JP3348613B2 - Photocatalytic hydrophilic coating composition - Google Patents
Photocatalytic hydrophilic coating compositionInfo
- Publication number
- JP3348613B2 JP3348613B2 JP34047296A JP34047296A JP3348613B2 JP 3348613 B2 JP3348613 B2 JP 3348613B2 JP 34047296 A JP34047296 A JP 34047296A JP 34047296 A JP34047296 A JP 34047296A JP 3348613 B2 JP3348613 B2 JP 3348613B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- photocatalytic
- silane
- coating
- coating composition
- 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 - Fee Related
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)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Description
【0001】[0001]
【発明の属する技術分野】本発明は、部材表面を高度の
親水性になし、かつ維持することの可能な塗膜を形成す
るための親水性コ−ティング組成物に関する。より詳し
くは、本発明は、鏡、ガラス、レンズ、プリズムその他
の透明部材の表面を高度に親水化することにより、部材
の曇りや水滴形成を防止することの可能な塗膜を形成す
るための防曇性コ−ティング組成物に関する。本発明
は、また、建物や窓ガラスや機械装置や物品の表面を高
度に親水化することにより、表面が汚れるのを防止し、
又は表面を水を用いて清浄化することの可能な塗膜を形
成するための易清浄性コ−ティング組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic coating composition for forming a coating film capable of making and maintaining the surface of a member highly hydrophilic. More specifically, the present invention provides a highly hydrophilic surface of a mirror, glass, lens, prism or other transparent member to form a coating film capable of preventing clouding and water droplet formation of the member. The present invention relates to an antifogging coating composition. The present invention also prevents the surface from being stained by highly hydrophilizing the surface of a building, a window glass, a mechanical device or an article,
Alternatively, the present invention relates to an easy-cleaning coating composition for forming a coating film whose surface can be cleaned using water.
【0002】[0002]
【従来の技術】寒冷時に自動車その他の乗物の風防ガラ
スや窓ガラス、建物の窓ガラス、眼鏡のレンズ、及び各
種計器盤のカバ−ガラスが凝縮湿分で曇るのはしばしば
経験されることである。また、浴室や洗面所の鏡や眼鏡
のレンズが湯気で曇ることも良く遭遇される。物品の表
面に曇りが生じるのは、表面が雰囲気の露点以下の温度
に置かれると雰囲気中の湿分が凝縮して表面に結露し、
水滴状に成長するからである。凝縮水滴が充分に細か
く、それらの直径が可視光の波長の1/2程度であれ
ば、水滴は光を散乱し、ガラスや鏡は見掛け上不透明と
なり、やはり可視性が失われる。湿分の凝縮が更に進行
し、細かい凝縮水滴が互いに融合してより大きな離散し
た水滴に成長すれば、水滴と表面との界面並びに水滴と
空気との界面における光の屈折により、それらの表面は
翳り、ぼやけ、斑模様になり、或いは曇る。その結果、
ガラスのような透明物品では透視像が歪んで透視性が低
下し、鏡では反射像が乱される。更に、車両の風防ガラ
スや窓ガラス、建物の窓ガラス、車両のバックミラ−、
眼鏡のレンズ、マスクやヘルメットのシ−ルドが降雨や
水しぶきを受け、離散した多数の水滴が表面に付着する
と、それらの表面は翳り、ぼやけ、斑模様になり、或い
は曇り、やはり可視性が失われる。ここで用いる“防
曇”の用語は、このような曇りや凝縮水滴の成長や水滴
の付着による光学的障害を防止する技術を広く意味す
る。言うまでもなく、上記“曇り”は安全性や種々の作
業の能率に深い影響を与える。例えば、車両の風防ガラ
スや窓ガラス、車両のバックミラ−が、寒冷時や雨天に
翳り或いは曇ると、視界の確保が困難となり、交通の安
全性が損われる。内視鏡レンズやデンタルミラ−、歯科
用レ−ザ−治療器の集束レンズが曇ると、的確な診断、
手術、処置の障害となる。計器盤のカバ−ガラスが曇る
とデ−タの読みが困難となる。BACKGROUND OF THE INVENTION It is often experienced that in cold weather, windshields and glazings of automobiles and other vehicles, glazings of buildings, lenses of eyeglasses, and cover glass of various instrument panels are fogged by condensed moisture. . In addition, mirrors and eyeglass lenses in bathrooms and washrooms are often fogged by steam. The fogging on the surface of the article is that if the surface is placed at a temperature below the dew point of the atmosphere, the moisture in the atmosphere will condense and condense on the surface,
This is because they grow like water drops. If the condensed water droplets are sufficiently fine and their diameter is about half the wavelength of visible light, the water droplets will scatter light and the glass or mirror will be apparently opaque, again losing visibility. If the condensation of moisture progresses further and the fine condensed water droplets fuse together and grow into larger discrete water droplets, their surfaces will be refracted by the refraction of light at the water droplet-surface interface and the water droplet-air interface. Dark, blurred, mottled or cloudy. as a result,
In a transparent article such as glass, the perspective image is distorted and the transparency is reduced, and the reflected image is disturbed by a mirror. Furthermore, windshields and window glasses of vehicles, window glasses of buildings, back mirrors of vehicles,
If eyeglass lenses, masks, or helmet shields are subjected to rainfall or splashes, and a large number of discrete water droplets adhere to the surface, those surfaces may become dark, blurred, mottled, or cloudy, and still lose visibility. Will be As used herein, the term "anti-fog" broadly refers to a technique for preventing optical hindrance due to such fogging, growth of condensed water droplets, and adhesion of water droplets. Needless to say, the above "clouding" has a profound effect on safety and efficiency of various operations. For example, if the windshield or window glass of the vehicle or the back mirror of the vehicle is shaded or clouded in cold weather or rainy weather, it is difficult to secure a view, and traffic safety is impaired. If the focusing lens of the endoscope lens, dental mirror, or dental laser treatment device becomes cloudy, accurate diagnosis,
It will hinder surgery and treatment. If the cover glass of the instrument panel becomes fogged, it becomes difficult to read the data.
【0003】他方、建築及び塗料の分野においては、環
境汚染に伴い、建築外装材料や屋外建造物やその塗膜の
汚れが問題となっている。大気中に浮遊する煤塵や粒子
は晴天には建物の屋根や外壁に堆積する。堆積物は降雨
に伴い雨水により流され、建物の外壁を流下する。更
に、雨天には浮遊煤塵は雨によって持ち運ばれ、建物の
外壁や屋外建造物の表面を流下する。その結果、表面に
は、雨水の道筋に沿って汚染物質が付着する。表面が乾
燥すると、表面には縞状の汚れが現れる。建築外装材料
や塗膜の汚れは、カ−ボンブラックのような燃焼生成物
や、都市煤塵や粘土粒子のような無機質物質の汚染物質
からなる。このような汚染物質の多様性が防汚対策を複
雑にしているものと考えられる(橘高義典著“外壁仕上
材料の汚染の促進試験方法”、日本建築学会構造系論文
報告集、第404号、1989年10月、p.15−2
4)。従来の通念では、上記建築外装などの汚れを防止
するためにはポリテトラフルオロエチレン(PTFE)
のような撥水性の塗料が好ましいと考えられていたが、
最近では、疎水性成分を多く含む都市煤塵に対しては、
塗膜の表面を出来るだけ親水性にするのがよいと考えら
れている(高分子、44巻、1995年5月号、p.3
07)。そこで、親水性のグラフトポリマ−で建物を塗
装することが提案されている(新聞“化学工業日報”、
1995年1月30日)。報告によれば、この塗膜は水
との接触角に換算して30〜40゜の親水性を呈する。
しかしながら、粘土鉱物で代表される無機質塵埃の水と
の接触角は20゜から50゜であり、水との接触角が3
0〜40゜のグラフトポリマ−に対して親和性を有し、
その表面に付着しやすいので、このグラフトポリマ−の
塗膜は無機質塵埃による汚れを防止することができない
と考えられる。On the other hand, in the field of construction and paints, stains on building exterior materials, outdoor buildings and their coatings have become a problem with environmental pollution. Dust and particles suspended in the air accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater as it rains and flows down the building's outer walls. Furthermore, in the rain, the floating dust is carried by the rain and flows down on the outer wall of the building or the surface of the outdoor building. As a result, pollutants adhere to the surface along the path of rainwater. When the surface dries, striped stains appear on the surface. Soil on building exterior materials and coatings consists of combustion products such as carbon black and inorganic contaminants such as urban dust and clay particles. It is considered that the diversity of such contaminants complicates antifouling measures (Yoshinori Tachibana, "Method of Accelerated Testing of Contamination of Exterior Wall Finishing Materials", Journal of Architectural Institute of Japan, Structural Transactions, No. 404, October 1989, pp. 15-2
4). According to conventional wisdom, polytetrafluoroethylene (PTFE) is used to prevent the above-mentioned dirt on the building exterior.
Although water-repellent paint such as was considered preferable,
Recently, for urban dust containing many hydrophobic components,
It is considered that the surface of the coating film should be made as hydrophilic as possible (Polymer, vol. 44, May 1995, p. 3).
07). Therefore, it has been proposed to paint a building with a hydrophilic graft polymer (newspaper "Chemical Industry Daily",
Jan. 30, 1995). According to reports, this coating exhibits a hydrophilicity of 30 to 40 ° in contact angle with water.
However, the contact angle of inorganic dust represented by clay minerals with water is 20 ° to 50 °, and the contact angle with water is 3 °.
Having an affinity for a graft polymer of 0 to 40 °;
It is considered that the coating of the graft polymer cannot prevent contamination by inorganic dust because it easily adheres to the surface.
【0004】[0004]
【発明が解決しようとする課題】本発明の目的は、部材
表面を高度の親水性になし、かつ維持することの可能な
塗膜を形成するための、保存安定性に優れた親水性コ−
ティング組成物を提供することにある。本発明の他の目
的は、鏡、ガラス、レンズ、プリズムその他の透明部材
の表面を高度に親水化することにより、部材の曇りや水
滴形成を防止することの可能な塗膜を形成するための、
保存安定性に優れた防曇性コ−ティング組成物を提供す
ることである。本発明の他の目的は、建物や窓ガラスや
機械装置や物品の表面を高度に親水化することにより、
表面が汚れるのを防止し、又は表面を水を用いて清浄化
することの可能な塗膜を形成するための、保存安定性に
優れた易清浄性コ−ティング組成物を提供することであ
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a hydrophilic coating having excellent storage stability for forming a coating film capable of maintaining and maintaining the surface of a member to a high degree of hydrophilicity.
The object of the present invention is to provide a sting composition. Another object of the present invention is to form a coating film capable of preventing clouding and water droplet formation of the member by making the surface of a mirror, glass, lens, prism or other transparent member highly hydrophilic. ,
An object of the present invention is to provide an antifogging coating composition having excellent storage stability. Another object of the present invention is to make the surfaces of buildings, windowpanes, machinery and articles highly hydrophilic,
It is an object of the present invention to provide an easy-to-clean coating composition excellent in storage stability for preventing a surface from being soiled or forming a coating film whose surface can be cleaned with water. .
【0005】[0005]
【課題を解決するための手段】本発明は、光触媒を含有
する表面層を形成した部材において、光触媒を光励起す
ると、部材の表面が高度に親水化されるという発見に基
づく。この現象は以下に示す機構により進行すると考え
られる。すなわち、光触媒の価電子帯上端と伝導帯下端
とのエネルギ−ギャップ以上のエネルギ−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、表面に極性が付与される。それによ
り、表面に、水が化学吸着し、さらに、その上に物理吸
着水層が形成され増加する。それにより、表面が水濡れ
角10゜以下の高度の親水性を呈するようになる。SUMMARY OF THE INVENTION The present invention is based on the discovery that, in a member having a surface layer containing a photocatalyst formed thereon, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the following mechanism. That is, when light having energy equal to or more than the energy gap between the upper end of the valence band and the lower end of the conduction band of the photocatalyst is irradiated on the photocatalyst, the electrons in the valence band of the photocatalyst are excited, and the conduction electrons and holes are generated. Produced and either or both actions impart polarity to the surface. As a result, water is chemically adsorbed on the surface, and a physically adsorbed water layer is formed thereon to increase. As a result, the surface exhibits a high degree of hydrophilicity with a water wetting angle of 10 ° or less.
【0006】本発明においては、平均組成式RpSiXq
O(4-p-q)/2(式中、Rは一価の有機基の1種若しくは
2種以上からなる官能基、又は、一価の有機基と水素基
から選ばれた2種以上からなる官能基であり、Xはアル
コキシ基、又は、ハロゲン原子であり、p及びqは0<
p<2、0<q<4を満足する数である)で表されるシ
ロキサンからなる塗膜形成要素であって、硬化させると
シリコ−ン樹脂の被膜を形成するものと;等電点がpH
で5以下の無機酸化物粒子で表面を被覆した光触媒性酸
化チタン粒子であって、前記塗膜形成要素中に分散さ
れ、光励起によって前記被膜の表面のシリコ−ン分子中
のケイ素原子に結合した有機基を光触媒作用により少な
くとも部分的に水酸基に置換させ、さらに光励起に応じ
て被膜の表面を親水化するための光触媒性酸化チタン粒
子;又は等電点がpHで9以上の無機酸化物粒子で表面
を被覆した光触媒性酸化チタン粒子であって、前記塗膜
形成要素中に分散され、光励起によって前記被膜の表面
のシリコ−ン分子中のケイ素原子に結合した有機基を光
触媒作用により少なくとも部分的に水酸基に置換させ、
さらに光励起に応じて被膜の表面を親水化するための光
触媒性酸化チタン粒子;を含有することを特徴とする光
触媒性親水性コ−ティング組成物を提供する。係るコ−
ティング組成物により基材表面に塗膜を形成すると、シ
リコ−ンの硬化反応により、基材表面には光触媒性酸化
物粒子とシリコ−ンを含有する表面層が形成されるよう
になる。この場合、光触媒の光励起によってシリコ−ン
分子中のケイ素原子に結合した有機基を光触媒作用によ
り少なくとも部分的に水酸基に置換され、さらにその上
に光触媒の光励起に応じて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。本発明では、さらに光触媒性酸化チタン粒子
に、表面が予め等電点が5以下の無機酸化物粒子又は等
電点が9以上の無機酸化物粒子で被覆されているように
したので、光触媒性酸化チタン粒子は中性液体中でも優
れた分散安定性を発揮できるようになる。ところで、請
求項1〜2の(a)で示されるシロキサンポリマ−成分
は、中性液体中で最も分散安定性が良好なことから、上
記被覆により、上記光触媒性親水性コ−ティング組成物
は、中性条件にすることにより、良好な保存安定性を発
揮するようになる。その理由は次のように考えられる。
すなわち、光触媒性酸化チタン粒子のみの場合は等電点
は7付近にあり、中性条件では粒子表面の等電点がほと
んどゼロになり凝集しやすくなるが、表面を上記物質に
より被覆することにより、粒子表面の等電点が酸性側又
は塩基性側にずれて優れた分散安定性を発揮できるよう
になると考えられる。In the present invention, the average composition formula R p SiX q
O (4-pq) / 2 (wherein, R is a functional group composed of one or more monovalent organic groups, or two or more selected from monovalent organic groups and hydrogen groups) X is an alkoxy group or a halogen atom, and p and q are 0 <
a film-forming element composed of a siloxane represented by the following formula: p <2, 0 <q <4), which forms a silicone resin film when cured; pH
A titanium oxide particle coated on the surface with inorganic oxide particles of 5 or less, wherein the titanium oxide particles are dispersed in the coating film forming element and are exposed to silicon molecules on the surface of the coating film by photoexcitation. Photocatalytic titanium oxide particles for at least partially replacing an organic group bonded to a silicon atom with a hydroxyl group by photocatalysis and further hydrophilizing the surface of the coating in response to photoexcitation; or an isoelectric point of 9 or more at pH a inorganic oxide particles by coating the surface with a photocatalytic oxidation of titanium particles, the coating film is dispersed forming element in silico of the surface of the coating by light excitation - organic bonded to the silicon atom in emissions molecule The group is at least partially replaced by a hydroxyl group by photocatalysis,
Further, there is provided a photocatalytic hydrophilic coating composition comprising: photocatalytic titanium oxide particles for hydrophilizing the surface of a film in response to photoexcitation. Such a core
When a coating film is formed on the surface of the substrate with the composition, the curing reaction of the silicone forms a surface layer containing the photocatalytic oxide particles and the silicon on the surface of the substrate. In this case, the organic group bonded to the silicon atom in the silicon molecule is at least partially replaced by a hydroxyl group by photocatalysis by the photoexcitation of the photocatalyst, and a physically adsorbed water layer is formed thereon in response to the photoexcitation of the photocatalyst. By doing so, the surface exhibits hydrophilicity close to the water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. In the present invention, the photocatalytic titanium oxide particles are further coated with an inorganic oxide particle having an isoelectric point of 5 or less or an inorganic oxide particle having an isoelectric point of 9 or more. The titanium oxide particles can exhibit excellent dispersion stability even in a neutral liquid. By the way, the siloxane polymer component represented by (a) of claims 1 and 2 has the best dispersion stability in a neutral liquid, so that the photocatalytic hydrophilic coating composition is coated by the coating. Under the neutral condition, good storage stability is exhibited. The reason is considered as follows.
That is, in the case of only the photocatalytic titanium oxide particles, the isoelectric point is around 7, and under neutral conditions, the isoelectric point on the particle surface becomes almost zero and the particles are easily aggregated. It is considered that by coating with the above-mentioned substance, the isoelectric point of the particle surface shifts to the acidic side or the basic side so that excellent dispersion stability can be exhibited.
【0007】[0007]
【発明の実施の形態】本発明において、光触媒性酸化チ
タンとは、その結晶の伝導帯と価電子帯との間のエネル
ギ−ギャップよりも大きなエネルギ−(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
うる酸化チタンをいい、例えば、アナタ−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が好適に
利用できる。本発明における高度の親水性とは、水との
接触角に換算して10゜以下、好ましくは5゜以下の水
濡れ性を呈する状態をいう。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, photocatalytic titanium oxide refers to light (excitation light) having an energy (ie, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. Irradiates a titanium oxide capable of generating conduction electrons and holes by excitation of electrons in the valence band (photoexcitation) upon irradiation with, for example, an anatase type titanium oxide and a rutile type titanium oxide. Crystalline titanium oxide can be suitably used. The high hydrophilicity in the present invention means a state exhibiting water wettability of 10 ° or less, preferably 5 ° or less in terms of a contact angle with water.
【0008】請求項1〜2の(a)に記述されるシリコ
−ンは、平均組成式RpSiO(4-p)/2(式中、Rは一価
の有機基の1種若しくは2種以上からなる官能基、又
は、一価の有機基と水素基から選ばれた2種以上からな
る官能基であり、Xはアルコキシ基、又は、ハロゲン原
子であり、pは0<p<2を満足する数である)で表さ
れる樹脂である。この樹脂は後述するシリコ−ンの前駆
体を部分的に加水分解、脱水縮重合することにより得る
ことができる。The silicone described in the first and second aspects (a) has an average compositional formula of R p SiO (4-p) / 2 (where R is one or two monovalent organic groups) X is an alkoxy group or a halogen atom, and p is 0 <p <2. Which satisfies the following formula). This resin can be obtained by partially hydrolyzing and dehydrating polycondensation of a silicone precursor described later.
【0009】ここでシリコ−ンの前駆体としては、平均
組成式RpSiXqO(4-p-q)/2(式中、Rは一価の有機
基の1種若しくは2種以上からなる官能基、又は、一価
の有機基と水素基から選ばれた2種以上からなる官能基
であり、Xはアルコキシ基、又は、ハロゲン原子であ
り、p及びqは0<p<2、0<q<4を満足する数で
ある)で表されるシロキサンからなる塗膜形成要素、又
は一般式RpSiX4-p(式中、Rは一価の有機基の1種
若しくは2種以上からなる官能基、又は、一価の有機基
と水素基から選ばれた2種以上からなる官能基であり、
Xはアルコキシ基、又は、ハロゲン原子であり、pは1
または2である)で表される加水分解性シラン誘導体か
らなる塗膜形成要素、が好適に利用できる。Here, the precursor of the silicone includes an average compositional formula RpSiXqO (4-pq) / 2 (where R is a functional group comprising one or more monovalent organic groups, or X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <q <4. A film-forming element comprising a siloxane represented by the following formula: or a general formula RpSiX4-p (wherein R is a functional group comprising one or more monovalent organic groups, or Functional group consisting of two or more selected from a valence organic group and a hydrogen group,
X is an alkoxy group or a halogen atom, and p is 1
Or 2), which is preferably composed of a hydrolyzable silane derivative represented by the formula (1).
【0010】ここで上記加水分解性シラン誘導体からな
る塗膜形成要素としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリブトキシシラン、エチルトリメトキシシ
ラン、エチルトリエトキシシラン、エチルトリプロポキ
シシラン、エチルトリブトキシシラン、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
トリプロポキシシラン、フェニルトリブトキシシラン、
ジメチルジメトキシシラン、ジメチルジエトキシシラ
ン、ジメチルジプロポキシシラン、ジメチルジブトキシ
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、ジエチルジプロポキシシラン、ジエチルジブ
トキシシラン、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、フェニルメチルジプロポ
キシシラン、フェニルメチルジブトキシシラン、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−プロピルトリプロポキシシラン、n−プロ
ピルトリブトキシシラン、γ−グリコキシドキシプロピ
ルトリメトキシシラン、γ−アクリロキシプロピルトリ
メトキシシラン等が好適に利用できる。Here, as the coating film forming element comprising the above hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.
【0011】また、上記シロキサンからなる塗膜形成要
素としては、上記加水分解性シラン誘導体の部分加水分
解及び脱水縮重合、又は上記加水分解性シラン誘導体の
部分加水分解物と、テトラメトキシシラン、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、ジエトキシジメトキシシラン等の部分加水分解
物との脱水縮重合等で作製することができる。The film-forming element composed of the above-mentioned siloxane includes partial hydrolysis and dehydration-condensation polymerization of the above-mentioned hydrolyzable silane derivative, or partially hydrolyzate of the above-mentioned hydrolyzable silane derivative, tetramethoxysilane and tetramethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.
【0012】請求項1の(b)に記述される等電点がp
Hで5以下の無機酸化物粒子としては、シリカ、アルミ
ノシリケ−ト等が好適に利用できる。請求項2の(b)
に記述される等電点がpHで9以上の無機酸化物粒子と
しては、ジルコニア等が好適に利用できる。The isoelectric point described in claim 1 (b) is p
As the inorganic oxide particles having an H of 5 or less, silica, aluminosilicate and the like can be suitably used. Claim 2 (b)
As the inorganic oxide particles having an isoelectric point of 9 or more at pH described in (1), zirconia and the like can be suitably used.
【0013】光触媒性酸化チタン粒子への上記被覆物の
固定方法は、例えば、スプレ−コ−ティング法、ディッ
プコ−ティング法、フロ−コ−ティング法、スピンコ−
ティング法、ロ−ルコ−ティング法、刷毛塗り、スポン
ジ塗り等の方法で被覆後、熱処理等の方法で固定する。[0013] the method of fixing the coating to the photocatalytic oxidation of titanium particles, for example, spray - co - plating method, a dip - coating method, flow - co - plating method, a spin -
After coating by a coating method, a roll coating method, brush coating, sponge coating or the like, it is fixed by a method such as heat treatment.
【0014】コ−ティング組成物には、Ag、Cu、Z
nのような金属を添加することができる。前記金属を添
加した場合、塗膜により形成される表面層は、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。The coating composition includes Ag, Cu, Z
A metal such as n can be added. When the metal is added, the surface layer formed by the coating film can kill bacteria and fungi attached to the surface even in a dark place.
【0015】コ−ティング組成物には、Pt、Pd、R
u、Rh、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場合、塗膜により形成
される表面層は、光触媒の酸化還元活性を増強でき、有
機物汚れの分解性、有害気体や悪臭の分解性を向上させ
ることができる。[0015] The coating composition includes Pt, Pd, R
A platinum group metal such as u, Rh, Ir, Os can be added. When the metal is added, the surface layer formed by the coating film can enhance the oxidation-reduction activity of the photocatalyst, and can improve the decomposability of organic contaminants and harmful gases and odors.
【0016】コ−ティング組成物は、その他に水、エタ
ノ−ル、プロパノ−ル等の溶媒や、塩酸、硝酸、硫酸、
酢酸、マレイン酸等のシリコ−ンの前駆体の加水分解を
促進する触媒や、トリブチルアミン、ヘキシルアミンな
どの塩基性化合物類、アルミニウムトリイソプロポキシ
ド、テトライソプロピルチタネ−トなどの酸性化合物類
等のシリコ−ンの前駆体を硬化させる触媒や、シランカ
ップリング剤等のコ−ティング液の分散性を向上させる
界面活性剤などを添加してもよい。The coating composition may further contain a solvent such as water, ethanol, propanol, hydrochloric acid, nitric acid, sulfuric acid,
Catalysts that promote hydrolysis of silicone precursors such as acetic acid and maleic acid, basic compounds such as tributylamine and hexylamine, and acidic compounds such as aluminum triisopropoxide and tetraisopropyl titanate For example, a catalyst for curing the precursor of the silicone such as silane coupling agent or a surfactant for improving the dispersibility of the coating liquid such as a silane coupling agent may be added.
【0017】本発明のコ−ティング組成物の利用方法
は、基本的には、基材表面にコ−ティング組成物を塗布
し、硬化させて塗膜を形成することによる。The method of using the coating composition of the present invention is basically based on applying the coating composition to the surface of a substrate and curing the coating composition to form a coating film.
【0018】上記コ−ティング組成物の塗布方法として
は、スプレ−コ−ティング法、ディップコ−ティング
法、フロ−コ−ティング法、スピンコ−ティング法、ロ
−ルコ−ティング法、刷毛塗り、スポンジ塗り等の方法
が好適に利用できる。硬化方法としては、熱処理、室温
放置、紫外線照射等により重合させて行うことができ
る。The coating method of the above coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.
【0019】上記方法で部材表面に塗膜を形成すると、
部材表面は光触媒の光励起に応じて親水性を呈するよう
になる。ここで、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0.001
mW/cm2以上あればよいが、0.01mW/cm2以
上だと好ましく、0.1mW/cm2以上だとより好ま
しい。光触媒の光励起に用いる光源としては、太陽光、
室内照明、蛍光灯、水銀灯、白熱電灯、キセノンラン
プ、高圧ナトリウムランプ、メタルハライドランプ、B
LBランプ等が好適に利用できる。When a coating film is formed on the member surface by the above method,
The surface of the member becomes hydrophilic in response to the photoexcitation of the photocatalyst. Here, in order for the substrate surface to be highly hydrophilized by photoexcitation of the photocatalyst, the illuminance of the excitation light must be 0.001.
mW / cm2 or more may be sufficient, but it is preferably 0.01 mW / cm2 or more, and more preferably 0.1 mW / cm2 or more. Light sources used for photoexcitation of the photocatalyst include sunlight,
Interior lighting, fluorescent lamp, mercury lamp, incandescent lamp, xenon lamp, high-pressure sodium lamp, metal halide lamp, B
An LB lamp or the like can be suitably used.
【0020】部材表面に塗膜により形成される表面層の
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、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。The thickness of the surface layer formed by the coating film on the member surface is preferably 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, the thickness of the surface layer is
It is more preferable that the thickness be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency.
Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.
【0021】PCT/JP96/00733号に示した
ように、部材表面が水との接触角に換算して10゜以下
の状態であれば、空気中の湿分や湯気が結露しても、凝
縮水が個々の水滴を形成せずに一様な水膜になる傾向が
顕著になる。従って、表面に光散乱性の曇りを生じない
傾向が顕著になる。同様に、窓ガラスや車両用バックミ
ラ−や車両用風防ガラスや眼鏡レンズやヘルメットのシ
−ルドが降雨や水しぶきを浴びた場合に、離散した目障
りな水滴が形成されずに、高度の視界と可視性を確保
し、車両や交通の安全性を保証し、種々の作業や活動の
能率を向上させる効果が飛躍的に向上する。また、同様
にPCT/JP96/00733号に示したように、部
材表面が水との接触角に換算して10゜以下、好ましく
は5゜以下の状態であれば、都市煤塵、自動車等の排気
ガスに含有されるカ−ボンブラック等の燃焼生成物、油
脂、シ−ラント溶出成分等の疎水性汚染物質、及び無機
粘土質汚染物質双方が付着しにくく、付着しても降雨や
水洗により簡単に落せる状態になる。As shown in PCT / JP96 / 00733, if the surface of the member is not more than 10 ° in terms of the contact angle with water, even if moisture or steam in the air is condensed, condensation occurs. Water tends to form a uniform water film without forming individual water droplets. Therefore, the tendency that light scattering fogging does not occur on the surface becomes remarkable. Similarly, when a window glass, a vehicle back mirror, a vehicle windshield, an eyeglass lens, or a shield of a helmet is subjected to rainfall or splashing, discrete unsightly water droplets are not formed, and high visibility and visibility are achieved. As a result, the effects of ensuring safety, ensuring the safety of vehicles and traffic, and improving the efficiency of various tasks and activities are greatly improved. Similarly, as shown in PCT / JP96 / 00733, if the surface of the member is less than or equal to 10 °, preferably less than or equal to 5 ° in terms of the contact angle with water, exhaust from city dust, automobiles, etc. Combustion products such as carbon black contained in gas, hydrophobic contaminants such as oils and fats, sealant eluting components, etc., and inorganic clay contaminants are unlikely to adhere to each other. It is in a state where it can be dropped.
【0022】部材表面が上記高度の親水性を呈し、かつ
その状態を維持するようになれば、上記防曇効果、表面
清浄化効果の他、帯電防止効果(ほこり付着防止効
果)、断熱効果、水中での気泡付着防止効果、熱交換器
における効率向上効果、生体親和性向上効果等が発揮さ
れるようになる。If the surface of the member exhibits the above-mentioned high hydrophilicity and maintains the state, the anti-fogging effect, the surface cleaning effect, the antistatic effect (dust adhesion preventing effect), the heat insulating effect, The effect of preventing bubbles from adhering in water, the effect of improving efficiency in a heat exchanger, the effect of improving biocompatibility, and the like are exhibited.
【0023】本発明が適用可能な基材としては、防曇効
果を期待する場合には透明な部材であり、その材質はガ
ラス、プラスチック等が好適に利用できる。適用可能な
基材を用途でいえば、車両用後方確認ミラ−、浴室用
鏡、洗面所用鏡、歯科用鏡、道路鏡のような鏡;眼鏡レ
ンズ、光学レンズ、照明用レンズ、半導体用レンズ、複
写機用レンズ、車両用後方確認カメラレンズのようなレ
ンズ;プリズム;建物や監視塔の窓ガラス;自動車、鉄
道車両、航空機、船舶、潜水艇、雪上車、ロ−プウエイ
のゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の
窓ガラス;自動車、オ−トバイ、鉄道車両、航空機、船
舶、潜水艇、雪上車、スノ−モ−ビル、ロ−プウエイの
ゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の風
防ガラス;防護用ゴ−グル、スポ−ツ用ゴ−グル、防護
用マスクのシ−ルド、スポ−ツ用マスクのシ−ルド、ヘ
ルメットのシ−ルド、冷凍食品陳列ケ−スのガラス、中
華饅頭等の保温食品の陳列ケ−スのガラス;計測機器の
カバ−、車両用後方確認カメラレンズのカバ−、レ−ザ
−歯科治療器等の集束レンズ、車間距離センサ−等のレ
−ザ−光検知用センサ−のカバ−、赤外線センサ−のカ
バ−;カメラ用フィルタ−、及び上記物品表面に貼着さ
せるためのフィルム、シ−ト、シ−ル等を含む。The substrate to which the present invention can be applied is a transparent member when an anti-fogging effect is expected, and glass, plastic, or the like can be suitably used as the material. Speaking of applicable base materials, mirrors such as rearview mirrors for vehicles, mirrors for bathrooms, mirrors for toilets, dental mirrors, road mirrors; spectacle lenses, optical lenses, illumination lenses, semiconductor lenses Lenses such as copier lenses, rear view camera lenses for vehicles; prisms; windows of buildings and towers; automobiles, railway vehicles, aircraft, ships, submersibles, snowmobiles, lowway gondola, amusement parks Gondolas, vehicle windows such as spaceships; cars, motorbikes, railway vehicles, aircraft, ships, submarines, snowmobiles, snowmobiles, lowway gondola, amusement park gondola, space Windshield for vehicles such as ships; protective goggles, sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display Case glass, Chinese bun, etc. Glass for display case of warm food; Cover for measuring equipment, Cover for rear view camera lens for vehicle, Focusing lens for laser dental treatment device, etc., Laser light detection for inter-vehicle distance sensor, etc. Cover for an infrared sensor, a cover for an infrared sensor, a filter for a camera, and a film, a sheet, a seal, and the like to be attached to the surface of the article.
【0024】本発明が適用可能な基材としては、表面清
浄化効果を期待する場合にはその材質は、例えば、金
属、セラミック、ガラス、プラスチック、木、石、セメ
ント、コンクリ−ト、繊維、布帛、それらの組合せ、そ
れらの積層体が好適に利用できる。適用可能な基材を用
途でいえば、建材、建物外装、建物内装、窓枠、窓ガラ
ス、構造部材、乗物の外装及び塗装、機械装置や物品の
外装、防塵カバ−及び塗装、交通標識、各種表示装置、
広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガ−ドレ
−ルの外装及び塗装、トンネル内装及び塗装、碍子、太
陽電池カバ−、太陽熱温水器集熱カバ−、ビニ−ルハウ
ス、車両用照明灯のカバ−、住宅設備、便器、浴槽、洗
面台、照明器具、照明カバ−、台所用品、食器、食器洗
浄器、食器乾燥器、流し、調理レンジ、キッチンフ−
ド、換気扇、及び上記物品表面に貼着させるためのフィ
ルム、シ−ト、シ−ル等を含む。When a surface cleaning effect is expected as a substrate to which the present invention can be applied, the material may be, for example, metal, ceramic, glass, plastic, wood, stone, cement, concrete, fiber, Fabrics, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, windowpanes, structural members, vehicle exteriors and coatings, machinery and articles exteriors, dustproof covers and coatings, traffic signs, Various display devices,
Advertising towers, noise barriers for roads, noise barriers for railways, bridges, exterior and coating of garages, tunnel interiors and coatings, insulators, solar battery covers, solar water heater collector covers, vinyl houses, vehicle lighting Light covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures, lighting covers, kitchen utensils, dishes, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods
And a film, a sheet, a seal, and the like for attaching to the surface of the article.
【0025】本発明が適用可能な基材としては、帯電防
止効果を期待する場合にはその材質は、例えば、金属、
セラミック、ガラス、プラスチック、木、石、セメン
ト、コンクリ−ト、繊維、布帛、それらの組合せ、それ
らの積層体が好適に利用できる。適用可能な基材を用途
でいえば、ブラウン管、磁気記録メディア、光記録メデ
ィア、光磁気記録メディア、オ−ディオテ−プ、ビデオ
テ−プ、アナログレコ−ド、家庭用電気製品のハウジン
グや部品や外装及び塗装、OA機器製品のハウジングや
部品や外装及び塗装、建材、建物外装、建物内装、窓
枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装
置や物品の外装、防塵カバ−及び塗装、及び上記物品表
面に貼着させるためのフィルム、シ−ト、シ−ル等を含
む。When the antistatic effect is expected as a substrate to which the present invention can be applied, the material is, for example, metal,
Ceramic, glass, plastic, wood, stone, cement, concrete, fiber, fabric, combinations thereof, and laminates thereof can be suitably used. Speaking of applicable substrates, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, housings and parts for household electrical appliances, Exterior and painting, OA equipment product housing and parts and exterior and painting, building materials, building exterior, building interior, window frames, window glass, structural members, vehicle exterior and painting, mechanical equipment and articles exterior, dustproof cover and Includes films, sheets, seals, etc. for painting and sticking to the surface of the article.
【0026】[0026]
【実施例】塩素法にて作製した光触媒性酸化チタン粒子
をγ−グリコキシドプロピルトリメトキシシランで表面
処理し、500℃で加熱して作製したシリカ被覆光触媒
性酸化チタン粒子を、pH7の水中に分散させた。この
分散液と、シロキサン樹脂塗料を混合後、エタノ−ルで
希釈し、3時間撹拌し、コ−ティング液を得た。このコ
−ティング液を1か月17℃で放置したが分散性は良好
であった。またこのコ−ティング液を石英ガラス板に塗
布し、150℃で硬化させた試料に、3日間紫外線照度
0.5mW/cm2のBLBランプを照射したところ、
水との接触角は0゜になった。EXAMPLES The photocatalytic oxidation of titanium particles produced by a chlorine method is surface-treated with γ- glycoxide trimethoxysilane, silica was prepared by heating at 500 ° C. under Kutsugaehikari catalyst
Sex acid titanium particles, dispersed in water of pH 7. After mixing the dispersion and the siloxane resin coating, the mixture was diluted with ethanol and stirred for 3 hours to obtain a coating liquid. This coating liquid was left at 17 ° C. for one month, but the dispersibility was good. When the coating liquid was applied to a quartz glass plate and cured at 150 ° C., the sample was irradiated with a BLB lamp having an ultraviolet illuminance of 0.5 mW / cm 2 for 3 days.
The contact angle with water became 0 °.
【0027】[0027]
【発明の効果】本発明の光触媒性親水性コ−ティング組
成物によれば、優れた長期保存安定性を有するととも
に、部材表面を高度の親水性になし、かつ維持すること
ができる。The photocatalytic hydrophilic coating composition of the present invention has excellent long-term storage stability and can maintain and maintain the surface of the member to a high degree of hydrophilicity.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C09D 183/04 C09C 3/12 C09D 5/00 C09D 7/12 C09K 3/18 104 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C09D 183/04 C09C 3/12 C09D 5/00 C09D 7/12 C09K 3/18 104
Claims (6)
成するシロキサンからなる塗膜形成要素と、この塗膜形
成要素中に分散され、光励起に応じて前記被膜の表面を
親水化するための光触媒性酸化チタンとを含有する光触
媒性親水性コーティング組成物であって、 前記シロキサンからなる塗膜形成要素は、加水分解性シ
ラン誘導体の部分加水分解及び脱水縮重合、又は加水分
解性シラン誘導体の部分加水分解物と、テトラメトキシ
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、ジエトキシジメトキシシラ
ンの部分加水分解物との脱水縮重合で作製され、 また、前記加水分解性シラン誘導体は、メチルトリメト
キシシラン、メチルトリエトキシシラン、メチルトリプ
ロポキシシラン、メチルトリブトキシシラン、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
トリプロポキシシラン、エチルトリブトキシシラン、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、フェニルトリプロポキシシラン、フェニルトリブト
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、ジメチルジプロポキシシラン、ジメチル
ジブトキシシラン、ジエチルジメトキシシラン、ジエチ
ルジエトキシシラン、ジエチルジプロポキシシラン、ジ
エチルジブトキシシラン、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
ルジプロポキシシラン、フェニルメチルジブトキシシラ
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−プロピルトリプロポキシシラ
ン、n−プロピルトリブトキシシラン、γ−グリコキシ
ドキシプロピルトリメトキシシラン、γ−アクリロキシ
プロピルトリメトキシシランのいずれかとし、 前記光触媒性酸化チタンは、等電点がpHで5以下の無
機酸化物粒子で表面を被覆したものである。1. A film forming element comprising a siloxane which forms a silicone resin film when cured, and a photocatalytic substance dispersed in the film forming element and hydrophilizing the surface of the film in response to photoexcitation. A photocatalytic hydrophilic coating composition containing titanium oxide, wherein the film-forming element comprising the siloxane comprises a hydrolyzable silicone.
Partial hydrolysis and dehydration polycondensation of orchid derivative or hydrolysis
Partial hydrolyzate of a decomposable silane derivative and tetramethoxy
Silane, tetraethoxysilane, tetrapropoxysila
, Tetrabutoxysilane, diethoxydimethoxysila
Produced by dehydration-condensation polymerization with a partial hydrolyzate of
Xysilane, methyltriethoxysilane, methyltrip
Lopoxysilane, methyltributoxysilane, ethylto
Limethoxysilane, ethyltriethoxysilane, ethyl
Tripropoxysilane, ethyltributoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysila
, Phenyltripropoxysilane, phenyltribute
Xysilane, dimethyldimethoxysilane, dimethyldie
Toxysilane, dimethyldipropoxysilane, dimethyl
Dibutoxy silane, diethyl dimethoxy silane, diethyl
Ludiethoxysilane, diethyldipropoxysilane, di
Ethyl dibutoxy silane, phenyl methyl dimethoxy
Orchid, phenylmethyldiethoxysilane, phenylmethyl
Ludipropoxysilane, phenylmethyldibutoxysila
N-propyltrimethoxysilane, n-propyl
Liethoxysilane, n-propyltripropoxysila
, N-propyltributoxysilane, γ-glycoxy
Doxypropyltrimethoxysilane, γ-acryloxy
Any one of propyltrimethoxysilane, and the photocatalytic titanium oxide has a surface coated with inorganic oxide particles having an isoelectric point of 5 or less at pH.
成するシロキサンからなる塗膜形成要素と、この塗膜形
成要素中に分散され、光励起に応じて前記被膜の表面を
親水化するための光触媒性酸化チタンとを含有する光触
媒性親水性コーティング組成物であって、 前記シロキサンからなる塗膜形成要素は、加水分解性シ
ラン誘導体の部分加水分解及び脱水縮重合、又は加水分
解性シラン誘導体の部分加水分解物と、テトラメトキシ
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、ジエトキシジメトキシシラ
ンの部分加水分解物との脱水縮重合で作製され、 また、前記加水分解性シラン誘導体は、メチルトリメト
キシシラン、メチルトリエトキシシラン、メチルトリプ
ロポキシシラン、メチルトリブトキシシラン、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
トリプロポキシシラン、エチルトリブトキシシラン、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、フェニルトリプロポキシシラン、フェニルトリブト
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、ジメチルジプロポキシシラン、ジメチル
ジブトキシシラン、ジエチルジメトキシシラン、ジエチ
ルジエトキシシラン、ジエチルジプロポキシシラン、ジ
エチルジブトキシシラン、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
ルジプロポキシシラン、フェニルメチルジブトキシシラ
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−プロピルトリプロポキシシラ
ン、n−プロピルトリブトキシシラン、γ−グリコキシ
ドキシプロピルトリメトキシシラン、γ−アクリロキシ
プロピルトリメトキシシランのいずれかとし、 前記光触媒性酸化チタンは、等電点がpHで9以上の無
機酸化物粒子で表面を被覆したものである。2. A film-forming element comprising a siloxane which forms a silicone resin film when cured, and a photocatalytic substance dispersed in the film-forming element for hydrophilizing the surface of the film in response to photoexcitation. A photocatalytic hydrophilic coating composition containing titanium oxide, wherein the film-forming element comprising the siloxane comprises a hydrolyzable silicone.
Partial hydrolysis and dehydration polycondensation of orchid derivative or hydrolysis
Partial hydrolyzate of a decomposable silane derivative and tetramethoxy
Silane, tetraethoxysilane, tetrapropoxysila
, Tetrabutoxysilane, diethoxydimethoxysila
Produced by dehydration-condensation polymerization with a partial hydrolyzate of
Xysilane, methyltriethoxysilane, methyltrip
Lopoxysilane, methyltributoxysilane, ethylto
Limethoxysilane, ethyltriethoxysilane, ethyl
Tripropoxysilane, ethyltributoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysila
, Phenyltripropoxysilane, phenyltribute
Xysilane, dimethyldimethoxysilane, dimethyldie
Toxysilane, dimethyldipropoxysilane, dimethyl
Dibutoxy silane, diethyl dimethoxy silane, diethyl
Ludiethoxysilane, diethyldipropoxysilane, di
Ethyl dibutoxy silane, phenyl methyl dimethoxy
Orchid, phenylmethyldiethoxysilane, phenylmethyl
Ludipropoxysilane, phenylmethyldibutoxysila
N-propyltrimethoxysilane, n-propyl
Liethoxysilane, n-propyltripropoxysila
, N-propyltributoxysilane, γ-glycoxy
Doxypropyltrimethoxysilane, γ-acryloxy
Any one of propyltrimethoxysilane, and the photocatalytic titanium oxide has a surface coated with inorganic oxide particles having an isoelectric point of 9 or more at pH.
前記被膜は、その表面に付着した湿分の凝縮水及び/又
は水滴が被膜の表面に広がるのを可能にし、以て、該被
膜によって被覆された基材が湿分の凝縮水及び/又は水
滴によって曇り若しくは翳るのを防止することを特徴と
する請求項1又は2に記載の光触媒性親水性コ−ティン
グ組成物。3. The coating, the surface of which has been hydrophilized in response to photoexcitation, allows the condensation of moisture and / or water droplets adhering to the surface to spread on the surface of the coating, whereby the coating The photocatalytic hydrophilic coating composition according to claim 1 or 2, wherein the substrate coated with the composition is prevented from being clouded or overcast by moisture condensed water and / or water droplets.
前記被膜は、降雨にさらされた時に付着堆積物及び/又
は汚染物が雨水により洗い流されるのを可能にし、以
て、表面の自己浄化を可能にすることを特徴とする請求
項1又は2に記載の光触媒性親水性コ−ティング組成
物。4. The coating, the surface of which has been hydrophilized in response to photoexcitation, enables attached sediments and / or contaminants to be washed away by rainwater when exposed to rainfall, whereby the surface self The photocatalytic hydrophilic coating composition according to claim 1 or 2, wherein purification is possible.
前記被膜は、汚染物を含んだ雨水が接触したときに汚染
物が表面に付着するのを防止することを特徴とする請求
項1又は2に記載の光触媒性親水性コ−ティング組成
物。5. The coating whose surface has been hydrophilized in response to photoexcitation prevents the contaminant from adhering to the surface when rainwater containing the contaminant comes into contact. Or the photocatalytic hydrophilic coating composition according to item 2.
前記被膜は、水に浸漬したとき又は水で濡らしたときに
付着堆積物及び/又は汚染物を釈放し、以て、表面を水
で洗浄するのを容易にすることを特徴とする請求項1又
は2に記載の光触媒性親水性コ−ティング組成物。6. The coating, the surface of which has been hydrophilized in response to photoexcitation, releases adhering deposits and / or contaminants when immersed in or wetted with water, so that the surface is exposed to water. The photocatalytic hydrophilic coating composition according to claim 1 or 2, wherein the composition is easily washed with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34047296A JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-354649 | 1995-12-22 | ||
| JP35464995 | 1995-12-22 | ||
| JP34047296A JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09227832A JPH09227832A (en) | 1997-09-02 |
| JP3348613B2 true JP3348613B2 (en) | 2002-11-20 |
Family
ID=93155440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3348613B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227779A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Rubber member for construction and method for imparting hydrophilicity to its surface |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174479A4 (en) | 1999-03-09 | 2009-08-19 | Toto Ltd | Hydrophilic member, method for preparation thereof, and coating agent and apparatus for preparation thereof |
| CN105349042A (en) * | 2015-11-20 | 2016-02-24 | 杨京广 | Silicon carbide coating and use method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996029375A1 (en) | 1995-03-20 | 1996-09-26 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
-
1996
- 1996-12-05 JP JP34047296A patent/JP3348613B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996029375A1 (en) | 1995-03-20 | 1996-09-26 | Toto Ltd. | Method of photocatalytically making the surface of base material ultrahydrophilic, base material having ultrahydrophilic and photocatalytic surface, and process for producing said material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227779A (en) * | 1995-12-22 | 1997-09-02 | Toto Ltd | Rubber member for construction and method for imparting hydrophilicity to its surface |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09227832A (en) | 1997-09-02 |
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