicity-maintaining property when the photocatalyst is not irradiated with the excitation light for a certain period of time. Also improves.

【0017】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 alkali network modifying ions are prevented from diffusing from the base material to the surface layer during firing, and the photocatalytic function is better exhibited.

【0018】親水性とは、表面に水を滴下したときにな
じみやすい性質をいい、一般に水濡れ角が90゜未満の
状態をいう。本発明における高度の親水性とは、表面に
水を滴下したときに非常になじみやすい性質をいい、よ
り具体的には水濡れ角が10゜以下程度になる状態をい
う。特に、防曇性にはPCT/JP96/00734に
開示したように、水濡れ角が10゜以下であると好まし
く、5゜以下ではより好ましい。
The term "hydrophilic" refers to the property of easily fitting when water is dripped onto the surface thereof, and generally refers to a state where the water wetting angle is less than 90 °. The high degree of hydrophilicity in the present invention refers to the property of being very easily blended when water is dropped on the surface, and more specifically, a state in which the water wetting angle is about 10 ° or less. In particular, as disclosed in PCT / JP96 / 00734, the antifogging property is preferably such that the water wetting angle is 10 ° or less, more preferably 5 ° or less.

【0019】本発明における固体酸には、硫酸担持Al
23、硫酸担持TiO2、硫酸担持ZrO2、硫酸担持S
nO2、硫酸担持Fe23、硫酸担持SiO2、硫酸担持
HfO2、TiO2/WO3、WO3/SnO2、WO3/Z
rO2、WO3/Fe23、SiO2・Al23、TiO2
/SiO2、TiO2/Al23、TiO2/ZrO2等が
好適に利用できる。
The solid acid in the present invention includes sulfuric acid carrying Al.
2 O 3 , sulfuric acid-supporting TiO 2 , sulfuric acid-supporting ZrO 2 , sulfuric acid-supporting S
nO 2 , Fe 2 O 3 supporting sulfuric acid, SiO 2 supporting sulfuric acid, HfO 2 supporting sulfuric acid, TiO 2 / WO 3 , WO 3 / SnO 2 , WO 3 / Z
rO 2 , WO 3 / Fe 2 O 3 , SiO 2 · Al 2 O 3 , TiO 2
/ SiO 2 , TiO 2 / Al 2 O 3 , TiO 2 / ZrO 2 and the like can be preferably used.

【0020】次に、表面層の形成方法について説明す
る。まず、表面層が光触媒性酸化物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形酸化チタンの層
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、無定形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、基材表面に無定形酸化チ
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、無定形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 of forming the surface layer will be described. First, the production method in the case where the surface layer is composed only of the photocatalytic oxide 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 firing method, another method is an organic titanate method, and another method is an electron beam evaporation method. (1) Sol coating firing method Anatase type titanium oxide sol
The surface of the base material is applied by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, or a roll coating method, and then baked. (2) Organic titanate method Titanium alkoxide (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, 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, It is applied by a method such as a flow coating method, a spin coating method or a roll coating method, and dried. Drying completes the hydrolysis of the organic titanate to produce titanium hydroxide,
A layer of amorphous titanium oxide is formed on the surface of the substrate by dehydration polycondensation of titanium hydroxide. Then, it is baked at a temperature equal to or higher than the crystallization temperature of anatase to transform the amorphous titanium oxide into anatase-type titanium oxide. (3) Electron beam evaporation method A target of titanium oxide is irradiated with an electron beam to form a layer of amorphous titanium oxide on the surface of the base material. Then, it is baked at a temperature equal to or higher than the crystallization temperature of anatase to transform the amorphous titanium oxide into anatase-type titanium oxide.

【0021】次に、表面層が光触媒性酸化物とシリカか
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形酸
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、無定形酸化チ
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
イング法、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 photocatalytic oxide and silica will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. In this case, there are the following three methods, for example. One is the sol coating firing method, the other is the organic titanate method, and the other is the tetrafunctional silane method. (1) Sol coating firing method A mixed solution of anatase type titanium oxide sol and silica sol is applied to the surface of a substrate by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method, a roll coating method, etc. and baked. To do. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelates and other organic titanates are added with a hydrolysis inhibitor (hydrochloric acid, ethylamine, etc.) and silica sol. Add alcohol (ethanol, propanol, butanol, etc.)
After diluting with a non-aqueous solvent such as, while partially proceeding the hydrolysis or after proceeding the hydrolysis completely, the mixture is spray-coated, dip-coated,
It is applied by a method such as a flow coating method, a spin coating method or a roll coating method, and dried. Drying completes the hydrolysis of the organic titanate to produce titanium hydroxide, and a dehydration condensation polymerization of titanium hydroxide forms an amorphous titanium oxide layer on the surface of the substrate. Then, it is baked at a temperature equal to or higher than the crystallization temperature of anatase to transform the amorphous titanium oxide into anatase-type 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 and the like, and if necessary, hydrolyzed to form silanol, and then silanol is subjected to dehydration polycondensation by a method such as heating.

【0022】次に、表面層が光触媒性酸化物と固体酸か
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。他の方法は、電子ビーム蒸着や、チタンアルコキシ
ド、チタンアセテート、チタンキレート等の有機チタネ
ートの加水分解及び脱水縮重合により、無定形酸化チタ
ン被膜を形成後、タングステン酸を塗布し、その後、無
定形酸化チタンが結晶化し、かつTiO2/WO3複合酸
化物が生成する温度で熱処理する。
Next, the case where the surface layer is composed of a photocatalytic oxide and a solid acid will be described by taking as an example the case where the photocatalyst is anatase type titanium oxide and the solid acid is TiO 2 / WO 3 . The method in this case is to mix an ammonia solution of tungstic acid with an anatase type titanium oxide sol and, if necessary, dilute the mixture with a diluent (water, ethanol, etc.) on the surface of the substrate by spray coating or dip coating. Method, flow coating method, spin coating method, roll coating method, etc., and baking. Other methods include electron beam evaporation and hydrolysis and dehydration polycondensation of organic titanates such as titanium alkoxide, titanium acetate, and titanium chelate to form an amorphous titanium oxide film, then apply tungstic acid, and then form amorphous titanium oxide. Heat treatment is performed at a temperature at which titanium oxide is crystallized and a TiO 2 / WO 3 composite oxide is formed.

【0023】次に、表面層が光触媒性酸化物とシリコー
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 photocatalytic oxide and silicone will be described by taking the case where the photocatalyst is anatase type titanium oxide as an example. The method in this case is to mix a coating composed of uncured or partially cured silicone or a precursor of silicone and anatase type titanium oxide sol, and hydrolyze the precursor of silicone as needed, and then mix the mixture. Is applied to the surface of the substrate by a method such as a spray coating method, a dip coating method, a flow coating method, a spin coating method and a roll coating method, and the hydrolyzate of the silicone precursor is dehydrated and polycondensed by a method such as heating. Then, a surface layer composed of anatase type titanium oxide particles and silicone is formed. 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 and 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, diethyldi Propoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, and their hydrolysates and their mixtures are preferably used. it can.

【0024】その他、上記コーティングを塗布したフィ
ルムを基材表面にセッケン水等の透明接着剤で貼着して
もよい。ここでフィルム基材には、ポリエチレンテレフ
タレート、ポリエステル、ポリエチレン等のプラスチッ
ク製フィルムが好適に利用できる。
In addition, the film coated with the above coating may be attached to the surface of the substrate with a transparent adhesive such as soapy water. Here, a plastic film such as polyethylene terephthalate, polyester, or polyethylene can be preferably used as the film substrate.

【0025】[0025]

【実施例】実施例1.アナターゼ型酸化チタンゾル(日
産化学、TA−15、固形分15重量%、硝酸解膠型、
pH=1)16重量部と、シリカゾル(日本合成ゴム、
グラスカA液、固形分13重量%、pH=4)9重量部
を混合後、メチルトリメトキシシラン(日本合成ゴム、
グラスカB液)3重量部とエタノール452重量部を添
加し、さらに2時間撹拌し、メチルトリメトキシシラン
を部分的に加水分解反応と脱水縮重合反応に付すること
により、コーティング液を調製した。このコーティング
液をフローコーティング法により、化粧無機建材(大建
工業、セラスター、WK1002−113,アイボリー
ホワイト、板厚4mm;オートクレーブ処理したセメン
トケイ酸カルシウム板の表面を素地調整した後、シリコ
ーン樹脂系の着色塗料を塗布した化粧無機建材)の表面
に塗布した後、150℃で30分間加熱した。次に、コ
ーティング液を塗布した面に、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
0.5mW/cm2の紫外線照度で約3日紫外線を照射
し、#1試料を得た。比較のため、化粧無機建材(大建
工業、セラスター、WK1002−113,アイボリー
ホワイト、板厚4mm)#2試料も準備した。#1試料
と#2試料に水滴を滴下し、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、#2試料では水との接触
角が90゜と疎水性を示したのに対し、#1試料では水
との接触角が0゜と高度の親水性を示した。
EXAMPLES Example 1. Anatase type titanium oxide sol (Nissan Chemical, TA-15, solid content 15% by weight, nitric acid peptization type,
16 parts by weight of pH = 1 and silica sol (Japan Synthetic Rubber,
Glasca A liquid, solid content 13% by weight, pH = 4) 9 parts by weight were mixed, and then methyltrimethoxysilane (Japan Synthetic Rubber,
3 parts by weight of Glasca B solution) and 452 parts by weight of ethanol were added, the mixture was further stirred for 2 hours, and methyltrimethoxysilane was partially subjected to a hydrolysis reaction and a dehydration polycondensation reaction to prepare a coating solution. This coating solution was applied by flow coating to a decorative inorganic building material (Daiken Kogyo, Cerastar, WK1002-113, ivory white, plate thickness 4 mm; after adjusting the surface of the autoclaved cement calcium silicate plate, the silicone resin-based material was used. After being applied to the surface of the decorative inorganic building material to which the coloring paint was applied, it was heated at 150 ° C. for 30 minutes. Then, the surface coated with the coating solution was irradiated with ultraviolet rays for about 3 days at an ultraviolet illuminance of 0.5 mW / cm 2 using an ultraviolet light source ((Sankyo Denki, Black Light Blue (BLB) fluorescent lamp), # 1. Samples were obtained.For comparison, a makeup inorganic building material (Taken Kogyo, Cerastar, WK1002-113, ivory white, plate thickness 4 mm) # 2 sample was also prepared. The contact angle with water was measured by using a contact angle measuring instrument (Kyowa Interface Science, CA-X150), and the contact angle with water 30 seconds after dropping was evaluated. As a result, the # 2 sample showed a high contact angle with water of 90 °, whereas the # 1 sample showed a high contact angle of 0 ° with water, indicating a high degree of hydrophilicity.

【0026】次に、#1試料、#2試料を屋外に設置し
て、降雨によるセルフクリーニング性について調べた。
降雨によるセルフクリーニング性は以下のようにして試
験した。すなわち、茅ケ崎市所在の建物の屋上に3図及
び4図に示す屋外汚れ加速試験装置を設置した。3図及
び4図を参照するに、この装置は、フレーム20に支持
された傾斜した試料支持面22を備え、試料24を取り
付けるようになっている。フレームの頂部には前方に傾
斜した屋根26が固定してある。この屋根は波形プラス
チック板からなり、集まった雨が試料支持面22に取り
付けた試料24の表面に筋を成して流下するようになっ
ている。この装置の試料支持面22に#1試料と、#2
試料を取り付け、1995年6月12日から1か月間天
候条件に暴露した。この間梅雨時のため、頻繁に雨が降
った。1か月後に観察したところ、光触媒被膜のない#
2試料では、試料表面に縦筋状の汚れが顕著に観察され
た。これに対して、光触媒被膜のある#1試料では、汚
れは観察されなかった。その様子を加速試験装置取り付
け前後に最も顕著に汚れた部分の色差変化で調べた。こ
こで色差は色差計(東京電色)を用い、日本工業規格
(JIS)H0201に従い、ΔE*表示を用いて調べ
た。その結果、光触媒被膜のない#2試料では色差変化
は7.2と非常に大きく、汚れが顕著であるのに対し、
光触媒被膜のある#1試料では、色差変化は0.8と非
常に小さかった。
Next, the # 1 sample and the # 2 sample were installed outdoors and examined for self-cleaning property by rainfall.
The self-cleaning property by rainfall was tested as follows. That is, the outdoor stain acceleration test device shown in FIGS. 3 and 4 was installed on the roof of a building located in Chigasaki City. With reference to FIGS. 3 and 4, the apparatus includes an inclined sample support surface 22 supported by a frame 20 for mounting a sample 24. A roof 26 that is inclined forward is fixed to the top of the frame. The roof is made of a corrugated plastic plate, and the collected rain flows down in a streak on the surface of the sample 24 attached to the sample support surface 22. On the sample support surface 22 of this device, # 1 sample and # 2 sample
The sample was attached and exposed to weather conditions for one month from June 12, 1995. During the rainy season, it rained frequently. Observed after 1 month, no photocatalyst coating #
In the two samples, vertical stripe-like stains were remarkably observed on the surface of the samples. In contrast, no stain was observed in the # 1 sample with the photocatalytic coating. The state was examined by the change in color difference of the most contaminated part before and after mounting the acceleration test device. Here, the color difference was examined by using a color difference meter (Tokyo Denshoku Co., Ltd.) according to Japanese Industrial Standard (JIS) H0201 and using ΔE * display. As a result, in the # 2 sample without the photocatalytic coating, the color difference change was as large as 7.2, and the stain was remarkable, while
In the # 1 sample having the photocatalytic coating, the change in color difference was 0.8, which was very small.

【0027】実施例2.テトラエトキシシラン(和光純
薬)0.69gとアナターゼ型酸化チタンゾル(日産化
学、TA−15、平均粒径10nm)1.07gとエタ
ノール29.88gと、純水0.36gを混合し、コー
ティング液を調製した。このコーティング液をフローコ
ーティング法により、5×10cm角の結晶化ガラス基
材上に塗布した。この結晶化ガラス板を約20分間約1
50℃の温度に保持することにより、テトラエトキシシ
ランを加水分解と脱水縮重合に付し、アナターゼ型酸化
チタン粒子が無定形シリカで結着されたコーティングを
結晶化ガラス板表面に形成した。このコーティング中
の、酸化チタンとシリカとの重量比は1であった。この
結晶化ガラス板を数日間暗所に放置した後、紫外線光源
(三共電気、ブラックライトブルー(BLB)蛍光灯)
を用いて試料の表面に0.5mW/cm2の紫外線照度
で約1時間紫外線を照射し、#3試料を得た。比較のた
め、10cm角の結晶化ガラス板を数日間暗所に放置し
た#4試料も準備した。まず、#3試料と#4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、#4試料ではマイクロシリンジか
ら試料表面に水滴を滴下されると、水滴は表面になじん
でいくものの、一様に水膜状になるまでには至らなかっ
た。また、30秒後の水との接触角は30゜であった。
Example 2. 0.69 g of tetraethoxysilane (Wako Pure Chemical Industries), 1.07 g of anatase type titanium oxide sol (TA-15, average particle size 10 nm), 29.88 g of ethanol, and 0.36 g of pure water are mixed to form a coating liquid. Was prepared. This coating liquid was applied on a 5 × 10 cm square crystallized glass substrate by a flow coating method. This crystallized glass plate for about 20 minutes about 1
By maintaining the temperature at 50 ° C., tetraethoxysilane was subjected to hydrolysis and dehydration polycondensation, and a coating in which anatase type titanium oxide particles were bound with amorphous silica was formed on the surface of the crystallized glass plate. The weight ratio of titanium oxide and silica in this coating was 1. After leaving this crystallized glass plate in the dark for a few days, it was exposed to an ultraviolet light source (Sankyo Denki, Black Light Blue (BLB) fluorescent lamp).
Was used to irradiate the surface of the sample with ultraviolet light having an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 3 sample. For comparison, a # 4 sample in which a 10 cm square crystallized glass plate was left in the dark for several days was also prepared. First, water drops were dropped on the # 3 sample and the # 4 sample, and the state after the drop was observed and the contact angle with water was measured. Here, the contact angle with water was evaluated by using a contact angle measuring device (Kyowa Interface Science, CA-X150) and the contact angle with water 30 seconds after dropping. As a result, it was observed that when water droplets were dropped from the microsyringe on the sample surface of the # 3 sample, the water droplets spread uniformly on 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 case of the # 4 sample, when a water droplet was dropped from the microsyringe on the surface of the sample, the water droplet adapted to the surface but did not reach a uniform water film shape. The contact angle with water after 30 seconds was 30 °.

【0028】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#1試料に上記スラリ
ー150mlを流下させて15分間乾燥させ、次いで蒸
留水150mlを流下させて15分間乾燥させ、このサ
イクルを25回反復した。試験前後の色差変化を、色差
計(東京電色)を用いて計測した。色差は日本工業規格
(JIS)H0201に従い、ΔE*表示を用いて評価
した。その結果、#1試料の試験前後の色差変化は0.
6とほとんど変化しなかった。
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. 150 ml of the above slurry was made to flow down on a # 1 sample inclined at 45 degrees and dried for 15 minutes, then 150 ml of distilled water was made to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standard (JIS) H0201 using ΔE * display. As a result, the color difference change of the # 1 sample before and after the test was 0.
There was almost no change from 6.

【0029】実施例3.アンモニア解膠アナターゼ型酸
化チタンゾル(石原産業、STS−11)1gと、2g
の25%アンモニア水に溶解させたタングステン酸を混
合し、さらに2gの蒸留水を加えてコーティング液中の
酸化チタン粒子とタングステン酸のモル比は10:1と
なるようにした。次いで、5×10cm四角の施釉タイ
ル板(東陶機器、AB02E11)に、上記コーティン
グ液を塗布し、700℃の温度で30分焼成して、アナ
ターゼ型酸化チタンとTiO2/WO3からなる#5試料
を得た。なお、表面層による発色は認められなかった。
次に、この#5試料を数日間暗所に放置した後、BLB
蛍光灯を用いて試料の表面に0.5mW/cm2の紫外
線照度で約1時間紫外線を照射し、#6試料を得た。比
較のため、5×10cm角の施釉タイル板(東陶機器、
AB02E11)を数日間暗所に放置した#7試料も準
備した。まず、#6試料と#7試料に水滴を滴下し、滴
下後の様子の観察及び水との接触角の測定を行った。そ
の結果#6試料はマイクロシリンジから試料表面に水滴
を滴下されると、水滴が一様に水膜状に試料表面を拡が
る様子が観察された。また30秒後の水との接触角は約
0゜まで高度に親水化されていた。それに対し、#7試
料ではマイクロシリンジから試料表面に水滴を滴下され
ると、水滴は表面になじんでいくものの、一様に水膜状
になるまでには至らなかった。また、30秒後の水との
接触角は30゜であった。さらに、#6試料を、その後
2日間暗所に放置し、#8試料を得た。そして#8試料
について、同様に水との接触角を接触角測定器により測
定した。その結果、#8試料にマイクロシリンジから試
料表面に水滴を滴下されると、#6試料と同様に、水滴
が一様に水膜状に試料表面を拡がる様子が観察された。
また水との接触角は約1゜に維持された。
Example 3. Ammonia peptization anatase type titanium oxide sol (Ishihara Sangyo, STS-11) 1g and 2g
Tungstic acid dissolved in 25% aqueous ammonia was mixed, and 2 g of distilled water was further added so that the molar ratio of titanium oxide particles to tungstic acid in the coating liquid was 10: 1. Next, a 5 × 10 cm square glazed tile plate (TO02, AB02E11) was coated with the above coating solution and baked at a temperature of 700 ° C. for 30 minutes to form anatase type titanium oxide and TiO 2 / WO 3. Five samples were obtained. No color development was observed due to the surface layer.
Next, after leaving this # 5 sample in the dark for several days,
The surface of the sample was irradiated with ultraviolet rays for about 1 hour using a fluorescent lamp at an ultraviolet illuminance of 0.5 mW / cm 2 to obtain a # 6 sample. For comparison, 5 × 10 cm square glazed tile board (Totoki Equipment,
A # 7 sample was also prepared in which AB02E11) was left in the dark for several days. First, water drops were dropped on the # 6 sample and the # 7 sample, and the state after the drop was observed and the contact angle with water was measured. As a result, when the # 6 sample was dropped from the microsyringe onto the sample surface, it was observed that the water droplet spreads uniformly on 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 # 7 sample, when a water droplet was dropped from the microsyringe on the surface of the sample, the water droplet adapted to the surface, but did not reach a uniform water film shape. The contact angle with water after 30 seconds was 30 °. Further, the # 6 sample was left in the dark for 2 days to obtain the # 8 sample. Then, with respect to the # 8 sample, the contact angle with water was similarly measured with a contact angle measuring device. As a result, when water droplets were dropped onto the sample surface of the # 8 sample from the microsyringe, it was observed that the water droplets spread uniformly on the sample surface in the form of a water film, similarly to the # 6 sample.
The contact angle with water was maintained at about 1 °.

【0030】次に#8試料の表面にオレイン酸を塗布
し、試料表面を水平姿勢に保持しながら夫々の試料を水
槽に満たした水の中に浸漬した。その結果、オレイン酸
は丸くなり、軽くこすると表面から離脱した。
Next, oleic acid was applied to the surface of the # 8 sample, and each sample was immersed in water filled in a water tank while keeping the sample surface in a horizontal position. As a result, the oleic acid became round and separated from the surface by light rubbing.

【0031】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#8試料に上記スラリ
ー150mlを流下させて15分間乾燥させ、次いで蒸
留水150mlを流下させて15分間乾燥させ、このサ
イクルを25回反復した。試験前後の色差変化を、色差
計(東京電色)を用いて計測した。色差は日本工業規格
(JIS)H0201に従い、ΔE*表示を用いて評価
した。その結果、#8試料の試験前後の色差変化は0.
4とほとんど変化しなかった。
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. 150 ml of the above slurry was made to flow down on a # 8 sample inclined at 45 degrees and dried for 15 minutes, then 150 ml of distilled water was made to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The change in color difference before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standard (JIS) H0201 using ΔE * display. As a result, the change in color difference of the # 8 sample before and after the test was 0.
There was almost no change from 4.

【0032】[0032]

【発明の効果】本発明では、外壁用建材の表面に、実質
的に透明な光触媒性酸化物粒子を含有する表面層を備え
ることにより、光触媒の光励起に応じて、表面層の表面
は親水性を呈する。それにより、降雨により前記表面層
の表面はセルフクリーニングされるようになる。さら
に、水で濯ぐ又は散水のみで前記表面層の表面は清浄化
されるようになる。
According to the present invention, the surface of the building material for outer walls is provided with a surface layer containing substantially transparent photocatalytic oxide particles, whereby the surface of the surface layer is hydrophilic in response to photoexcitation of the photocatalyst. Present. As a result, the surface of the surface layer is self-cleaned by the rainfall. Furthermore, the surface of the surface layer is cleaned only by rinsing with water or sprinkling water.

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

【図1】本発明に係る外壁用建材の表面構造を示す図。FIG. 1 is a diagram showing a surface structure of a building material for outer wall according to the present invention.

【図2】本発明に係る外壁用建材の他の表面構造を示す
図。
FIG. 2 is a view showing another surface structure of the building material for outer wall according to the present invention.

【図3】本発明の実施例に係る屋外汚れ加速試験装置の
正面図。
FIG. 3 is a front view of an outdoor stain acceleration test apparatus according to an embodiment of the present invention.

【図4】本発明の実施例に係る屋外汚れ加速試験装置の
側面図。
FIG. 4 is a side view of an outdoor dirt acceleration test apparatus according to an embodiment of the present invention.

フロントページの続き (56)参考文献 特開 平6−278241(JP,A) 特開 平9−173783(JP,A) 特開 平8−302856(JP,A) 特開 平7−171408(JP,A) (58)調査した分野(Int.Cl.7,DB名) E04F 13/08 E04B 1/92 B01D 53/86 B01J 35/02 Continuation of the front page (56) Reference JP-A-6-278241 (JP, A) JP-A-9-173783 (JP, A) JP-A-8-302856 (JP, A) JP-A-7-171408 (JP , A) (58) Fields investigated (Int.Cl. 7 , DB name) E04F 13/08 E04B 1/92 B01D 53/86 B01J 35/02

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 高層ビル等の外壁用建材基体の表面に、
光触媒性酸化物粒子及びシリカ又はシリコーンを含有す
る表面層を備え、前記光触媒性酸化物の光励起に応じ
て、前記表面層の表面は親水性を呈し、前記外壁用建材
表面が、降雨にさらされた時に、空気中に含まれる煤塵
や排気ガスなどの燃焼生成物や、上方にあるシーラント
から溶出する汚れや、建物の排気口から排出される汚染
物質等の疎水性汚れ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外壁用建材。
1. A surface of a building material substrate for an outer wall of a high-rise building,
A surface layer containing photocatalytic oxide particles and silica or silicone is provided, and the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalytic oxide, and the surface of the outer wall building material is exposed to rainfall. When it does, raindrops wash away combustion products such as dust and exhaust gas contained in the air, dirt eluted from the upper sealant, and hydrophobic dirt such as pollutants discharged from the exhaust port of the building. Self-cleaning outer wall building material that enables
【請求項2】 高層ビル等の外壁用建材基体の表面に、
光触媒性酸化物粒子及びシリカ又はシリコーンを含有す
る表面層を備え、前記光触媒性酸化物の光励起に応じ
て、前記表面層の表面は親水性を呈し、前記外壁用建材
表面が、空気中に含まれる煤塵や排気ガスなどの燃焼生
成物や、上方にあるシーラントから溶出する汚れや、建
物の排気口から排出される汚染物質等の疎水性汚れを水
で洗浄するのを容易とする易清掃性外壁用建材。
2. The surface of a building material substrate for outer wall of a high-rise building,
A surface layer containing photocatalytic oxide particles and silica or silicone is provided, and the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalytic oxide, and the outer wall building material surface is contained in the air. Easy-to-clean property that facilitates cleaning with water of combustion products such as soot dust and exhaust gas, dirt eluted from the sealant above, and hydrophobic dirt such as pollutants discharged from the exhaust port of the building Building material for outer walls.
JP2000180301A 1995-12-22 2000-06-15 Building materials for exterior walls Expired - Lifetime JP3414365B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35464995 1995-12-22
JP7-354649 1995-12-22

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP28281296A Division JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them

Publications (2)

Publication Number Publication Date
JP2001049828A JP2001049828A (en) 2001-02-20
JP3414365B2 true JP3414365B2 (en) 2003-06-09

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JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
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JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
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JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
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JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
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JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
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
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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
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JP2000181286A Expired - Lifetime JP3414367B2 (en) 1995-12-22 2000-06-16 Building materials for exterior walls
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JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
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Family Applications Before (61)

Application Number Title Priority Date Filing Date
JP8083499A Pending JPH09231821A (en) 1995-12-22 1996-04-05 Luminaire and method for maintaining illuminance
JP13408196A Expired - Lifetime JP3385850B2 (en) 1995-12-22 1996-04-19 Composite material with hydrophilicity
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JP15017196A Expired - Lifetime JP3760509B2 (en) 1995-12-22 1996-05-22 Greenhouse ceiling and its condensation prevention method
JP8150410A Pending JPH09225263A (en) 1995-12-22 1996-05-23 Air pollutant removing filter, air pollutant removing fan and ventilator using the fan
JP8156383A Pending JPH09231849A (en) 1995-12-22 1996-05-29 Insulator and dirt preventing method therefore
JP8136777A Pending JPH09227178A (en) 1995-12-22 1996-05-30 Laminated glass and its production
JP13653596A Expired - Lifetime JP3339304B2 (en) 1995-12-22 1996-05-30 Painted object and painting method
JP13782996A Ceased JP3189682B2 (en) 1995-12-22 1996-05-31 Antifouling material
JP8168643A Pending JPH09232096A (en) 1995-12-22 1996-06-06 Electrification preventing method, and electrification preventive composite material
JP8145265A Pending JPH09225276A (en) 1995-12-22 1996-06-07 Separating membrane and formation of surface layer to separating membrane
JP8168662A Pending JPH09225389A (en) 1995-12-22 1996-06-10 Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture
JP8158518A Pending JPH09225021A (en) 1995-12-22 1996-06-19 Medical material
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JP8272815A Pending JPH09224957A (en) 1995-12-22 1996-09-06 Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop
JP8272814A Pending JPH09226041A (en) 1995-12-22 1996-09-06 Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member
JP27280996A Expired - Fee Related JP3588202B2 (en) 1995-12-22 1996-09-07 Anti-fog road mirror and its anti-fog method
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
JP27519096A Expired - Lifetime JP3277983B2 (en) 1995-12-22 1996-09-10 Outdoor display panel and its cleaning method
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
JP8282807A Pending JPH09224874A (en) 1995-12-22 1996-09-18 Water-closet bowl made of resin
JP08282811A Expired - Fee Related JP3075195B2 (en) 1995-12-22 1996-09-18 Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror
JP8282809A Pending JPH09230108A (en) 1995-12-22 1996-09-18 Anti-fogging plastic lens and its anti-fogging method
JP8282805A Pending JPH09231499A (en) 1995-12-22 1996-09-18 Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal
JP8246180A Pending JPH09230493A (en) 1995-12-22 1996-09-18 Camera
JP28281296A Expired - Lifetime JP3612896B2 (en) 1995-12-22 1996-09-18 Exterior wall building materials and methods for cleaning them
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
JP8284533A Pending JPH09227161A (en) 1995-12-22 1996-09-19 Pane, film for applying thereto and antifogging and cleaning thereof
JP28453496A Expired - Lifetime JP3173391B2 (en) 1995-12-22 1996-09-19 Hydrophilic film, and method for producing and using the same
JP8284532A Pending JPH09227805A (en) 1995-12-22 1996-09-19 Photocatalytic hydrophilic coating composition
JP28579796A Expired - Lifetime JP3697795B2 (en) 1995-12-22 1996-09-20 Display and cleaning method thereof
JP28895696A Expired - Fee Related JP3588206B2 (en) 1995-12-22 1996-09-25 Self-cleaning road decorative panel, and method of cleaning road decorative panel
JP28895596A Expired - Lifetime JP3774955B2 (en) 1995-12-22 1996-09-25 Self-cleaning handrail and handrail cleaning method
JP28895496A Expired - Fee Related JP3588205B2 (en) 1995-12-22 1996-09-25 Self-cleaning guard fence and method of cleaning guard fence
JP8291007A Pending JPH09225054A (en) 1995-12-22 1996-09-26 Gas mask and storing device for gas mask
JP8291005A Pending JPH09230031A (en) 1995-12-22 1996-09-26 Inter-vehicle distance detecting device and automobile having it
JP8291006A Pending JPH09229767A (en) 1995-12-22 1996-09-26 Pyroelectric infrared detector
JP8297248A Pending JPH09227169A (en) 1995-12-22 1996-10-18 Transfer sheet, and transferring of photocatalytic and hydrophilic thin film
JP8298235A Pending JPH09230119A (en) 1995-12-22 1996-10-22 Road mirror for assuring visual field in rainy weather
JP8298237A Pending JPH09229546A (en) 1995-12-22 1996-10-22 Door for refrigerated showcase having see-through ensuring property
JP8298236A Pending JPH09227162A (en) 1995-12-22 1996-10-22 Vehicle pane for securing rainy weather view, and automobile mounted therewith
JP8298234A Pending JPH09226531A (en) 1995-12-22 1996-10-22 Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it
JP8307000A Pending JPH09224800A (en) 1995-12-22 1996-11-01 Glassware and water-washing method
JP8306997A Pending JPH09226060A (en) 1995-12-22 1996-11-01 Lid for heating container having fog resistance
JP8323516A Pending JPH09241038A (en) 1995-12-22 1996-11-19 Photocatalytic hydrophilic member and its production
JP8340470A Pending JPH09225387A (en) 1995-12-22 1996-12-05 Hydrophilic member and method to make surface of member hydrophilic
JP34047196A Expired - Lifetime JP3303696B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
JP34047296A Expired - Fee Related JP3348613B2 (en) 1995-12-22 1996-12-05 Photocatalytic hydrophilic coating composition
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

Family Applications After (9)

Application Number Title Priority Date Filing Date
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
JP2000181284A Pending JP2001048679A (en) 1995-12-22 2000-06-16 Photocatalytic hydrophilic tile and its production
JP2000227056A Pending JP2001129916A (en) 1995-12-22 2000-07-27 Photocatalytic hydrophilic member
JP2000227055A Withdrawn JP2001089752A (en) 1995-12-22 2000-07-27 Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof
JP2000247609A Pending JP2001122679A (en) 1995-12-22 2000-08-17 Antifouling tile
JP2001140242A Pending JP2002030258A (en) 1995-12-22 2001-05-10 Coated material and method for coating
JP2002020533A Expired - Fee Related JP3882625B2 (en) 1995-12-22 2002-01-29 Sound insulation wall and cleaning method for sound insulation wall
JP2002244772A Pending JP2003113345A (en) 1995-12-22 2002-08-26 Antistatic coating composition

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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
JPH09230105A (en) * 1995-12-22 1997-09-05 Toto Ltd Antifogging method and facility applied with the method
JPH09227779A (en) * 1995-12-22 1997-09-02 Toto Ltd Rubber member for construction and impartment of hydrophilicity to surface thereof
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance
JPH09186949A (en) * 1995-12-27 1997-07-15 Toshiba Lighting & Technol Corp Video equipment
JP3400259B2 (en) * 1996-08-26 2003-04-28 セントラル硝子株式会社 Hydrophilic coating and method for producing the same
JP3949788B2 (en) * 1996-09-17 2007-07-25 大野 隆司 Goods storage container
JP4305001B2 (en) * 1996-09-20 2009-07-29 株式会社日立製作所 Articles with a photocatalytic film
CN1254365C (en) * 1996-09-20 2006-05-03 株式会社日立制作所 Thin photocatalytic film and articles provided with the same
JPH10148705A (en) * 1996-11-21 1998-06-02 Hitachi Chem Co Ltd Antifog treatment
JP3467994B2 (en) * 1996-11-27 2003-11-17 松下電工株式会社 Silicone transfer film and transfer structure thereof
JPH10237352A (en) * 1997-02-24 1998-09-08 Tao:Kk Polyfunctional coating agent
JP4672822B2 (en) * 1997-02-24 2011-04-20 株式会社ティオテクノ Hydrophilic coating agent and surface hydrophilic substrate
JP3518251B2 (en) * 1997-05-20 2004-04-12 株式会社日立製作所 Oxide photocatalytic thin film and article provided with the same
JPH1190236A (en) * 1997-09-22 1999-04-06 Ebara Corp Photocatalyst and reaction device using photocatalyst
JPH11100695A (en) * 1997-09-26 1999-04-13 Nippon Alum Co Ltd Production of titanium material having photocatalytic activity
JPH11100526A (en) * 1997-09-29 1999-04-13 Toto Ltd Photocatalytic hydrophilic member and photocatalytic hydrophilic coating composition
JP3996682B2 (en) * 1997-10-20 2007-10-24 日本デコール株式会社 Decorative sheet having organic substance decomposing function and method for producing the same
JPH11152447A (en) * 1997-11-21 1999-06-08 Toto Ltd Surface-treating agent for forming photocatalyzing coating film, and formation of photocatalyzing coating film using the surface-treating agent
KR100740055B1 (en) * 1997-12-25 2007-10-18 산젠 가꼬 가부시키가이샤 Anti-fogging laminates
JPH11197516A (en) * 1998-01-09 1999-07-27 Takenaka Komuten Co Ltd Photocatalyst material and its production
WO1999041322A1 (en) * 1998-02-10 1999-08-19 Toto Ltd. Coating material for forming photocatalytic hydrophilic film, method of forming photocatalytic hydrophilic film, and photocatalytic hydrophilic member
JPH11263950A (en) * 1998-03-16 1999-09-28 Nippon Carbide Ind Co Inc Transparent adhesive sheet for preventing dew condensation and dew condensation-preventing deflective sign
WO1999052983A1 (en) * 1998-04-10 1999-10-21 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
WO2000046154A1 (en) * 1999-02-04 2000-08-10 Japan Science And Technology Corporation Process for producing anatase titania or composite oxide containing anatase titania
JP2000234892A (en) * 1999-02-12 2000-08-29 Zexel Corp Method for reducing heat exchanger and heat exchanger manufactured by that method
WO2000053689A1 (en) * 1999-03-09 2000-09-14 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
DE60001764T2 (en) 1999-05-21 2003-11-13 Jsr Corp Coating agents and films and glass coated with them
FR2794225B3 (en) * 1999-05-25 2001-06-15 Saint Gobain Vitrage REFRIGERATED ENCLOSURE DOOR WITH VACUUM WINDOWS
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
JP4513141B2 (en) * 1999-06-21 2010-07-28 パナソニック株式会社 air purifier
JP4507302B2 (en) * 1999-08-10 2010-07-21 凸版印刷株式会社 High refractive index composition
EP1081108B1 (en) 1999-09-02 2004-02-25 Central Glass Company, Limited Article with photocatalytic film
JP2001080974A (en) * 1999-09-08 2001-03-27 Fuji Photo Film Co Ltd Composite base plate material and method for producing the same
WO2001025362A1 (en) * 1999-10-01 2001-04-12 Nippon Soda Co., Ltd. Sheet for transferring photocatalyst
JP2001164117A (en) * 1999-12-07 2001-06-19 Toppan Printing Co Ltd High-refractive-index composition and antireflection laminate
TW468053B (en) * 1999-12-14 2001-12-11 Nissan Chemical Ind Ltd Antireflection film, process for forming the antireflection film, and antireflection glass
EP1167953A4 (en) 2000-02-07 2003-07-09 Organo Corp 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
WO2002064877A2 (en) 2001-01-30 2002-08-22 The Procter & Gamble Company Coating compositions for modifying surfaces
WO2002074451A1 (en) * 2001-03-21 2002-09-26 Bridgestone Corporation Method for forming antifouling coating and antifouling material having antifouling coating
JP2002285036A (en) * 2001-03-23 2002-10-03 Seiichi Rengakuji Photocatalyst supported aluminum material and its manufacturing method
KR100393733B1 (en) * 2001-03-28 2003-08-06 홍국선 Ceramic Compositions for superhydrophilic coating and its manufacturing method
US6827966B2 (en) * 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
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
DE60307053T2 (en) * 2002-02-14 2007-02-15 Lg Electronics Inc. DOOR FOR WASHING MACHINE AND METHOD FOR THE PRODUCTION THEREOF
US6938546B2 (en) 2002-04-26 2005-09-06 Mitsubishi Heavy Industries, Ltd. Printing press, layered formation and making method thereof, and printing plate and making method thereof
US7211543B2 (en) 2002-06-03 2007-05-01 Asahi Kasei Kabushiki Kaisha 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
US8268340B2 (en) 2002-09-26 2012-09-18 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
AU2003272710B2 (en) 2002-09-26 2008-05-15 Vactronix Scientific, Llc 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
CA2575586A1 (en) * 2004-08-10 2006-02-23 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
CA2580774C (en) 2004-09-20 2013-12-03 Afg Industries, 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
CN101120055B (en) * 2005-02-18 2014-07-23 日本曹达株式会社 Organic-inorganic composite body
US7722923B2 (en) 2005-02-24 2010-05-25 Central Research Institute Of Electric Power Industry Process for producing multifunctional material
WO2006090631A1 (en) 2005-02-24 2006-08-31 Central Research Institute Of Electric Power Industry 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
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
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
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
JP4480014B2 (en) * 2005-02-28 2010-06-16 財団法人電力中央研究所 Rocket parts
JP4843231B2 (en) * 2005-02-28 2011-12-21 財団法人電力中央研究所 Kitchen products
JP4541929B2 (en) * 2005-02-28 2010-09-08 財団法人電力中央研究所 Flying object
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
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
JP2006247760A (en) * 2005-03-08 2006-09-21 Disco Abrasive Syst Ltd Machining apparatus
TW200631899A (en) 2005-03-09 2006-09-16 Tokai Ryokaku Tetsudo Kk Titanium oxide-coating agent, and forming method for titanium oxide-coating film
JP4659494B2 (en) * 2005-03-23 2011-03-30 株式会社ミクニ Infrared transmitting window material, infrared sensor unit, and combustion apparatus
US7757629B2 (en) * 2005-04-14 2010-07-20 Transitions Optical, Inc. Method and apparatus for coating an optical article
KR100796718B1 (en) * 2005-08-10 2008-01-21 요시노리 나카가와 Method for manufacturing photoelectro-chemical cell and photoelectro-chemical cell
JP3795515B1 (en) 2005-08-10 2006-07-12 善典 中川 Manufacturing method of semiconductor photoelectrochemical cell
ES2397093T3 (en) * 2005-11-04 2013-03-04 Tokuyama Corporation Coating machine
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
JP2008184357A (en) * 2007-01-30 2008-08-14 National Institute Of Advanced Industrial & Technology Method of making surface of oxide amphiphilic
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
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
CN104759297B (en) 2010-07-29 2018-02-23 Toto株式会社 Object with photo-catalyst coating and photocatalyst coating liquid
US9221031B2 (en) 2010-07-29 2015-12-29 Toto Ltd. Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material
BR112013003705B1 (en) * 2010-09-28 2020-02-04 Dow Global Technologies Llc mixing duct, static mixer and method for mixing
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
WO2016017686A1 (en) 2014-07-30 2016-02-04 三菱マテリアル株式会社 Hydrophilic oil repellent agent and method for manufacturing same, and surface covering material, coating film, resin composition, oil-water separation filter medium, and porous body
CN106659948B (en) 2014-07-30 2019-08-16 三菱综合材料株式会社 Filter material, the manufacturing method of filter material, water process module and water treatment facilities
CN106574166B (en) 2014-07-30 2018-10-02 三菱综合材料株式会社 Surface covering material, coated film and hydrophilic oil repellent material
JP6461573B2 (en) 2014-07-30 2019-01-30 三菱マテリアル株式会社 Oil / water separator / collector
KR101942261B1 (en) * 2014-09-24 2019-01-28 (주)엘지하우시스 Visible light active photocatalyst tile
KR101642870B1 (en) * 2014-10-21 2016-08-29 가천대학교 산학협력단 Endoscope
JP2016104681A (en) * 2014-12-01 2016-06-09 大日本印刷株式会社 Method for producing laminated glass, and laminated glass
WO2016136395A1 (en) 2015-02-27 2016-09-01 富士フイルム株式会社 Gas separation asymmetric membrane, gas separation module, gas separation device, and gas separation method
CN106580154B (en) * 2015-03-18 2018-11-27 杭州桑莱特卫浴有限公司 The production method of bathroom cabinet and bathroom cabinet
CN104848985B (en) * 2015-06-05 2017-03-08 合肥工业大学 A kind of vacuum detecting method based on infrared laser spectroscopy and system
WO2017022075A1 (en) * 2015-08-04 2017-02-09 三菱電機株式会社 Elevator car panel
JP2017090380A (en) * 2015-11-16 2017-05-25 株式会社デンソーウェーブ Laser radar device, window member for laser radar device, and control program for laser radar device
CN105349042A (en) * 2015-11-20 2016-02-24 杨京广 Silicon carbide coating and use method thereof
CN105444486A (en) * 2015-12-31 2016-03-30 广西路桥工程集团有限公司 Multi-way valve circulation system for cooling system
JP6811415B2 (en) * 2016-01-29 2021-01-13 パナソニックIpマネジメント株式会社 urinal
JP2017165612A (en) * 2016-03-16 2017-09-21 Towa株式会社 Translucent material, low adhesion material and molding member
CN105694688B (en) * 2016-03-16 2017-09-26 曲阜师范大学 A kind of fast preparation method of high intensity super-hydrophobic coat
CN107313490A (en) * 2016-04-26 2017-11-03 厦门致杰智能科技有限公司 A kind of Split intelligent toilet seat
CN105860692A (en) * 2016-04-29 2016-08-17 南京晨光艺术工程有限公司 Self-cleaning Buddha statue
CN106242314A (en) * 2016-08-23 2016-12-21 张洪建 A kind of glass copper-plating technique
CN108261086A (en) * 2017-01-03 2018-07-10 佛山市顺德区美的电热电器制造有限公司 The preparation method of Anti-fog mirror, cooking apparatus and Anti-fog mirror
JP6814473B2 (en) * 2017-02-28 2021-01-20 国立大学法人東北大学 Photocatalytic functional member and its manufacturing method
JP6428864B2 (en) * 2017-07-03 2018-11-28 大日本印刷株式会社 Transparent film and method for producing the same
KR102138411B1 (en) * 2017-07-07 2020-07-27 주식회사 엘지화학 Coating composition including the same, organic light emitting device using the same and method of manufacturing the same
JP2019070247A (en) * 2017-10-06 2019-05-09 スリーエム イノベイティブ プロパティズ カンパニー Window film
MX2019000869A (en) 2018-01-30 2019-12-19 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
JP2019158247A (en) * 2018-03-14 2019-09-19 株式会社デンソー Heat exchanger
CN110157224A (en) * 2018-03-14 2019-08-23 成都今天化工有限公司 A method of preparing nano ceramics anti-pollution flashover coating
PL425045A1 (en) * 2018-03-28 2019-10-07 Uniwersytet Jagielloński Method for producing nanoporous semiconducting layers of metal oxides
KR101917149B1 (en) 2018-05-17 2018-11-09 주식회사 대수하이테크 Anti-fouling coating composition having excellent weatherability
JP7086744B2 (en) * 2018-06-22 2022-06-20 株式会社東芝 Camera system
JP7329909B2 (en) * 2018-06-28 2023-08-21 小林製薬株式会社 Coating agent for toilet bowl
JP2020069684A (en) * 2018-10-30 2020-05-07 三井化学株式会社 Multilayer structure
JP7290938B2 (en) * 2018-12-11 2023-06-14 イビデン株式会社 Manufacturing method of cover for infrared detection element
JP2020106751A (en) * 2018-12-28 2020-07-09 ホヤ レンズ タイランド リミテッドHOYA Lens Thailand Ltd Spectacle lens
CN109667139B (en) * 2018-12-31 2021-06-29 盐城工学院 Anti-ultraviolet self-cleaning composition and preparation method and application thereof
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
CN116235016A (en) 2020-10-21 2023-06-06 三菱电机株式会社 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
JPH09129012A (en) * 1995-03-31 1997-05-16 Toshiba Lighting & Technol Corp Photocatalyst, fluorescent lamp and luminaire
JPH08277147A (en) * 1995-03-31 1996-10-22 Nippon Muki Co Ltd Plate glass
JP3101537B2 (en) * 1995-05-10 2000-10-23 ワイケイケイ株式会社 Antifouling building material and exterior building material unit
JPH0929103A (en) * 1995-05-17 1997-02-04 Toshiba Lighting & Technol Corp Photocatalytic body, photocatalytic device, light source and lightening equipment
JPH08313705A (en) * 1995-05-22 1996-11-29 Seiko Epson Corp Anti-clouding article and its production
JP3127827B2 (en) * 1995-06-14 2001-01-29 東陶機器株式会社 Anti-fog seal
CN1081490C (en) * 1995-06-19 2002-03-27 日本曹达株式会社 Photocatalyst-carrying structure and photocatalyst coating material
JPH0990889A (en) * 1995-09-27 1997-04-04 Toshiba Lighting & Technol Corp Sign body and externally illuminated sign device
JPH09173783A (en) * 1995-10-27 1997-07-08 Matsushita Electric Ind Co Ltd Sheet glass and resin plate and their production and method for removing contaminant
JP4237830B2 (en) * 1995-12-20 2009-03-11 日本曹達株式会社 Photocatalyst-carrying lighting fixture
JPH09231821A (en) * 1995-12-22 1997-09-05 Toto Ltd Luminaire and method for maintaining illuminance

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JPH09229585A (en) 1997-09-05
JPH09225021A (en) 1997-09-02
JPH09224957A (en) 1997-09-02
JP2002302646A (en) 2002-10-18
JP3588206B2 (en) 2004-11-10
JPH09241038A (en) 1997-09-16
JPH09229767A (en) 1997-09-05
JPH09230493A (en) 1997-09-05
JPH09225389A (en) 1997-09-02
JP2003113345A (en) 2003-04-18
JPH09227178A (en) 1997-09-02
JP3613085B2 (en) 2005-01-26
JPH09224960A (en) 1997-09-02
JP3075195B2 (en) 2000-08-07
JP3414367B2 (en) 2003-06-09
JPH09231821A (en) 1997-09-05
JPH09227161A (en) 1997-09-02
JP3339304B2 (en) 2002-10-28
JPH09226531A (en) 1997-09-02
JPH09227159A (en) 1997-09-02
JPH09231807A (en) 1997-09-05
JP3774955B2 (en) 2006-05-17
JP2001049828A (en) 2001-02-20
JP3003593B2 (en) 2000-01-31
JPH09226060A (en) 1997-09-02
JP3141802B2 (en) 2001-03-07
JPH09225276A (en) 1997-09-02
JPH09225396A (en) 1997-09-02
JP3465664B2 (en) 2003-11-10
JP3743075B2 (en) 2006-02-08
JPH09230108A (en) 1997-09-05
JPH09231849A (en) 1997-09-05
JPH09225388A (en) 1997-09-02
JP2001048679A (en) 2001-02-20
JP3588202B2 (en) 2004-11-10
JP3063968B2 (en) 2000-07-12
JPH09231499A (en) 1997-09-05
JP2001122679A (en) 2001-05-08
JPH09226042A (en) 1997-09-02
JPH09228057A (en) 1997-09-02
JPH09225054A (en) 1997-09-02
JP3385850B2 (en) 2003-03-10
JPH09226041A (en) 1997-09-02
JPH09228602A (en) 1997-09-02
JPH09230796A (en) 1997-09-05
JPH09229724A (en) 1997-09-05
JP2000136370A (en) 2000-05-16
JPH09227162A (en) 1997-09-02
JP2002030258A (en) 2002-01-31
JPH09225263A (en) 1997-09-02
JP3003581B2 (en) 2000-01-31
JP3588205B2 (en) 2004-11-10
JPH09230031A (en) 1997-09-05
JPH09225387A (en) 1997-09-02
JPH09226040A (en) 1997-09-02
JPH09227169A (en) 1997-09-02
JPH09224793A (en) 1997-09-02
JPH09230810A (en) 1997-09-05
JPH09230106A (en) 1997-09-05
JP2001089752A (en) 2001-04-03
JP3303696B2 (en) 2002-07-22
JP3740736B2 (en) 2006-02-01
JPH09228022A (en) 1997-09-02
JP3348613B2 (en) 2002-11-20
JPH09227156A (en) 1997-09-02
JP3612896B2 (en) 2005-01-19
JP3882625B2 (en) 2007-02-21
JPH09228320A (en) 1997-09-02
JPH09227805A (en) 1997-09-02
JPH09227160A (en) 1997-09-02
JPH09228332A (en) 1997-09-02
JPH09228765A (en) 1997-09-02
JPH09228134A (en) 1997-09-02
JP3189682B2 (en) 2001-07-16

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