JPH09230493A - Camera - Google Patents
CameraInfo
- Publication number
- JPH09230493A JPH09230493A JP8246180A JP24618096A JPH09230493A JP H09230493 A JPH09230493 A JP H09230493A JP 8246180 A JP8246180 A JP 8246180A JP 24618096 A JP24618096 A JP 24618096A JP H09230493 A JPH09230493 A JP H09230493A
- Authority
- JP
- Japan
- Prior art keywords
- surface layer
- camera
- photocatalyst particles
- lens
- titania
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
- F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Landscapes
- 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)
- Illuminated Signs And Luminous Advertising (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Greenhouses (AREA)
- Joining Of Glass To Other Materials (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Panels For Use In Building Construction (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
- Bridges Or Land Bridges (AREA)
- Devices Affording Protection Of Roads Or Walls For Sound Insulation (AREA)
- Optical Radar Systems And Details Thereof (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は監視カメラ等のカバ
ーケース内にカメラ本体を収納したカメラに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a camera having a camera body housed in a cover case of a surveillance camera or the like.
【0002】[0002]
【従来の技術】店内の監視、建物への侵入者の監視、道
路の混雑状態や車両の速度の監視、トンネル内の状態の
監視に用いるカメラは、一旦設置した後はそのままの状
態で長期間使用する場合が多い。そのため、カメラ本体
の傷つき等を防止すべく、例えば全面を強化ガラスとし
たカバーケース内にカメラ本体を収納している。また、
監視カメラに限らず通常のカメラにおいても、レンズの
前方に強化ガラス製の保護カバーを設けたものがある。2. Description of the Related Art Cameras used for in-store monitoring, building intruder monitoring, road congestion and vehicle speed monitoring, and tunnel condition monitoring have been installed for a long time without any change. Often used. Therefore, in order to prevent the camera body from being scratched, for example, the camera body is housed in a cover case whose entire surface is tempered glass. Also,
Not only surveillance cameras but also ordinary cameras include those having a protective cover made of tempered glass in front of the lens.
【0003】[0003]
【発明が解決しようとする課題】監視カメラは一般的に
高所、狭所等に設置されるため、清掃が困難で降雨に晒
されたままになってしまう。その結果、前面ガラスの外
側面が汚れて見にくくなったり、湿気が多い季節には内
部に蒸気がこもり、レンズ表面や前面ガラスの内側面に
結露が生じてしまう。また、レンズの前方に保護カバー
を設けたカメラにあっても、湿気の多い場所で使用する
場合に、保護カバーの表面に結露が生じることがある。Since surveillance cameras are generally installed in high places, narrow places, etc., they are difficult to clean and remain exposed to rainfall. As a result, the outer surface of the front glass becomes dirty and hard to see, and in the humid season, vapor is accumulated inside, and dew condensation occurs on the lens surface and the inner surface of the front glass. Further, even in a camera provided with a protective cover in front of the lens, when used in a humid place, dew condensation may occur on the surface of the protective cover.
【0004】[0004]
【課題を解決するための手段】本発明者らは、酸化チタ
ン等の光触媒粒子に物品の表面を親水化(超親水化)す
る作用を有するという知見に基づいて本発明をなしたも
のである。The present inventors have made the present invention based on the finding that photocatalyst particles such as titanium oxide have a function of hydrophilizing (superhydrophilizing) the surface of an article. .
【0005】光触媒粒子の親水化作用は、今まで知られ
ていなかったが、本発明者らの実験により最近新たに知
見されたものである。その理論的根拠は完全には解明さ
れていないが、光が光触媒粒子に照射されると、光触媒
粒子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、上記極性成分の協調的な作用により、吸着表面と表
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ものと考えられる。The hydrophilizing action of the photocatalyst particles has not been known until now, but it has recently been newly discovered by the experiments of the present inventors. The rationale for this is not completely understood, but when light is applied to the photocatalyst particles, the electrons in the valence band of the photocatalyst particles are excited to generate conduction electrons and holes, and either or Both actions probably polarize the surface and collect polar components such as water and hydroxyl groups. Then, by the cooperative action of either or both of conduction electrons and holes and the polar component, the chemical bond between the adsorbed surface and the pollutant chemically adsorbed on the surface is cut, and chemisorbed water is formed on the surface. It is considered that the water is adsorbed and a physically adsorbed water layer is further formed thereon.
【0006】具体例として、表面層がSi−O結合を有
するシリコーン樹脂からなる場合を説明すると、光触媒
粒子に光を照射する前は図1(a)に示すように、Si
原子にアルキル基(R)が結合しているため、表面層は
疎水性を示すが、光触媒粒子のバンドギャップエネルギ
よりも高いエネルギの光を照射すると、図1(b)に示
すように、まず光触媒効果によってアルキル基(R)が
水酸基(OH-)に置換(化学吸着)され、更にこの水
酸基(OH-)に空気中の水分子が物理吸着して親水性
を発揮する。As a specific example, a case where the surface layer is made of a silicone resin having a Si--O bond will be described. Before the photocatalyst particles are irradiated with light, as shown in FIG.
Since the alkyl group (R) is bonded to the atom, the surface layer shows hydrophobicity. However, when light having an energy higher than the band gap energy of the photocatalyst particles is irradiated, first, as shown in FIG. alkyl group (R) by the photocatalytic effects hydroxyl - is substituted (chemisorption), further the hydroxyl (OH) - exhibit hydrophilic water molecules in the air are physically adsorbed (OH).
【0007】また、光触媒粒子として酸化チタン(Ti
O2)のみからなる場合を説明すると、光を照射する前
は図2(a)に示す状態であったものが、光を照射する
と、図2(b)に示すように、空気中の水分を構成する
水酸基(OH-)がTi原子に、水素原子(H+)が酸素
原子(O)に化学吸着し、更にこの水酸基(OH-)や
水素原子(H+)に空気中の水分子が物理吸着して親水
性を発揮する。In addition, titanium oxide (Ti
O 2 ) will be described. The state shown in FIG. 2A before the light irradiation is changed to the state shown in FIG. 2A when the light is irradiated, as shown in FIG. 2B. hydroxyl group constituting the (OH -) is a Ti atom, a hydrogen atom (H +) is chemically adsorbed to the oxygen atom (O), further the hydroxyl - water molecules and in the air a hydrogen atom (H +) (OH) Exerts hydrophilicity by physical adsorption.
【0008】上記の説明で、物質の分解作用と親水化作
用とは全く別のものであることが明らかであるが、具体
的事例を示せば、TiO2でもアナターゼ型のTiO2は酸
化還元反応に基づく物質の分解作用を示すがルチル型の
TiO2は殆ど酸化還元反応に基づく物質の分解作用を示
さない。また光触媒のうちでも酸化錫も酸化還元反応に
基づく物質の分解作用を示さない。これらの光触媒粒子
は伝導帯のエネルギ準位が十分に高くないため還元反応
が進行せず、その結果、伝導帯に光励起された電子が過
剰となり、光励起により生じた電子−正孔対が酸化還元
反応に関与せずに再結合するためと考えられている。し
かしながら、これらルチル型TiO2及び酸化錫のいずれ
も親水化作用は示す。[0008] In the above description, it is apparent that the decomposition and hydrophilization effect of a substance is completely different, if Shimese concrete examples, TiO 2 anatase even TiO 2 oxidation-reduction reaction However, rutile-type TiO 2 shows almost no decomposition action of the substance based on the redox reaction. Also, among the photocatalysts, tin oxide does not show a decomposition effect of a substance based on a redox reaction. In these photocatalyst particles, the energy level of the conduction band is not sufficiently high, so that the reduction reaction does not proceed. As a result, the electrons excited by the photoexcitation in the conduction band become excessive, and the electron-hole pairs generated by the photoexcitation are oxidized and reduced. It is believed that they recombine without participating in the reaction. However, both rutile TiO 2 and tin oxide exhibit a hydrophilizing action.
【0009】また、物質の分解作用を発揮するには、光
触媒層の厚みとして少なくとも100nm以上必要であ
ったが、親水化作用をを発揮するには、数nm以上あれ
ば可能である。これらの事実から光触媒による物質の分
解作用と親水化作用とは全く別のものであると言える。Further, the thickness of the photocatalyst layer needs to be at least 100 nm or more in order to exert the decomposing action of the substance, but it may be several nm or more in order to exert the hydrophilizing action. From these facts, it can be said that the decomposition action of the substance by the photocatalyst and the hydrophilization action are completely different.
【0010】本発明は以上の知見に基づき、従来の課題
を解決すべくなしたものであり、本願の第1発明に係る
カメラは、カバーケース内にカメラ本体を収納してなる
カメラであって、前記カバーケースの外側面または内側
面若しくはレンズの表面に、光触媒粒子単独からなる表
面層または光触媒粒子を含む表面層を形成した。The present invention has been made to solve the conventional problems based on the above knowledge, and a camera according to the first invention of the present application is a camera in which a camera body is housed in a cover case. A surface layer consisting of photocatalyst particles alone or a surface layer containing photocatalyst particles was formed on the outer surface or inner surface of the cover case or the surface of the lens.
【0011】また、本願の第2発明に係るカメラは、レ
ンズの前方に設けた保護カバーの外側面または内側面若
しくはレンズの表面に、光触媒粒子単独からなる表面層
または光触媒粒子を含む表面層を形成した。In the camera according to the second aspect of the present invention, a surface layer made of only photocatalyst particles or a surface layer containing photocatalyst particles is provided on the outer or inner surface of the protective cover provided in front of the lens or the surface of the lens. Formed.
【0012】光触媒粒子単独からなる表面層または光触
媒粒子を含む表面層は、紫外線を照射されることで親水
性を呈し、自浄効果、防曇効果等を発揮する。これらの
効果を効果的に発揮するには、表面の親水性が水との接
触角に換算して10°以下となるようにすることが好ま
しい。表面に水との接触角が10°以下の親水性を付与
すると、部材表面に付着した水滴は瞬間的に表面全体に
広がる。The surface layer consisting of the photocatalyst particles alone or the surface layer containing the photocatalyst particles exhibits hydrophilicity by being irradiated with ultraviolet rays and exhibits a self-cleaning effect, an antifogging effect and the like. In order to effectively exhibit these effects, it is preferable that the hydrophilicity of the surface be 10 ° or less in terms of the contact angle with water. When the surface is made hydrophilic so that the contact angle with water is 10 ° or less, the water droplets attached to the surface of the member instantaneously spread over the entire surface.
【0013】前記光触媒粒子としては、アナターゼ型、
ルチル型等の結晶性酸化チタンが好ましいが、光触媒粒
子としては、この他にも、ZnO、SnO2、SrTiO3、
WO3、Bi2O3、Fe2O3などの金属酸化物が挙げられ
る。また、表面層を光触媒粒子単独で構成しない場合に
は、光触媒粒子の他に、シリカやシリコーンを含むこと
が好ましい。シリコーンは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ることで親水性
を発揮する。The photocatalyst particles are anatase type,
Rutile-type crystalline titanium oxide is preferable, but other photocatalyst particles include ZnO, SnO 2 , SrTiO 3 , and
Examples thereof include metal oxides such as WO 3 , Bi 2 O 3 and Fe 2 O 3 . Further, when the surface layer is not composed of the photocatalyst particles alone, it is preferable to contain silica or silicone in addition to the photocatalyst particles. Silicone exhibits hydrophilicity by substituting at least a part of organic groups bonded to silicon atoms with hydroxyl groups.
【0014】光触媒粒子を含有する親水性の表面層を形
成方法として、チタニア(酸化チタン)を例にとって説
明すると、無定形チタニアの形成、シリカ配合チタニア
の塗布、酸化錫配合チタニアの塗布、チタニア含有シリ
コーン塗料の塗布等が挙げられる。Titania (titanium oxide) will be described as an example of a method of forming a hydrophilic surface layer containing photocatalyst particles. The formation of amorphous titania, the application of silica-containing titania, the application of tin oxide-containing titania, the application of titania-containing Application of a silicone paint and the like can be mentioned.
【0015】無定形チタニアの形成は、先ず被塗装面を
無定形チタニアで被覆し、これを焼成して結晶性チタニ
アに相変化させる方法であり、次のいずれかの方法を採
用することができる。 (1)有機チタン化合物の加水分解と脱水縮重合 チタンのアルコキシド、例えば、テトラエトキシチタ
ン、テトライソプロポキシチタン、テトラn−プロポキ
シチタン、テトラブトキシチタン、テトラメトキシチタ
ン、に塩酸またはエチルアミンのような加水分解抑制剤
を添加し、エタノールやプロパノールのようなアルコー
ルで希釈した後、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、混合物を塗布し、常
温から200℃の温度で乾燥させる。乾燥により、チタ
ンのアルコキシド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チタニ
アの層が形成される。チタンのアルコキシドに代えて、
チタンのキレート又はチタンのアセテートのような他の
有機チタン化合物を用いてもよい。 (2)無機チタン化合物による無定形チタニアの形成 無機チタン化合物、例えば、TiCl4またはTi(S
O4)2の酸性水溶液を塗布し、100〜200℃の温度
で乾燥させることにより加水分解と脱水縮重合を行い、
無定形チタニアの層を形成する。或いはTiCl4の化学
蒸着により被塗装面に無定形チタニアの層を形成しても
よい。 (3)スパッタリングによる無定形チタニアの形成 金属チタンのターゲットに酸化雰囲気で電子ビームを照
射することにより、被塗装面に無定形チタニアの層を形
成する。The formation of amorphous titania is a method in which a surface to be coated is first coated with amorphous titania, which is baked to change the phase to crystalline titania, and any of the following methods can be employed. . (1) Hydrolysis and dehydration condensation polymerization of an organic titanium compound An alkoxide of titanium, for example, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, or a hydrochloride such as hydrochloric acid or ethylamine After adding a decomposition inhibitor and diluting with an alcohol such as ethanol or propanol, the mixture is applied after partially or completely promoting the hydrolysis, and then the mixture is applied, and the temperature is from room temperature to 200 ° C. And dry. By drying, the hydrolysis of the alkoxide of titanium is completed to form titanium hydroxide, and a layer of amorphous titania is formed by dehydration-condensation polymerization of titanium hydroxide. Instead of titanium alkoxide,
Other organic titanium compounds such as titanium chelates or titanium acetate may be used. (2) Formation of amorphous titania by inorganic titanium compound Inorganic titanium compound such as TiCl 4 or Ti (S
Hydrolysis and dehydration polycondensation are performed by applying an acidic aqueous solution of O 4 ) 2 and drying at a temperature of 100 to 200 ° C.
Form a layer of amorphous titania. Or it may form a layer of amorphous titania on the surface to be coated by chemical vapor deposition of TiCl 4. (3) Formation of amorphous titania by sputtering A target of metal titanium is irradiated with an electron beam in an oxidizing atmosphere to form a layer of amorphous titania on the surface to be coated.
【0016】シリカ配合チタニアの塗布は、チタニアと
シリカとの混合物からなる層を被塗装面に形成すること
である。チタニアとシリカの合計に対するシリカの割合
は、5〜90モル%、好ましくは10〜70モル%、よ
り好ましくは10〜50モル%である。またシリカ配合
チタニアからなる表面層の形成方法には以下の方法を採
用することができる。 (1)アナターゼ型又はルチル型チタニアの粒子とシリ
カの粒子を含む懸濁液を被塗装面に塗布し、基材(被塗
装物)の軟化点以下の温度で焼成する。 (2)無定形シリカの前駆体(例えば、テトラエトキシ
チタン、テトライソプロポキシチタン、テトラn−プロ
ポキシチタン、テトラブトキシチタン、テトラメトキシ
チタン、等のテトラアルコキシシラン)と結晶性チタニ
アゾルとの混合物を基材の表面に塗布し、必要に応じて
加水分解させてシラノールを形成した後、約100℃以
上の温度で加熱してシラノールを脱水縮重合に付すこと
により、チタニアが無定形シリカで結着された表面層
(光触媒コーティング)を得る。特に、シラノールの脱
水縮重合を約200℃以上の温度で行えば、シラノール
の重合度を増し、光触媒コーティングの耐アルカリ性能
を向上させることができる。 (3)無定形チタニアの前駆体(チタンのアルコキシ
ド、キレート又はアセテートのような有機チタン化合
物、又はTiCl4またはTi(SO4)2のような無機チタ
ン化合物)の溶液にシリカの粒子を分散させてなる懸濁
液を基材の表面に塗布し、チタン化合物を常温から20
0℃の温度で加水分解と脱水縮重合に付すことにより、
シリカ粒子が分散された無定形チタニアの薄膜を形成す
る。次いで、チタニアの結晶化温度以上の温度、且つ基
材の軟化点以下の温度に加熱することにより、無定形チ
タニアを結晶性チタニアに相変化させる。 (4)無定形チタニアの前駆体(チタンのアルコキシ
ド、キレート又はアセテートのような有機チタン化合
物、又はTiCl4またはTi(SO4)2のような無機チタ
ン化合物)の溶液に無定形シリカの前駆体(例えば、テ
トラエトキシチタン、テトライソプロポキシチタン、テ
トラn−プロポキシチタン、テトラブトキシチタン、テ
トラメトキシチタン、等のテトラアルコキシシラン、そ
れらの加水分解物であるシラノール、または平均分子量
3000以下のポリシロキサン)を混合し、基材の表面
に塗布する。次いで、これらの前駆体を加水分解と脱水
縮重合に付すことにより、無定形チタニアと無定形シリ
カの混合物からなる薄膜を形成する。次いで、チタニア
の結晶化温度以上の温度、且つ基材の軟化点以下の温度
に加熱することにより、無定形チタニアを結晶性チタニ
アに相変化させる。The application of the silica-containing titania is to form a layer made of a mixture of titania and silica on the surface to be coated. The ratio of silica to the total of titania and silica is 5 to 90 mol%, preferably 10 to 70 mol%, more preferably 10 to 50 mol%. The following method can be employed for forming the surface layer made of silica-containing titania. (1) A suspension containing particles of anatase type or rutile type titania and particles of silica is applied to a surface to be coated, and fired at a temperature equal to or lower than the softening point of the substrate (object to be coated). (2) Based on a mixture of a precursor of amorphous silica (for example, tetraalkoxysilane such as tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, etc.) and crystalline titania sol After applying to the surface of the material and hydrolyzing it as necessary to form silanol, heating at a temperature of about 100 ° C. or more and subjecting the silanol to dehydration polycondensation, the titania is bound with amorphous silica. Obtained surface layer (photocatalytic coating). In particular, if the dehydration condensation polymerization of silanol is performed at a temperature of about 200 ° C. or higher, the degree of polymerization of silanol can be increased, and the alkali resistance performance of the photocatalytic coating can be improved. (3) Dispersing silica particles in a solution of amorphous titania precursor (organic titanium compound such as alkoxide, chelate or acetate of titanium, or inorganic titanium compound such as TiCl 4 or Ti (SO 4 ) 2 ) Is applied to the surface of the base material, and the titanium compound is cooled to room temperature for 20 minutes.
By subjecting it to hydrolysis and dehydration polycondensation at a temperature of 0 ° C.,
A thin film of amorphous titania in which silica particles are dispersed is formed. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate. (4) Amorphous titania precursor (organic titanium compound such as alkoxide, chelate or acetate of titanium, or inorganic titanium compound such as TiCl 4 or Ti (SO 4 ) 2 ) in a solution of amorphous titania precursor (For example, tetraalkoxysilanes such as tetraethoxytitanium, tetraisopropoxytitanium, tetran-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, etc., silanols which are hydrolysates thereof, or polysiloxanes having an average molecular weight of 3000 or less) And apply to the surface of the substrate. Next, these precursors are subjected to hydrolysis and dehydration condensation polymerization to form a thin film composed of a mixture of amorphous titania and amorphous silica. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate.
【0017】酸化錫配合チタニアの塗布は、チタニアと
酸化錫との混合物からなる層を被塗装面に形成すること
である。チタニアと酸化錫との合計に対する酸化錫の割
合は、1〜95モル%、好ましくは1〜50モル%であ
る。また酸化錫配合チタニアからなる表面層の形成方法
には以下の方法を採用することができる。 (1)アナターゼ型又はルチル型チタニアの粒子と酸化
錫の粒子を含む懸濁液を被塗装面に塗布し、基材(被塗
装物)の軟化点以下の温度で焼成する。 (2)無定形チタニアの前駆体(チタンのアルコキシ
ド、キレート又はアセテートのような有機チタン化合
物、又はTiCl4またはTi(SO4)2のような無機チタ
ン化合物)の溶液に酸化錫の粒子を分散させてなる懸濁
液を基材の表面に塗布し、チタン化合物を常温から20
0℃の温度で加水分解と脱水縮重合に付すことにより、
酸化錫粒子が分散された無定形チタニアの薄膜を形成す
る。次いで、チタニアの結晶化温度以上の温度、且つ基
材の軟化点以下の温度に加熱することにより、無定形チ
タニアを結晶性チタニアに相変化させる。The application of the tin oxide-containing titania is to form a layer made of a mixture of titania and tin oxide on the surface to be coated. The ratio of tin oxide to the total of titania and tin oxide is 1 to 95 mol%, preferably 1 to 50 mol%. The following method can be adopted as a method for forming a surface layer made of titania mixed with tin oxide. (1) A suspension containing particles of anatase type or rutile type titania and particles of tin oxide is applied to a surface to be coated, and fired at a temperature equal to or lower than the softening point of the substrate (object to be coated). (2) Dispersion of tin oxide particles in a solution of a precursor of amorphous titania (organic titanium compound such as titanium alkoxide, chelate or acetate, or inorganic titanium compound such as TiCl 4 or Ti (SO 4 ) 2 ) The resulting suspension is applied to the surface of the substrate, and the titanium compound is heated to room temperature for 20 minutes.
By subjecting it to hydrolysis and dehydration polycondensation at a temperature of 0 ° C.,
A thin film of amorphous titania in which tin oxide particles are dispersed is formed. Next, the amorphous titania is changed into crystalline titania by heating to a temperature higher than the crystallization temperature of titania and lower than the softening point of the substrate.
【0018】チタニア含有シリコーン塗料の塗布は、未
硬化の若しくは部分的に硬化したシリコーン(オルガノ
ポリシロキサン)またはシリコーンの前駆体からなる塗
膜形成要素にチタニア(光触媒粒子)を分散させた塗料
を用いる。具体的には、上記塗料を基材の表面に塗布
し、塗膜形成要素を硬化させた後、光触媒を光励起する
と、シリコーン分子の珪素原子に結合した有機基は光触
媒の作用により水酸基に置換され、表面の水に対する接
触角が0°近くになり親水化(超親水化)される。この
方法は、比較的低温で塗膜形成要素を硬化せしめること
ができ、また必要に応じ何度でも塗布することができ、
且つ太陽光でも容易に親水化せしめることができる等の
利点がある。尚、用いる樹脂としては以下のものが挙げ
られる。メチルトリクロルシラン、メチルトリブロムシ
ラン、メチルトリメトキシシラン、メチルトリエトキシ
シラン、メチルトリイソプロポキシシラン、メチルトリ
t−ブトキシシラン、エチルトリクロルシラン、エチル
トリブロムシラン、エチルトリメトキシシラン、エチル
トリエトキシシラン、エチルトリイソプロポキシシラ
ン、エチルトリt−ブトキシシラン、n−プロピルトリ
クロルシラン、n−プロピルトリブロムシラン、n−プ
ロピルトリメトキシシラン、n−プロピルトリエトキシ
シラン、n−プロピルトリイソプロポキシシラン、n−
プロピルトリt−ブトキシシラン、n−ヘキシルトリク
ロルシラン、n−ヘキシルトリブロムシラン、n−ヘキ
シルトリメトキシシラン、n−ヘキシルトリエトキシシ
ラン、n−ヘキシルトリイソプロポキシシラン、n−ヘ
キシルトリt−ブトキシシラン、n−デシルトリクロル
シラン、n−デシルトリブロムシラン、n−デシルトリ
メトキシシラン、n−デシルトリエトキシシラン、n−
デシルトリイソプロポキシシラン、n−デシルトリt−
ブトキシシラン、n−オクタデシルトリクロルシラン、
n−オクタデシルトリブロムシラン、n−オクタデシル
トリメトキシシラン、n−オクタデシルトリエトキシシ
ラン、n−オクタデシルトリイソプロポキシシラン、n
−オクタデシルトリt−ブトキシシラン、フェニルトリ
クロルシラン、フェニルトリブロムシラン、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
ニルトリイソプロポキシシラン、フェニルトリt−ブト
キシシラン、テトラクロルシラン、テトラブロムシラ
ン、テトラメトキシシラン、テトラエトキシシラン、テ
トライソプロポキシシラン、テトラブトキシシラン、ジ
メトキシジエトキシシラン、ジメチルジクロルシラン、
ジメチルジブロムシラン、ジメチルジメトキシシラン、
ジメチルジエトキシシラン、ジフェニルジクロルシラ
ン、ジフェニルジブロムシラン、ジフェニルジメトキシ
シラン、ジフェニルジエトキシシラン、フェニルメチル
ジクロルシラン、フェニルメチルジブロムシラン、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、トリエトキシヒドロシラン、トリブロムヒド
ロシラン、トリメトキシヒドロシラン、イソプロポキシ
ヒドロシラン、トリt−ブトキシヒドロシラン、ビニル
トリクロルシラン、ビニルトリブロムシラン、ビニルト
リメトキシシラン、ビニルトリエトキシシラン、ビニル
トリイソプロポキシシラン、ビニルトリt−ブトキシシ
ラン、トリフルオロプロピルトリクロルシラン、トリフ
ルオロプロピルトリブロムシラン、トリフルオロプロピ
ルトリメトキシシラン、トリフルオロプロピルトリエト
キシシラン、トリフルオロプロピルトリイソプロポキシ
シラン、トリフルオロプロピルトリt−ブトキシシラ
ン、γ−グリシドキシプロピルメチルジメトキシシラ
ン、γ−グリシドキシプロピルメチルジエトキシシラ
ン、γ−グリシドキシプロピルトリメトキシシラン、γ
−グリシドキシプロピルトリエトキシシラン、γ−グリ
シドキシプロピルトリイソプロポキシシラン、γ−グリ
シドキシプロピルトリt−ブトキシシラン、γ−メタア
クリロキシプロピルメチルジメトキシシラン、γ−メタ
アクリロキシプロピルメチルジエトキシシラン、γ−メ
タアクリロキシプロピルトリメトキシシラン、γ−メタ
アクリロキシプロピルトリイソプロポキシシラン、γ−
メタアクリロキシプロピルトリt−ブトキシシラン、γ
−アミノプロピルメチルジメトキシシラン、γ−アミノ
プロピルメチルジエトキシシラン、γ−アミノプロピル
トリメトキシシラン、γ−アミノプロピルトリエトキシ
シラン、γ−アミノプロピルトリイソプロポキシシラ
ン、γ−アミノプロピルトリt−ブトキシシラン、γ−
メルカプトプロピルメチルジメトキシシラン、γ−メル
カプトプロピルメチルジエトキシシラン、γ−メルカプ
トプロピルトリメトキシシラン、γ−メルカプトプロピ
ルトリエトキシシラン、γ−メルカプトプロピルトリイ
ソプロポキシシラン、γ−メルカプトプロピルトリt−
ブトキシシラン、β−(3、4−エポキシシクロヘキシ
ル)エチルトリメトキシシラン、β−(3、4−エポキ
シシクロヘキシル)エチルトリエトキシシラン、及びこ
れらの部分加水分解物若しくはこれらの混合物を使用す
ることができる。The application of the titania-containing silicone paint uses a paint in which titania (photocatalyst particles) is dispersed in a film-forming element made of uncured or partially cured silicone (organopolysiloxane) or a silicone precursor. . Specifically, after the above coating material is applied to the surface of the base material, and after the film-forming element is cured, when the photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule is replaced with a hydroxyl group by the action of the photocatalyst. Then, the contact angle of the surface with water becomes close to 0 °, and the surface becomes hydrophilic (super-hydrophilic). This method can cure the film forming element at a relatively low temperature, and can be applied as many times as necessary,
In addition, there is an advantage that it can be easily made hydrophilic even by sunlight. The following resins can be used as the resin. Methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-
Propyltri-t-butoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit-butoxysilane, n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-
Decyltriisopropoxysilane, n-decyltri-t-
Butoxysilane, n-octadecyltrichlorosilane,
n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n
-Octadecyltri-t-butoxysilane, phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane, tetrachlorosilane, tetrabromosilane, tetramethoxy Silane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane,
Dimethyldibromosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, triethoxyhydrosilane , Tribromohydrosilane, trimethoxyhydrosilane, isopropoxyhydrosilane, tri-t-butoxyhydrosilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltrit-butoxysilane, Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane , Trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Xypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-
Methacryloxypropyltri-t-butoxysilane, γ
-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltrit-butoxysilane , Γ-
Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltrit-
Butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and their partial hydrolysates or mixtures thereof can be used. .
【0019】シリコーン樹脂膜の良好な硬度と平滑性を
確保するためには、3次元架橋型シロキサンを10モル
%以上含有させるのが好ましい。更に良好な硬度と平滑
性を確保しながら樹脂膜の十分な可撓性を提供するため
には、2次元架橋型シロキサンを60モル%以下含有さ
せるのが好ましい。また、シリコーン分子の珪素原子に
結合した有機基が光励起により水酸基に置換される速度
を速めるには、シリコーン分子の珪素原子に結合する有
機基がn−プロピル基若しくはフェニル基からなるシリ
コーンを使用するのが好ましい。シロキサン結合を有す
るシリコーンに替えて、シラザン結合を有するオルガノ
ポリシラザン化合物を使用することもできる。In order to ensure good hardness and smoothness of the silicone resin film, it is preferable to contain 10 mol% or more of the three-dimensionally crosslinked siloxane. In order to provide sufficient flexibility of the resin film while securing good hardness and smoothness, it is preferable to contain 60 mol% or less of the two-dimensional crosslinked siloxane. In order to increase the rate at which the organic group bonded to the silicon atom of the silicone molecule is replaced with a hydroxyl group by photoexcitation, use is made of a silicone in which the organic group bonded to the silicon atom of the silicone molecule is an n-propyl group or a phenyl group. Is preferred. An organopolysilazane compound having a silazane bond can be used instead of the silicone having a siloxane bond.
【0020】また、表面層には酸化物超強酸を含ませる
ことが可能である。酸化物超強酸としては、TiO2/W
O3、WO3/ZrO2、WO3/SnO2、Al2O3/SiO2
等が挙げられ、これら酸化物超強酸を表面層に含有せし
めると、表面の極性が光の有無に拘らず極端に大きな状
態になるため、疎水分子よりも極性分子である水分子を
選択的に吸着して物理的吸着水層を形成する。The surface layer may contain an oxide superacid. As the oxide superacid, TiO 2 / W
O 3 , WO 3 / ZrO 2 , WO 3 / SnO 2 , Al 2 O 3 / SiO 2
, Etc., and when these oxide superacids are contained in the surface layer, the polarity of the surface becomes extremely large regardless of the presence or absence of light, so that water molecules that are polar molecules are selectively selected over hydrophobic molecules. Adsorb to form a physically adsorbed water layer.
【0021】尚、室内やトンネル内等に本発明に係るカ
メラを設置する場合には、表面層に紫外線を照射する光
源を備えることが好ましい。When the camera according to the present invention is installed indoors or in a tunnel, it is preferable to provide a light source for irradiating the surface layer with ultraviolet rays.
【0022】[0022]
【発明の実施の形態】以下に本発明の実施の形態を添付
図面に基づいて説明する。図3は本発明に係るカメラの
全体斜視図であり、このカメラはカバーケース1内にカ
メラ本体2を収納してなり、カバーケース1の前面には
ガラス板3が取付けられている。Embodiments of the present invention will be described below with reference to the accompanying drawings. FIG. 3 is an overall perspective view of a camera according to the present invention. This camera has a camera body 2 housed in a cover case 1, and a glass plate 3 is attached to the front surface of the cover case 1.
【0023】ガラス板3の外側面には図4に示すよう
に、紫外線を照射することで親水性を発揮する表面層4
が形成されている。表面層4は光触媒粒子単独で形成し
てもよいが、シリカ、シリコーン樹脂或いは酸化物超強
酸とともに形成してもよい。そして、酸化物超強酸等と
ともに表面層4を形成するにあたっては、単純に光触媒
粒子と混合してもよいが、いずれか一方が上層になり、
他方が下層になるようにしてもよい。更に、表面層4は
ガラス板3の外側面ではなく、ガラス板3の内側面やカ
メラ本体2のレンズの表面、或いはカバーケース1の外
表面や内表面の全域に亘って形成してもよい。As shown in FIG. 4, the outer surface of the glass plate 3 has a surface layer 4 which exhibits hydrophilicity by being irradiated with ultraviolet rays.
Are formed. The surface layer 4 may be formed of photocatalyst particles alone, or may be formed together with silica, a silicone resin, or an oxide superacid. Then, in forming the surface layer 4 together with the oxide superacid or the like, they may be simply mixed with the photocatalyst particles, but one of them becomes the upper layer,
The other may be the lower layer. Furthermore, the surface layer 4 may be formed not on the outer surface of the glass plate 3 but on the entire inner surface of the glass plate 3, the surface of the lens of the camera body 2, or the outer surface or inner surface of the cover case 1. .
【0024】また、カバーケース1にはアーム5を設
け、このアーム5の先端に光源6を取付け、光源6から
の紫外線を表面層4に照射するようにしている。尚、光
源6はカバーケース1内に配置してもよい。An arm 5 is provided on the cover case 1, and a light source 6 is attached to the tip of the arm 5 so that the surface layer 4 is irradiated with ultraviolet rays from the light source 6. The light source 6 may be arranged inside the cover case 1.
【0025】図5は別実施例に係るカメラを示す図であ
り、この実施例にあってはカメラ本体2のレンズ7の前
方に強化ガラスからなる保護カバー8を設け、この保護
カバー8の外側面または内側面に表面層4を形成してい
る。FIG. 5 is a diagram showing a camera according to another embodiment. In this embodiment, a protective cover 8 made of tempered glass is provided in front of the lens 7 of the camera body 2, and the outside of the protective cover 8 is provided. The surface layer 4 is formed on the side surface or the inner surface.
【0026】(実験例)上記の前面ガラス板或いは保護
カバーとして用いる強化ガラスに、テトラエトキシシラ
ンを塗布し、加水分解、脱水縮重合させてシリカ層を形
成し、更にその上にテトラエトキシチタンを塗布し、加
水分解、脱水縮重合させて無定形チタニア層を形成し
た。その後、500℃で焼成することにより無定形チタ
ニアをアナターゼ型チタニアに相変化させた。この後、
BLBランプを用い、0.5mW/cm2の強度で紫外
線を1時間照射して試料を得た。(Experimental Example) Tetraethoxysilane was coated on the above-mentioned front glass plate or the tempered glass used as a protective cover, and hydrolyzed and dehydrated by polycondensation to form a silica layer, and tetraethoxytitanium was further formed thereon. After coating, hydrolysis and dehydration polycondensation were performed to form an amorphous titania layer. Then, the amorphous titania was phase-changed to anatase type titania by firing at 500 ° C. After this,
A sample was obtained by using a BLB lamp and irradiating with ultraviolet rays at an intensity of 0.5 mW / cm 2 for 1 hour.
【0027】得られた試料とチタニア層を形成していな
い通常の強化ガラスとを、水との接触角、防曇性及び防
汚性について調べた。水との接触角については、本発明
試料は0°であるのに対し、通常の強化ガラスは40°
であった。防曇性については、息を吹きかけて調べた。
結果は、本発明試料の表面には曇りは生じなかったが、
通常の強化ガラスは曇りが生じた。防汚性については、
本発明試料及び通常の強化ガラスを45°傾斜させた状
態とし、これに親水性カーボンブラックと疎水性カーボ
ンブラックを1.05g/リットル含む懸濁液を流し、これ
を乾燥させ、さらに水洗した後乾燥させるというサイク
ルを25回繰り返した後、試験前後の色差ΔE*の変化
を色差計(東京電色製)で測定(JIS H0201)
した。その結果、本発明試料はΔE*の変化値<1と良
好な防汚性を示したが、通常の強化ガラスはΔE*の変
化値>4であった。The obtained sample and a normal tempered glass having no titania layer formed were examined for contact angle with water, antifogging property and antifouling property. Regarding the contact angle with water, the sample of the present invention is 0 °, whereas the ordinary tempered glass is 40 °.
Met. The anti-fog property was examined by blowing.
As a result, no haze was generated on the surface of the sample of the present invention,
Normal tempered glass became cloudy. For antifouling property,
The sample of the present invention and ordinary tempered glass were tilted at 45 °, and a suspension containing hydrophilic carbon black and hydrophobic carbon black at 1.05 g / l was poured into the sample, dried, and washed with water. After repeating the drying cycle 25 times, the change in color difference ΔE * before and after the test was measured with a color difference meter (manufactured by Tokyo Denshoku) (JIS H0201).
did. As a result, the sample of the present invention showed a good change in ΔE * of <1 and good antifouling property, whereas the ordinary tempered glass had a change of ΔE * of> 4.
【0028】[0028]
【発明の効果】以上に説明した如く本発明によれば、監
視カメラ等のカバーケースの内側面又はカバーケース内
に収納されているレンズの表面に、酸化チタン等の光触
媒粒子単独からなる表面層または光触媒粒子を含む表面
層を形成したので、カバーケース内の湿度が高くなって
も、カバーケースの内側面及びレンズの表面には薄い水
膜が形成されるので曇りや結露が生じ難くなる。As described above, according to the present invention, a surface layer composed of photocatalyst particles such as titanium oxide alone is formed on the inner surface of a cover case of a surveillance camera or the surface of a lens housed in the cover case. Alternatively, since the surface layer containing the photocatalyst particles is formed, a thin water film is formed on the inner surface of the cover case and the surface of the lens even if the humidity in the cover case is high, so that fogging and dew condensation hardly occur.
【0029】また本発明によれば、監視カメラ等のカバ
ーケースの外側面に、光触媒粒子単独からなる表面層ま
たは光触媒粒子を含む表面層を形成したので、降雨の際
に自浄作用によってカバーケースに付着した汚れを落と
すことができるので、長期間メンテナンスフリーで使用
することができる。更に、トンネル内等の降雨等のない
箇所に設置されるカメラに対しても、ホースで水をかけ
るだけで簡単に洗うことができる。尚、カバーケース内
等に紫外線を照射する光源を設ければ、太陽光が照射さ
れない場所に設置しても蒸気の自浄効果を発揮すること
ができる。Further, according to the present invention, since the surface layer composed of the photocatalyst particles alone or the surface layer containing the photocatalyst particles is formed on the outer surface of the cover case of the surveillance camera or the like, the cover case is self-cleaning during rain. Since the adhered dirt can be removed, it can be used without maintenance for a long time. Furthermore, even a camera installed in a place where there is no rainfall, such as in a tunnel, can be easily washed by watering it with a hose. If a light source that irradiates ultraviolet rays is provided in the cover case or the like, the self-cleaning effect of steam can be exhibited even if the light source is installed in a place where sunlight is not irradiated.
【0030】また、光触媒粒子を含む表面層にシリカ、
若しくは結合する有機基の一部が水酸基に置換されたシ
リコーンを含ませることで、紫外線を照射しなくとも比
較的長期間親水性を維持できるため、暗所においてもあ
る程度の期間であれば使用することができる。Further, silica is added to the surface layer containing photocatalyst particles,
Or, by including silicone in which some of the organic groups to be bonded are substituted with hydroxyl groups, it is possible to maintain hydrophilicity for a relatively long time without irradiating ultraviolet rays, so use it for a certain period even in the dark. be able to.
【0031】また、光触媒粒子を含む表面層にTiO2/
WO3、WO3/ZrO2、WO3/SnO2、Al2O3/Si
O2などの酸化物超強酸を含ませることで、表面の極性
が光の有無に拘らず極端に大きな状態になるため、疎水
分子よりも極性分子である水分子を選択的に吸着して物
理的吸着水層を形成し、暗所でもある程度の期間親水性
を維持できる。Further, the surface layer containing the photocatalyst particles contains TiO 2 /
WO 3 , WO 3 / ZrO 2 , WO 3 / SnO 2 , Al 2 O 3 / Si
By including an oxide super strong acid such as O 2 , the polarity of the surface becomes extremely large regardless of the presence or absence of light. Therefore, water molecules, which are polar molecules, are selectively adsorbed over the hydrophobic molecules to physically A hydrophilic water layer is formed, and the hydrophilicity can be maintained for a certain period even in a dark place.
【図1】光触媒粒子を含有するシリコーン樹脂表面に親
水性が付与される過程を説明した図FIG. 1 is a diagram illustrating a process of imparting hydrophilicity to the surface of a silicone resin containing photocatalyst particles.
【図2】光触媒粒子からなる表面層に親水性が付与され
る過程を説明した図FIG. 2 is a diagram illustrating a process of imparting hydrophilicity to a surface layer made of photocatalytic particles.
【図3】本発明に係るカメラの斜視図FIG. 3 is a perspective view of a camera according to the present invention.
【図4】表面層を形成したカバーケースの断面図FIG. 4 is a sectional view of a cover case having a surface layer formed thereon.
【図5】別実施例に係るカメラを示す図FIG. 5 is a diagram showing a camera according to another embodiment.
1…カバーケース、2…カメラ本体、3…ガラス板、4
…表面層、5…アーム、6…光源。1 ... Cover case, 2 ... Camera body, 3 ... Glass plate, 4
... surface layer, 5 ... arm, 6 ... light source.
Claims (8)
なるカメラにおいて、前記カバーケースの外側面または
内側面若しくはレンズの表面に、光触媒粒子単独からな
る表面層または光触媒粒子を含む表面層が形成されてい
ることを特徴とするカメラ。1. In a camera having a camera body housed in a cover case, a surface layer comprising photocatalyst particles alone or a surface layer containing photocatalyst particles is formed on an outer surface or an inner surface of the cover case or a surface of a lens. A camera that is characterized by being.
ラにおいて、前記保護カバーの外側面または内側面若し
くはレンズの表面に、光触媒粒子単独からなる表面層ま
たは光触媒粒子を含む表面層が形成されていることを特
徴とするカメラ。2. A camera having a protective cover in front of a lens, wherein a surface layer comprising photocatalyst particles alone or a surface layer containing photocatalyst particles is formed on an outer surface or an inner surface of the protection cover or a surface of the lens. A camera characterized by being.
おいて、前記光触媒粒子は結晶性酸化チタンであること
を特徴とするカメラ。3. The camera according to claim 1 or 2, wherein the photocatalytic particles are crystalline titanium oxide.
おいて、前記光触媒粒子を含む表面層にはシリカが含ま
れていることを特徴とするカメラ。4. The camera according to claim 1, wherein the surface layer containing the photocatalyst particles contains silica.
おいて、前記光触媒粒子を含む表面層には有機基が結合
するシリコーンが含まれ、且つ前記有機基の少なくとも
一部は水酸基に置換されていることを特徴とするカメ
ラ。5. The camera according to claim 1, wherein the surface layer containing the photocatalyst particles contains a silicone to which an organic group is bonded, and at least a part of the organic group is substituted with a hydroxyl group. A camera characterized by being.
おいて、前記光触媒粒子を含む表面層には酸化物超強酸
が含まれていることを特徴とするカメラ。6. The camera according to claim 1, wherein the surface layer containing the photocatalyst particles contains a superoxide oxide.
おいて、前記カメラは建物、乗物、道路またはトンネル
内に設置される監視カメラであることを特徴とするカメ
ラ。7. The camera according to claim 1, wherein the camera is a surveillance camera installed in a building, a vehicle, a road or a tunnel.
おいて、前記光触媒粒子単独からなる表面層または光触
媒粒子を含む表面層に紫外線を照射する光源を備えてい
ることを特徴とするカメラ。8. The camera according to claim 1, further comprising a light source for irradiating the surface layer made of the photocatalyst particles alone or the surface layer containing the photocatalyst particles with ultraviolet rays.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8246180A JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP35464995 | 1995-12-22 | ||
JP7-354649 | 1995-12-22 | ||
JP8246180A JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09230493A true JPH09230493A (en) | 1997-09-05 |
Family
ID=18438979
Family Applications (71)
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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JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
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JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
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 |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog 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 |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror 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 |
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 |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
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 |
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JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
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 |
JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
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 |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
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 |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
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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JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
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JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
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 |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
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 |
Family Applications Before (27)
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 |
JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
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 |
JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
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 |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
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 |
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 |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog 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 |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror 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 |
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 |
Family Applications After (43)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
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JP (71) | JPH09231821A (en) |
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1999
- 1999-08-26 JP JP23956799A patent/JP3613084B2/en not_active Expired - Lifetime
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- 1999-12-02 JP JP34300999A patent/JP3844182B2/en not_active Expired - Fee Related
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2000
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- 2000-06-16 JP JP2000181284A patent/JP2001048679A/en active Pending
- 2000-07-27 JP JP2000227056A patent/JP2001129916A/en active Pending
- 2000-07-27 JP JP2000227055A patent/JP2001089752A/en not_active Withdrawn
- 2000-08-17 JP JP2000247609A patent/JP2001122679A/en active Pending
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2001
- 2001-05-10 JP JP2001140242A patent/JP2002030258A/en active Pending
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2002
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US7387454B2 (en) | 2004-09-22 | 2008-06-17 | Murakami Corporation | Camera |
JP2013113908A (en) * | 2011-11-25 | 2013-06-10 | Panasonic Corp | Camera cover and camera |
JP2019219627A (en) * | 2018-06-22 | 2019-12-26 | 株式会社東芝 | Camera unit |
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