JP2003306347A - Stain-proofing glass - Google Patents
Stain-proofing glassInfo
- Publication number
- JP2003306347A JP2003306347A JP2002111523A JP2002111523A JP2003306347A JP 2003306347 A JP2003306347 A JP 2003306347A JP 2002111523 A JP2002111523 A JP 2002111523A JP 2002111523 A JP2002111523 A JP 2002111523A JP 2003306347 A JP2003306347 A JP 2003306347A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- treatment
- antifouling
- coating layer
- layer
- 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
- 239000011521 glass Substances 0.000 title claims abstract description 77
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 230000001699 photocatalysis Effects 0.000 claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003851 corona treatment Methods 0.000 claims abstract description 21
- 208000028659 discharge Diseases 0.000 claims abstract description 19
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims description 49
- 230000003373 anti-fouling effect Effects 0.000 claims description 30
- 239000010410 layer Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002519 antifouling agent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000009257 reactivity Effects 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- -1 siloxane compounds Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は防汚機能及び空気浄
化機能を付与した住宅の窓ガラスや車両用のガラス（以
下、単にガラスという）の構造に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure of a window glass of a house or a glass for a vehicle (hereinafter, simply referred to as glass) provided with an antifouling function and an air purifying function.
【０００２】[0002]
【従来の技術】ガラスの特に屋外側は排気ガスや埃によ
って極めて汚れやすい。更に、屋内側はたばこの煙やペ
ット臭、塵、埃、石油ストーブ等から発生するＮＯX 、
ＳＯX等による空気の汚れが問題となっており、特に近
年における最大の問題は素材（建材）からのホルムアル
デヒドの発生である。これに対して新素材の開発や空気
清浄器の開発が行われている。また、ガラス表面に撥水
性をもたらすような主として車両用のウインドウオッシ
ャー液が提案され、酸化チタンをガラスの表面に高温で
処理する親水性に富んだ防曇ガラスが提案されている。2. Description of the Related Art Glass, especially on the outdoor side, is extremely susceptible to contamination by exhaust gas and dust. In addition, the indoor side of cigarette smoke and pet odors, to generate dust, dust, from petroleum stove, such as NO X,
Air pollution due to SO X and the like has become a problem, and in particular, the biggest problem in recent years is generation of formaldehyde from a material (building material). On the other hand, new materials and air purifiers are being developed. Further, a window washer liquid for vehicles, which brings water repellency to the glass surface, has been proposed, and a hydrophilic anti-fog glass that treats titanium oxide on the glass surface at high temperature has been proposed.
【０００３】しかるに、空気清浄器では機器を作動させ
た時しか効果が得られず、作動させるためには電気エネ
ルギーが必要であり、エネルギーを消費するという問題
もある。又、ノンホルムアルデヒド建材として、建材か
らの汚染は防げるが、その他から発生する汚染物質を積
極的に除去する効果はない。更に、防曇ガラスでは、親
水化の効果のみで、汚染物質に対する分解活性はなく、
防汚効果を発揮することはなく、また、空気を浄化する
機能を持っていない。However, the air purifier is effective only when the equipment is operated, requires electric energy to operate, and consumes energy. Further, as a non-formaldehyde building material, it is possible to prevent pollution from building materials, but it is not effective in actively removing pollutants generated from other materials. Furthermore, with anti-fog glass, there is no hydrolytic effect and there is no decomposition activity for pollutants.
It has no antifouling effect and does not have the function of purifying air.
【０００４】[0004]
【発明が解決しようとする課題】本発明では、電力等の
人工的エネルギーを必要とせず、かつ汚染物質が発生す
ると自発的に物質を分解、除去する光触媒作用をガラス
表面に付加したガラス構造にかかり、更に言えば、ガラ
ス表面を親水化する機能とガラス表面に付着する油分等
の汚れを分解する機能を備え、これらを分解・除去する
ことにより常に清潔性を保つと共に、見通しのよいガラ
ス構造を提供することを目的とする。DISCLOSURE OF THE INVENTION According to the present invention, a glass structure which does not require artificial energy such as electric power and which has a photocatalytic action on the glass surface for decomposing and removing substances spontaneously when pollutants are generated is provided. In addition, it has a function to hydrophilize the glass surface and a function to decompose dirt such as oil adhering to the glass surface.By disassembling and removing these, it is always possible to maintain cleanliness and a glass structure with good visibility. The purpose is to provide.
【０００５】[0005]
【課題を解決するための手段】本発明は、住宅用或いは
自動車等に使用されるガラス構造であって、ガラス基材
の少なくとも一方の表面に親水処理を施し、当該処理面
上に水系の防汚剤を塗工（第２塗膜層）することを特徴
とするもので、好ましくは、水系の防汚剤は光触媒能を
有する光触媒体であり、これがアナターゼ型酸化チタン
である防汚性ガラス構造に係るものである。SUMMARY OF THE INVENTION The present invention is a glass structure used for houses or automobiles, in which at least one surface of a glass substrate is subjected to hydrophilic treatment, and a water-based protective coating is applied on the treated surface. It is characterized in that a stain agent is applied (second coating layer), and preferably the water-based stainproof agent is a photocatalyst having photocatalytic ability, and this is anatase type titanium oxide stainproof glass. It is related to the structure.
【０００６】そして、更に好ましくは、親水処理が施さ
れたガラスの表面と防汚剤（第２塗膜層）との間に中間
層（第１塗膜層）を設けた構造のものであって、上記中
間層（第１塗膜層）が光触媒能を有さないアモルフアス
型過酸化チタンからなり、アモルフアス型酸化チタンと
の混合物であってもよい。場合によっては、この中間層
（第１塗膜層）が界面活性剤及び／又は親水剤を含有す
るものである。More preferably, the structure is such that an intermediate layer (first coating layer) is provided between the surface of the glass subjected to hydrophilic treatment and the antifouling agent (second coating layer). The intermediate layer (first coating layer) is made of amorphous titanium peroxide having no photocatalytic activity, and may be a mixture with amorphous titanium oxide. In some cases, this intermediate layer (first coating layer) contains a surfactant and / or a hydrophilic agent.
【０００７】上記防汚性ガラス構造にあって、ガラス基
材の表面を親水処理するものであり、係る親水処理手段
がコロナ放電処理、プラズマ放電処理、紫外線処理、オ
ゾン処理を施したものである。尚、コロナ放電処理によ
る当該表面の親水化は、水の接触角は１０〜４０度程度
がよい。In the above-mentioned antifouling glass structure, the surface of the glass base material is subjected to hydrophilic treatment, and the hydrophilic treatment means performs corona discharge treatment, plasma discharge treatment, ultraviolet treatment and ozone treatment. . In order to make the surface hydrophilic by corona discharge treatment, the contact angle of water is preferably about 10 to 40 degrees.
【０００８】[0008]
【発明の実施の形態】本発明について更に言及すると、
各種の用途に用いられるガラスの表面に上記した特殊な
塗膜層を形成したもので、光触媒能を有する酸化物粒子
が外気と接触し、有機物分解能と親水性をもたらす表面
層が形成されている。このため、ガラスの表面に付着し
た汚れは分解され簡単に水にて洗浄可能となったもので
ある。即ち、この塗膜層は光触媒作用による防汚機能と
親水性をもたらし、更に塗膜層による光触媒とガラス面
との固着バインダー機能とガラスへのぬれ性（均一塗膜
層の形成を目的）を向上させる機能を付与したものであ
る。BEST MODE FOR CARRYING OUT THE INVENTION With further reference to the present invention,
The above-mentioned special coating layer is formed on the surface of glass used for various purposes, and the oxide particles having photocatalytic activity come into contact with the outside air to form a surface layer that brings organic matter decomposing ability and hydrophilicity. . Therefore, the dirt attached to the surface of the glass is decomposed and can be easily washed with water. That is, this coating layer provides an antifouling function and hydrophilicity due to the photocatalytic action, and further has the function of a binder binding between the photocatalyst and the glass surface by the coating layer and the wettability to glass (for forming a uniform coating layer) It has a function to improve it.
【０００９】更に具体的には、ガラスの表面に形成する
塗装層は、光触媒機能を有さないアモルファス型過酸化
チタンからなる第１層と、光触媒能を有する光触媒体か
らなる第２層（光触媒層）である。そして、その塗工性
をよくするため、好ましくはガラス側にコロナ放電処理
等を行ってぬれ性を改良し、更なる性能を向上させたも
のである。More specifically, the coating layer formed on the surface of the glass is a first layer made of amorphous titanium peroxide having no photocatalytic function and a second layer (photocatalyst having a photocatalytic function). Layer). Then, in order to improve its coatability, preferably the glass side is subjected to corona discharge treatment or the like to improve the wettability and further improve the performance.
【００１０】第１塗膜層を構成するアモルファス型過酸
化チタンＴｉＯ3 やアモルファス型酸化チタンＴｉＯ2
は、紫外線によって光励起して光触媒能を有するアナタ
ーゼ型酸化チタンやルチル型酸化チタンとは異なり光触
媒機能はない。これら光触媒機能を有さないアモルファ
ス型チタン酸化物の中でも、水を溶媒とするアモルファ
ス型過酸化チタンゾルが膜形成性等の点から好ましい。
かかる塗装層を構成する場合、ノニオン系界面活性（花
王株式会社製「クリンスル」、アニオン系界面活性剤
（ライオン株式会社製「サンノール」）等の界面活性
剤、或いは親水剤としては、ｎーメチルピロリドンやコ
ロイダルシリカ等の二酸化珪素、シロキサン類化合物、
水ガラス等のケイ素酸化物の含有剤が挙げられる。Amorphous titanium peroxide TiO 3 and amorphous titanium oxide TiO 2 forming the first coating layer
Has no photocatalytic function, unlike anatase-type titanium oxide and rutile-type titanium oxide, which have photocatalytic activity when photoexcited by ultraviolet rays. Among these amorphous titanium oxides having no photocatalytic function, amorphous titanium peroxide sol using water as a solvent is preferable from the viewpoint of film forming property and the like.
In the case of forming such a coating layer, as nonionic surfactants (“Krinsuru” manufactured by Kao Co., Ltd., anionic surfactants (“SANNOL” manufactured by Lion Co., Ltd.)) or hydrophilic agents, n-methyl is used. Silicon dioxide such as pyrrolidone and colloidal silica, siloxane compounds,
Examples include silicon oxide containing agents such as water glass.
【００１１】このアモルファス型過酸化チタンゾルの製
造例としては、例えば、四塩化チタンＴｉＣｌ4 等のチ
タン塩水溶液に、例えば、水酸化ナトリウム等のアルカ
リを加えて生成された無定型の水酸化チタンＴｉ（Ｏ
Ｈ）4 を洗浄・分離した後、これを過酸化水素水で処理
することにより、アモルファス形態の過酸化チタン液を
得る。上記アモルファス型過酸化チタンゾルは常温では
アモルファス状態で、未だアナターゼ型酸化チタンには
結晶化していないため、密着性に優れ、膜生成性が高
く、均一でフラットな薄膜を形成することができ、乾燥
皮膜は水に溶けないという性質の他に、親水機能性が付
与され、かつ、光触媒に対して安定であるという特性を
有する。An example of the production of this amorphous titanium peroxide sol is amorphous titanium hydroxide Ti produced by adding an alkali such as sodium hydroxide to an aqueous solution of a titanium salt such as titanium tetrachloride TiCl 4. (O
After H) 4 is washed and separated, it is treated with hydrogen peroxide solution to obtain an amorphous titanium peroxide solution. The above amorphous type titanium peroxide sol is in an amorphous state at room temperature and has not yet been crystallized in anatase type titanium oxide, so that it has excellent adhesion, high film-forming property, and can form a uniform and flat thin film, and can be dried. In addition to the property that the film is not soluble in water, it has hydrophilic properties and is stable to the photocatalyst.
【００１２】更に、防汚機能を相乗させるため、光触媒
機能を有する光触媒体を含有させたもので、紫外線照射
時には優れた親水機能と光触媒による防汚磯能とを有
し、紫外線非照射時には光触媒による防汚機能は発揮し
得ないが優れた親水機能を有するという特徴をもつ。即
ち、この光触媒能を有する光触媒体を含有する塗装層を
備えたガラスは、紫外線照射時には優れた親水性と光触
媒による防汚機能とを有し、紫外線の非照射時に光触媒
による防汚機能は発揮し得ないが、優れた親水機能を有
するという特徴をもつ。Furthermore, in order to make the antifouling function synergistic, a photocatalyst having a photocatalytic function is contained, and it has an excellent hydrophilic function at the time of ultraviolet irradiation and an antifouling property by the photocatalyst, and a photocatalyst at the time of non-irradiation of the ultraviolet. Although it cannot exhibit the antifouling function, it has an excellent hydrophilic function. That is, the glass having a coating layer containing a photocatalyst having this photocatalytic activity has excellent hydrophilicity and antifouling function due to the photocatalyst when irradiated with ultraviolet rays, and exhibits the antifouling function due to the photocatalyst when not irradiated with ultraviolet rays. Although not possible, it is characterized by having an excellent hydrophilic function.
【００１３】ここで光触蝶とはその結晶の伝導帯と価電
子帯との間のエネルギーギャップよりも大きなエネルギ
ーの光を照射したときに価電子帯中の電子の励起が生じ
て伝導電子と正孔を生成しうる物質をいい、上記活性化
された光触媒体が空気中の水分や酸素から活性酸素を作
り出し、この活性酸素により空気中の有機物や無機ガス
と反応する。光触媒酸化物としてはアナターゼ型酸化チ
タン、ルチル型酸化チタン、酸化亜鉛、酸化錫、三酸化
ニビスマス等の酸化物が用いられる。中でもゾル状のア
ナターゼ型酸化チタンＴｉＯ2 が好ましい。ゾル状のも
のは接触する相手側が親水性であれば、極めて平滑な面
を構成することとなるからである。Here, the photocatalyst is a conduction electron due to the excitation of electrons in the valence band when irradiated with light having an energy larger than the energy gap between the conduction band and the valence band of the crystal. A substance capable of generating holes. The activated photocatalyst produces active oxygen from moisture and oxygen in the air, and the active oxygen reacts with organic substances and inorganic gas in the air. As the photocatalyst oxide, oxides such as anatase type titanium oxide, rutile type titanium oxide, zinc oxide, tin oxide and nibismuth trioxide are used. Of these, sol-like anatase type titanium oxide TiO 2 is preferable. This is because the sol-like material forms an extremely smooth surface if the contacting side is hydrophilic.
【００１４】光触媒体の好ましい材料としては、光触媒
機能を有するアナターゼ型酸化チタンやルチル型酸化チ
タン等を含有する光触媒体が用いられるが、光触媒機能
を有さないアモルファス型過酸化チタンゾル等と、上記
光触媒機能を有する光触媒体との混合物を含有したもの
である。As a preferable material of the photocatalyst, a photocatalyst containing anatase type titanium oxide or rutile type titanium oxide having a photocatalytic function is used, and an amorphous titanium peroxide sol having no photocatalytic function, It contains a mixture with a photocatalyst having a photocatalytic function.
【００１５】光触媒の光励起に用いる光源としては太陽
光がそのまま利用できる。そして、光励起に応じて基材
表面が親水化されるためには、励起光の照度は０．００
１ｍｗ／ｃｍ2 以上、好ましくは０．０１ｍｗ／ｃｍ2
以上、更に好ましくは０．１ｍｗ／ｃｍ2 以上とするの
がよい。As the light source used for photoexcitation of the photocatalyst, sunlight can be used as it is. And, in order to make the surface of the base material hydrophilic in response to photoexcitation, the illuminance of the excitation light is 0.00
1 mw / cm 2 or more, preferably 0.01 mw / cm 2
More preferably, it is 0.1 mw / cm 2 or more.
【００１６】ここで、光触媒性酸化物粒子が外気と接す
るように霧出した親水性を呈する塗装層は、スプレー
法、ディップ法、フローコーティング法、ロール法、刷
毛塗り等の公知の方法が採用される。形成された塗膜層
の膜厚は、０．０５〜０．５μｍ、好ましくは０．０８
〜０．４μｍ、更に好ましくは０．１〜０．２μｍであ
る。この範囲では光の乱反射に起因する白濁を防止でき
実質的に透明となり、表面層の発色を防止することがで
きる。更に、薄膜とすればそれだけ耐摩耗性が向上す
る。尚、あまり薄くなると塗りむらが生じ、コーティン
グされていないガラス表面が存在することとなってしま
う。尚、表面層にはＡｇ、Ｃｕ、Ｚｎのような金属を添
加することができ、これによって抗菌効果をもたらすこ
とも可能となる。又、Ｐｔ、Ｐｄ、Ｒｕ、Ｒｈ、Ｔｒの
ような白金族の金属を添加することもでき、この場合に
は光触媒の活性を増強できることとなり、汚れの分解、
有害臭気や悪臭の分解をもたらすこととなる。Here, as the hydrophilic coating layer in which the photocatalytic oxide particles are sprayed so as to come into contact with the outside air, a known method such as a spray method, a dip method, a flow coating method, a roll method or a brush coating method is adopted. To be done. The thickness of the formed coating layer is 0.05 to 0.5 μm, preferably 0.08.
˜0.4 μm, more preferably 0.1 to 0.2 μm. In this range, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent, so that coloration of the surface layer can be prevented. Furthermore, the use of a thin film improves wear resistance accordingly. If it becomes too thin, uneven coating will occur, and there will be an uncoated glass surface. In addition, a metal such as Ag, Cu, or Zn can be added to the surface layer, which can also bring about an antibacterial effect. Further, a platinum group metal such as Pt, Pd, Ru, Rh, Tr can be added, and in this case, the activity of the photocatalyst can be enhanced, and the decomposition of dirt,
This will lead to the decomposition of harmful odors and malodors.
【００１７】尚、ガラスの表面と塗膜層との積層には、
両者が完全に行われなくてはならないが、ガラスの表面
に、コロナ放電処理、紫外線処理、プラズマ処理、オゾ
ン処理等を施して、塗膜層に対してぬれ特性及び／又は
反応性を向上させることが好ましい。In addition, for the lamination of the glass surface and the coating layer,
Both must be completely performed, but the glass surface is subjected to corona discharge treatment, ultraviolet treatment, plasma treatment, ozone treatment, etc. to improve the wetting property and / or reactivity with respect to the coating layer. It is preferable.
【００１８】尚、コロナ放電処理等による当該表面の親
水化は、水の接触角は１０〜４０度程度がよい。４０度
以上であるとこの上に塗布される水溶液をはじいて均一
な塗膜を得ることが難しくなり、一方、１０度以上であ
れば水溶液を十分に塗膜することができるからである。In order to make the surface hydrophilic by corona discharge treatment or the like, the contact angle of water is preferably about 10 to 40 degrees. When it is 40 degrees or more, it becomes difficult to repel the aqueous solution applied thereon to obtain a uniform coating film, while when it is 10 degrees or more, the aqueous solution can be sufficiently coated.
【００１９】ここでコロナ放電処理を説明する。即ち、
被処理物であるガラス基材の表面にコロナ放電処理を行
う。かかる被処理面は、コロナ放電による電子の衝突や
二次的に発生するオゾンや紫外線の作用により、反応性
の高い活性基が発生するので、上記処理面のぬれ特性や
反応性を向上させることができる。Here, the corona discharge treatment will be described. That is,
Corona discharge treatment is performed on the surface of the glass substrate that is the object to be treated. On the surface to be treated, an active group having high reactivity is generated by collision of electrons due to corona discharge and the action of ozone or ultraviolet rays generated secondarily, so that the wettability and reactivity of the treated surface should be improved. You can
【００２０】上記コロナ放電処理装置２０は、図１に示
すように、上記被処理面１０Ｓに近接して設置される第
１の電極２１と、上記第１の電極２１と被処理物１０に
対して同じ側に、上記第１の電極２１に近接して設置さ
れた第２の電極２２との間に、高周波発振器２３Ａと高
圧トランス２３Ｂとを備えた高電圧発生装置２３によ
り、高電庄の高周波電圧を印加して上記電極２１、２２
間にコロナ放電を発生させるもので、具体的には、上記
第１の電極２１は、被処理面１０Ｓを回転しながら移動
するロール状の被覆部材２４により被覆されたステンレ
ス製棒から構成される。又、第２の電極２２はステンレ
ス製の平板から構成され、上記被覆部材２４の回転に伴
って、上記第１の電極２１と所定の距離を保持しながら
被処理面１０Ｓ上を移動する。従って、上記第１の電極
２１と第２の電極間でコロナ放電を発生させながら、上
記第１の電極２１と第２の電極を被処理面１０Ｓ上に沿
って移動させることにより、被処理面１０Ｓを均一にコ
ロナ放電処理することができる。尚、被処理物を互いに
対向する放電電極と対向電極との間に設置するタイプの
コロナ放電処理装置を用いてもよいことは勿論である。As shown in FIG. 1, the corona discharge treatment apparatus 20 is provided with respect to the first electrode 21 installed near the surface 10S to be treated, the first electrode 21 and the object 10 to be treated. On the same side, a high voltage generator 23 including a high frequency oscillator 23A and a high voltage transformer 23B is provided between the first electrode 21 and a second electrode 22 which is installed close to the first electrode 21. Applying a high frequency voltage to the electrodes 21, 22
Corona discharge is generated between them. Specifically, the first electrode 21 is composed of a stainless rod covered with a roll-shaped covering member 24 that moves while rotating the surface to be processed 10S. . The second electrode 22 is composed of a flat plate made of stainless steel, and moves on the surface 10S to be processed while keeping a predetermined distance from the first electrode 21 as the covering member 24 rotates. Therefore, the corona discharge is generated between the first electrode 21 and the second electrode while the first electrode 21 and the second electrode are moved along the surface 10S to be processed, Corona discharge treatment can be performed uniformly on 10S. Needless to say, a corona discharge treatment device of the type in which the object to be treated is installed between the discharge electrode and the counter electrode facing each other may be used.
【００２１】次いで、上記コロナ放電処理した被処理面
に防汚剤を塗布して防汚層を形成する。本発明では、上
記防汚剤として、水とチタン酸化物とを含む水系の防汚
剤を用いて形成することが推奨される。Then, an antifouling agent is applied to the treated surface subjected to the corona discharge treatment to form an antifouling layer. In the present invention, it is recommended to use an aqueous antifouling agent containing water and titanium oxide as the antifouling agent.
【００２２】この防汚層１２としては、例えば、上記コ
ロナ放電処理された被処理面１０Ｓ上に形成された過酸
化チタン層（第１塗膜層）と、上記過酸化チタン層上に
形成された酸化チタン層（第２塗膜層）から構成され
る。即ち、上記過酸化チタン層は、光触媒能を有さない
アモルフアス型過酸化チタンからなり、場合によっては
アモルフアス型酸化チタンとの混合物を含有する光触媒
機能を有さないアモルフアス型過酸化チタン（ＴｉＯ
3 ）から形成され、界面活性剤及び／又は親水剤とを含
有していてもよい。The antifouling layer 12 is formed, for example, on the titanium peroxide layer (first coating layer) formed on the corona discharge-treated surface 10S and on the titanium peroxide layer. And a titanium oxide layer (second coating layer). That is, the titanium peroxide layer is composed of amorphous titanium peroxide having no photocatalytic activity, and in some cases, contains a mixture with amorphous titanium oxide and does not have a photocatalytic function.
3 ) and may contain a surfactant and / or a hydrophilic agent.
【００２３】酸化チタン層は光触媒機能を有するアナタ
ーゼ型酸化チタン（ＴｉＯ2 ）やルチル型酸化チタン
（ＴｉＯ2 ）等の光触媒体から形成されるが、光触媒機
能を有さないアモルフアス型過酸化チタンゾル等と、上
記光触媒機能を有する光触媒体との混合物を含有したも
のであってもよい。かかるコロナ放電処理した後に塗布
して形成した上記の第１及び第２塗膜層は、ぬれ性も高
く、又、接触角も小さいので、優れた防汚効果を得るこ
とができる。[0023] While titanium oxide layer is formed from a photocatalyst such as an anatase type titanium oxide (TiO 2) and rutile-type titanium oxide having a photocatalytic function (TiO 2), no photocatalytic function Amorufuasu titanium peroxide sol and the like And a mixture of the above-mentioned photocatalyst having a photocatalytic function. The above-mentioned first and second coating layers formed by coating after such corona discharge treatment have high wettability and a small contact angle, so that an excellent antifouling effect can be obtained.
【００２４】本発明における表面処理の第２は、紫外線
処理を行うことで被処理面（通常は樹脂表面）を親水化
するものであり、その紫外線の波長が１５０〜３６５ｎ
ｍであることが好ましい。波長が３６５ｎｍ以上の紫外
線では、被処理面の親水化を十分に行うことができず、
一方、広範囲で使用されている紫外線ランプから１５０
ｎｍ以下の波長を得ることは困難だからである。更に、
上記紫外線処理をする際に、空気、水蒸気、オゾン雰囲
気下で行うことが好ましく、空気中の酸素やオゾン、水
を反応させることで、被処理面にカルボニル基、カルボ
キシル基、水酸基等を生成させ、被処理面を親水化させ
ることによって水系塗料を均一かつ強固に塗工しやすく
するからである。特に、被処理面に水を付着させ、紫外
線処理を行うと表面の親水化効率を上げることができ
る。The second surface treatment in the present invention is to make the surface to be treated (usually a resin surface) hydrophilic by performing an ultraviolet treatment, and the wavelength of the ultraviolet rays is 150 to 365 n.
It is preferably m. UV rays having a wavelength of 365 nm or more cannot sufficiently hydrophilize the surface to be treated,
On the other hand, from the widely used UV lamps 150
This is because it is difficult to obtain a wavelength of nm or less. Furthermore,
When the above-mentioned ultraviolet treatment, air, water vapor, it is preferable to be carried out in an ozone atmosphere, by reacting oxygen and ozone in the air, water to produce a carbonyl group, a carboxyl group, a hydroxyl group, etc. on the surface to be treated. By making the surface to be treated hydrophilic, the water-based paint can be applied uniformly and firmly. In particular, if water is adhered to the surface to be treated and UV treatment is carried out, the hydrophilicity of the surface can be increased.
【００２５】紫外線処理は被処理面を洗浄した後に処理
を行うのが好ましく、被処理面は紫外線処理による電子
の衝突等により反応性の高い活性基が発生するので、ぬ
れ性や反応性を向上させることができることになる。こ
のため、接着性が極めて向上することとなる。The UV treatment is preferably carried out after cleaning the surface to be treated. Since the active group having high reactivity is generated on the surface to be treated due to collision of electrons due to the UV treatment, wettability and reactivity are improved. You will be able to Therefore, the adhesiveness is extremely improved.
【００２６】紫外線処理装置に用いられる紫外線光源と
しては、低圧紫外線ランプが好ましい。低圧紫外線ラン
プは、２５４ｎｍと１８４．９ｎｍの光を主成分とし
た、短波長がピークとなっており、照射されるエネルギ
ーは非常に大きく、基材の親水化に適しているからであ
る。即ち、被処理面に対し所定の距離を保ちつつ紫外線
を照射していくことにより、被処理面を均一に処理する
ことができる。A low-pressure ultraviolet lamp is preferable as the ultraviolet light source used in the ultraviolet processing apparatus. This is because the low-pressure ultraviolet lamp is mainly composed of light of 254 nm and 184.9 nm, has a short wavelength, and has a very large irradiation energy, and is suitable for making the base material hydrophilic. That is, the surface to be processed can be uniformly processed by irradiating the surface to be processed with ultraviolet rays while maintaining a predetermined distance.
【００２７】上記被処理面は、前記コロナ放電処理と同
じくぬれ特性や反応性が向上する。水の接触角について
も同様である。又、既に説明した防汚層の形成等も前例
と同様にして行うことができることは言うまでもない。The surface to be treated has improved wettability and reactivity as in the corona discharge treatment. The same applies to the contact angle of water. Needless to say, the formation of the antifouling layer, etc., which has already been described, can be performed in the same manner as in the previous example.
【００２８】本発明の第３の表面処理手段として、プラ
ズマ放電処理が採用されるが、この場合、活性ガス種中
で行うのがよく、ガス種がＡｒ、０2 、ＣＯ、ＣＯ2 、
Ｎ2、ＮＯ、ＮＯ2 、ＮＨ3 、空気（０2 ＋ＣＯ2 ＋Ｎ2
等）が用いられ、極性基を表面に導入できるものであ
れば特に限定はない。望ましくは、Ａｒ、０2 、Ｎ2が
よい。プラズマ処理する際のチヤンバー内の真空度は１
０〜０．１ｔｏｒｒ、好ましくは１〜０．１ｔｏｒｒで
ある。これにより、被処理面を均一に処理することがで
きる。処理時間は１〜６０分である。As the third surface treatment means of the present invention, plasma discharge treatment is adopted. In this case, it is preferable to perform it in an active gas species, and the gas species are Ar, 0 2 , CO, CO 2 ,
N 2 , NO, NO 2 , NH 3 , air (0 2 + CO 2 + N 2
Etc. are used and there is no particular limitation as long as a polar group can be introduced on the surface. Desirably, Ar, O 2 and N 2 are good. The degree of vacuum in the chamber during plasma processing is 1
It is 0 to 0.1 torr, preferably 1 to 0.1 torr. As a result, the surface to be processed can be uniformly processed. The processing time is 1 to 60 minutes.
【００２９】アーク放電の発生の際に生じる電離したガ
スの電子による自由電子とそれによる陽イオン及び未だ
電離されていない中性ガスからなり、正電荷と負電荷の
夫々の密度が等しく電気的中性状態に有るガスをプラズ
マというが、被処理面はこのプラズマ放電処理による電
子の衝突や、処理雰囲気中に含まれる気体の作用によ
り、反応性の高い活性基が発生するので、ぬれ性や反応
性を向上させることができるものである。それにより、
前例の処理と同じくこの層上に形成される表面層との接
着性が極めて向上することとなる。It consists of free electrons due to the electrons of the ionized gas generated when the arc discharge occurs, cations due to the electrons, and neutral gas that has not been ionized, and the positive and negative charges have the same density. The gas in the neutral state is called plasma, but the surface to be treated has a highly reactive active group due to the collision of electrons due to this plasma discharge treatment and the action of the gas contained in the treatment atmosphere. It is possible to improve the property. Thereby,
Similar to the treatment of the previous example, the adhesion with the surface layer formed on this layer is extremely improved.
【００３０】ここでプラズマ放電処理の概要を述べる
と、ガラス基材の被処理面をプラズマ放電処理すると、
プラズマ放電による電子の衝突や二次的に発生するオゾ
ンや紫外線の作用により、反応性の高い活性基が発生す
るので、被処理面のぬれ特性や反応性を向上させること
ができる。水の接触角の関係も前記例と同様である。勿
論、第１塗膜層及び第２塗膜層の形成も前述したと同様
に形成されることは言うまでもない。The plasma discharge treatment will be outlined below. When the surface of the glass substrate to be treated is subjected to plasma discharge treatment,
Highly reactive active groups are generated by the collision of electrons due to plasma discharge and the action of ozone and ultraviolet rays that are secondarily generated, so that the wettability and reactivity of the surface to be treated can be improved. The relationship of the contact angle of water is the same as in the above example. Of course, it goes without saying that the first coating layer and the second coating layer are also formed in the same manner as described above.
【００３１】図２はプラズマ放電処理装置４０の概要も
示すが、チャンバー４１内に被処理面１０Ｓに近接して
設置される第１の電極４２と、上記第１の電極４２と上
記被処理面１０Ｓに対して反対側に設置された第２の電
極４３と、高圧トランス４４を備えた電源装置４５を備
えたものである。チヤンバー４１は真空ポンプ４６と気
体ボンべ４７を備え、チヤンバー４１内の雰囲気ガスを
入れ替えるものであり、電極４２と４３との間に高電圧
を印加して上記電極４２、４３間にプラズマ放電を発生
させて、気体を活性化させて被処理面１０Ｓを均一に処
理するものである。図２における被処理面１０Ｓへの防
汚層も同様である。FIG. 2 also shows an outline of the plasma discharge processing apparatus 40. The first electrode 42 installed in the chamber 41 close to the surface 10S to be processed, the first electrode 42 and the surface to be processed. It is provided with a second electrode 43 installed on the opposite side of 10S and a power supply device 45 having a high voltage transformer 44. The chamber 41 is equipped with a vacuum pump 46 and a gas cylinder 47 to replace the atmospheric gas inside the chamber 41. A high voltage is applied between the electrodes 42 and 43 to generate plasma discharge between the electrodes 42 and 43. It is generated to activate the gas and uniformly process the surface 10S to be processed. The same applies to the antifouling layer on the surface 10S to be processed in FIG.
【００３２】尚、オゾン処理についても特に言及はしな
いが、適当な容量のオゾナイザーを用いて被処理面を処
理し、水の接触角を上記のような関係とする処理を行う
こととなる。Although the ozone treatment is not particularly mentioned, the surface to be treated is treated by using an ozonizer having an appropriate capacity, and the treatment is performed so that the contact angle of water has the above relationship.
【００３３】第１塗膜層及び第２塗膜層（防汚剤層・光
触媒層）の厚さについて言えば、第１塗膜層としての
（ＴｉＯ３保護層）は、０．０２〜４．０μｍ、好まし
くは０．１〜２．０μｍ、更に好ましくは０．２〜０．
５μｍの厚さ、第２塗膜層である光触媒としてのアナタ
ーゼ型ＴｉＯ２層は、０．０２〜４．０μｍ、好ましく
は０．１〜２．０μｍ、更に好ましくは０．３〜１．０
μｍの厚さである。いずれも余り薄過ぎるとピンホール
等の塗装の欠陥等の不具合が出やすくなり、厚過ぎても
光の干渉による外観の不具合が生じてしまう。As for the thickness of the first coating layer and the second coating layer (antifouling agent layer / photocatalyst layer), the (TiO3 protective layer) as the first coating layer has a thickness of 0.02-4. 0 μm, preferably 0.1 to 2.0 μm, more preferably 0.2 to 0.
The anatase-type TiO2 layer as a photocatalyst that is a second coating layer having a thickness of 5 μm has a thickness of 0.02 to 4.0 μm, preferably 0.1 to 2.0 μm, and more preferably 0.3 to 1.0.
The thickness is μm. If both are too thin, defects such as coating defects such as pinholes are likely to occur, and if they are too thick, defects in appearance due to light interference occur.
【００３４】従来の光触媒層は、シリコン等の中にアナ
ターゼ型ＴｉＯ2 粒子を分散させた塗装層を直接有機物
表面に塗るものであったが、ＴｉＯ2 が母材を分解して
しまうため触媒効果が弱く、光触媒能の持続は比較的短
かった。しかるに、本発明の場合には、例えばコロナ放
電処理をすることによって基材との間で接着性が極めて
良好となり、しかも第１塗装層は基材を分解する機能は
ほとんどなく、第２塗装層の光分解能は基材を分解する
おそれもなく、これらの塗装層が劣化することもないの
で親水能や光分解能が長い間持続することとなる。In the conventional photocatalyst layer, a coating layer in which anatase-type TiO 2 particles are dispersed in silicon or the like is directly applied to the surface of an organic material, but since TiO 2 decomposes the base material, a catalytic effect is obtained. Was weak, and the duration of photocatalytic activity was relatively short. However, in the case of the present invention, for example, by performing corona discharge treatment, the adhesiveness with the base material becomes extremely good, and the first coating layer has almost no function of decomposing the base material, and the second coating layer The optical resolution of No. 1 does not cause the base material to be decomposed and these coating layers are not deteriorated, so that the hydrophilicity and the optical resolution are maintained for a long time.
【００３５】防汚効果を発現するためのガラスの表面の
水の接触角は、４０度以下、好ましくは２５度以下、更
に好ましくは１０度以下である。４０度より大きい場合
には、ガラスの凸部等水の流れにくいところで雨だれが
残ることがあり、十分な防汚効果が得られない。The contact angle of water on the surface of the glass for exhibiting the antifouling effect is 40 degrees or less, preferably 25 degrees or less, and more preferably 10 degrees or less. If it is greater than 40 degrees, raindrops may remain in places where water does not easily flow, such as convex portions of glass, and a sufficient antifouling effect cannot be obtained.
【００３６】[0036]
【実施例】以下、実施例をもって更に説明する。（コロ
ナ放電処理の例）実施例として、ガラスの表面にコロナ
放電処理を施した（水の接触角は２０度）。その後、第
１塗膜層としてアモルフアス型過酸化チタンゾル（ＴＫ
−１００、０．８５重量％の過酸化チタンを含む水溶
液、（ＴＡＯ社製））を均一にスプレー塗布し、室温に
て乾燥し、これを３回繰り返した。更に第２塗膜層（光
触媒層）としてその上にアモルフアス型過酸化チタンゾ
ルとアナターゼ型酸化チタンの混合液（ＴＡＫ−７０、
１．７０重量％の酸化チタンと過酸化チタンを含む水溶
液、酸化チタン：過酸化チタン＝７：３（ＴＡＯ社
製））を均一にスプレー塗布し、室温で乾燥し、これを
３回繰り返した。その後、１４０℃で１時間焼き付け、
表面に親水性を備えたガラス構造体を得た。コロナ放電
処理した場合、水の接触角は小さく、ぬれ性も高いの
で、優れた塗工性を得ることができる。又、塗工性の向
上により各塗膜層が強固に基材に固定し、優れた防汚効
果を得ることとなる。この効果はいずれの処理によって
も同様に発揮される。EXAMPLES Hereinafter, examples will be further described. (Example of corona discharge treatment) As an example, a glass surface was subjected to corona discharge treatment (contact angle of water was 20 degrees). Then, as the first coating layer, amorphous type titanium peroxide sol (TK
An aqueous solution containing -100 and 0.85% by weight of titanium peroxide (manufactured by TAO) was uniformly spray-coated, dried at room temperature, and this was repeated 3 times. Further, as a second coating layer (photocatalyst layer), a mixed liquid of an amorphous type titanium peroxide sol and anatase type titanium oxide (TAK-70,
An aqueous solution containing 1.70% by weight of titanium oxide and titanium peroxide, titanium oxide: titanium peroxide = 7: 3 (manufactured by TAO) was uniformly spray-coated, dried at room temperature, and this was repeated 3 times. . After that, bake at 140 ℃ for 1 hour,
A glass structure having a hydrophilic surface was obtained. In the case of corona discharge treatment, the contact angle of water is small and the wettability is high, so that excellent coatability can be obtained. Further, by improving the coatability, each coating layer is firmly fixed to the substrate, and an excellent antifouling effect is obtained. This effect is similarly exhibited by any processing.
【００３７】図３は得られたガラス構造体の断面図であ
り、５１はガラス基材（１０）、５２はガラス被処理面
（１０Ｓ）、５３は第１塗膜層、５４は第２塗膜層であ
る。尚、図示はしないが、必要であれば、ガラスの表裏
両面に各塗膜層を形成できることは言うまでもない。FIG. 3 is a cross-sectional view of the obtained glass structure, in which 51 is the glass substrate (10), 52 is the glass treated surface (10S), 53 is the first coating layer, and 54 is the second coating. It is a membrane layer. Although not shown, it goes without saying that each coating layer can be formed on both the front and back surfaces of the glass, if necessary.
【００３８】比較例として、表面に上記塗膜層を形成し
なかったガラスを用いた。尚、水の接触角は６０度であ
り、上記第１及び第２塗膜層を塗工してもはじいてしま
い膜の形成はできなかった。As a comparative example, a glass on which the coating layer was not formed was used. The contact angle of water was 60 degrees, and even if the first and second coating layers were applied, they were repelled and a film could not be formed.
【００３９】（比較試験・１）実施例及び比較例のガラ
ス構造体をもって窓枠に嵌め込み、被処理面を屋外側と
して１２か月放置し、色差計をもって色差を測定した。
実施例のガラス構造体では６．２（△Ｅ）、比較例の場
合は１５（△Ｅ）であった。比較例ではその表面に油状
の黒い付着物が多く見られた。尚、色差の測定はミノル
タＣＭ−５０８ｄを用いて測定した。測定方法は汚れる
前のＥ0 を測定しておき、汚れた後のＥｌとの差△Ｅの
値が大きい程汚れていることを示す。(Comparison Test 1) The glass structures of Examples and Comparative Examples were fitted in a window frame, left to stand for 12 months with the surface to be treated outdoors, and the color difference was measured with a color difference meter.
The glass structure of the example had 6.2 (ΔE), and the glass structure of the comparative example had 15 (ΔE). In the comparative example, many oily black deposits were found on the surface. The color difference was measured using Minolta CM-508d. As a measuring method, E 0 before being soiled is measured, and the larger the difference ΔE with the El after soiling is, the more soiling is.
【００４０】（プラズマ放電処理の例）実施例として、
ガラス基材の表面にプラズマ放電処理を施した。即ち、
パネルをエタノールにて脱脂しチヤンバー内に入れ、チ
ヤンバー内を真空引き後、０2、Ｎ2 、Ａｒガスを夫々
充填し圧力１ｔｏｒｒとし、１００Ｗの電圧を１０分か
け放電処理した。(Example of Plasma Discharge Treatment) As an example,
Plasma discharge treatment was applied to the surface of the glass substrate. That is,
The panel was degreased with ethanol and placed in the chamber, and the chamber was evacuated, then filled with 0 2 , N 2 and Ar gas, respectively, to a pressure of 1 torr, and discharged at a voltage of 100 W for 10 minutes.
【００４１】夫々のガラス構造体の水の接触角は夫々２
３度、３２度、３５度であった。第１塗膜層の塗工及び
第２塗膜層の塗工は前例と同様である。ＴｉＯ2 の塗工
性は実施例の場合は容易である。The water contact angles of the glass structures are 2 respectively.
It was 3 degrees, 32 degrees, and 35 degrees. The coating of the first coating layer and the coating of the second coating layer are the same as in the previous example. The coating property of TiO 2 is easy in the case of the examples.
【００４２】（比較試験・１）実施例及び比較例のガラ
スを窓枠内に嵌め込み、これを１２か月屋外に放置し、
色差計をもって色差を測定した。実施例のものは、夫々
１、６、８（△Ｅ）であった。(Comparison Test 1) The glass of the example and the comparative example were fitted in a window frame and left outdoors for 12 months,
The color difference was measured with a color difference meter. In the examples, the values were 1, 6, and 8 (ΔE), respectively.
【００４３】（紫外線処理の例）実施例として、ガラス
基材の表面に紫外線処理を施した。即ち、ガラス基材表
面をエタノールにて脱脂し、センエンジニアリング社製
１１０Ｗ低庄紫外線ランプＳＵＶｌｌＯＧＳ−３６を用
いて、処理面と低庄紫外線ランプとの距離を１．５ｃｍ
に保って、常圧にて５分間、紫外線処理を行った。水の
接触角は２５度であった。各塗膜層の形成は前記と同様
に行った。(Example of Ultraviolet Treatment) As an example, the surface of a glass substrate was subjected to ultraviolet treatment. That is, the glass substrate surface was degreased with ethanol, and the distance between the treated surface and the low-pressure ultraviolet lamp was 1.5 cm using a 110 W low-pressure ultraviolet lamp SUVllOGS-36 manufactured by Sen Engineering Co., Ltd.
Then, UV treatment was carried out at normal pressure for 5 minutes. The contact angle of water was 25 degrees. The formation of each coating layer was performed as described above.
【００４４】（比較試験１：空気清浄化）いわゆる新建
材より発生するといわれているホルムアルデヒドガスの
分解性について試験を行った。初期ガスとして濃度１．
０ｐｐｍのガス（１０リットル）を作成した。本実施例
のガラスサンプルをもってホルムアルデヒドの分解につ
いて試験した。照射した紫外線ランプはＵＰＬＡＮＤ・
ＵＶＭ−２８を用い、サンプルまでの距離を５０ｍｍに
保ち、１時間照射した。一方、紫外線を全く照射せずに
１時間ホルムアルデヒド雰囲気中に放置した。(Comparative Test 1: Air Cleaning) A test was conducted on the decomposability of formaldehyde gas, which is said to be generated from so-called new building materials. Concentration as initial gas 1.
A 0 ppm gas (10 liters) was created. The glass samples of this example were tested for formaldehyde decomposition. The irradiated UV lamp is UPLAND.
Using UVM-28, the distance to the sample was kept at 50 mm and irradiation was carried out for 1 hour. On the other hand, it was left in a formaldehyde atmosphere for 1 hour without being irradiated with ultraviolet rays.
【００４５】測定の結果、前者の場合ではホルムアルデ
ヒドの濃度は０．０ｐｐｍであったが、後者の濃度は
０．６ｐｐｍであった。後者の試験より０．４ｐｐｍ分
がサンプルに吸収されることが分かるが、前者との差即
ち、０．６ｐｐｍのホルムアルデヒドはサンプルを紫外
線照射することによって分解されたことが証明される。
かかる大気中のガスの分解能はタバコの煙、ＮＯx 、Ｓ
Ｏx 、アンモニア、トリメチルアミン等の人体に有害と
いわれているガス体の分解も可能であることを示すもの
である。As a result of the measurement, the concentration of formaldehyde was 0.0 ppm in the former case, but the concentration of the latter was 0.6 ppm. The latter test shows that 0.4 ppm is absorbed by the sample, but it is proved that the difference from the former, that is, 0.6 ppm of formaldehyde was decomposed by irradiating the sample with ultraviolet rays.
The resolution of such atmospheric gases is determined by the smoke of cigarettes, NO x , S
O x, ammonia, and shows that it is possible decomposition of the gas body is said to be harmful to the human body trimethylamine.
【００４６】[0046]
【発明の効果】本発明はガラスの表面に光触媒性酸化物
により親水性を呈する表面層が形成されたことにより、
汚れ等がガラス表面に付着することがなくなり、その表
面は清浄な状態が保たれることとなった。又、室内の汚
れ物質を分解し、空気清浄化の効果が得られることとも
なった。そして、波及効果としては室内への紫外線カッ
トにも大きな効果をもたらされるものである。INDUSTRIAL APPLICABILITY According to the present invention, a surface layer having hydrophilicity is formed by a photocatalytic oxide on the surface of glass,
Dirt and the like did not adhere to the glass surface, and the surface was kept clean. In addition, it has also been possible to obtain the effect of air purification by decomposing indoor pollutants. And, as a ripple effect, a great effect can be brought also to the ultraviolet ray cut in the room.
【図１】図１は本発明のコロナ放電処理装置の構成を示
す図である。FIG. 1 is a diagram showing a configuration of a corona discharge treatment device of the present invention.
【図２】図２は本発明のプラズマ放電処理装置の構成を
示す図である。FIG. 2 is a diagram showing a configuration of a plasma discharge treatment apparatus of the present invention.
【図３】図３はガラス構造体の断面を示す図である。FIG. 3 is a view showing a cross section of a glass structure.
１０‥基材、 １０Ｓ‥処理面、 ２０‥コロナ放電処理装置、 ２１‥第１の電極、 ２２‥第２の電極、 ２３‥高電圧発生装置、 ２４‥ロール状の被覆部材、 ４０‥プラズマ放電処理装置、 ４１‥チヤンバー、 ４２‥第１の電極、 ４３‥第２の電極、 ４４‥高圧トランス、 ４５‥電源装置、 ４６‥真空ポンプ、 ４７‥気体ボンべ、 ５０‥ガラス構造体、 ５１‥ガラス基材（１０）、 ５２‥ガラス被処理面（１０Ｓ）、 ５３‥第１塗膜層、 ５４‥第２塗膜層。 10 ... Base material 10S: Processing surface, 20. Corona discharge treatment device, 21 ... the first electrode, 22 ... second electrode, 23. High voltage generator, 24 ... Roll-shaped covering member, 40 ... Plasma discharge treatment device, 41 ... Chamber, 42 ... the first electrode, 43 ... the second electrode, 44: High voltage transformer, 45: power supply, 46 ... vacuum pump, 47 ... Gas cylinder, 50: glass structure, 51 ... Glass base material (10), 52 ... Glass treated surface (10S), 53 ... the first coating layer, 54. Second coating layer.
フロントページの続き Ｆターム(参考） 4F100 AA21B AA21H AG00A BA02 BA03 BA05 BA06 BA10A BA10B CA18C CA30C CC00B CC00C EJ54 EJ55 EJ61 EJ64 GB07 GB32 JB05C JL06B JL08B YY00B 4G059 AA01 AB01 AC22 AC30 EA01 EA02 EA04 EA18 EB05 GA01 GA04 GA12 4G069 AA03 AA08 BA04B BA48A CA01 CA11 EA08 EC22Y ED02 FA03 FB24 Continued front page F-term (reference) 4F100 AA21B AA21H AG00A BA02 BA03 BA05 BA06 BA10A BA10B CA18C CA30C CC00B CC00C EJ54 EJ55 EJ61 EJ64 GB07 GB32 JB05C JL06B JL08B YY00B 4G059 AA01 AB01 AC22 AC30 EA01 EA02 EA04 EA18 EB05 GA01 GA04 GA12 4G069 AA03 AA08 BA04B BA48A CA01 CA11 EA08 EC22Y ED02 FA03 FB24
Claims (13)
ス構造であって、その少なくとも一方の表面に親水処理
を施し、当該処理面上に水系の防汚剤を塗工（第２塗膜
層）することを特徴とする防汚性ガラス。1. A glass structure used for homes or automobiles, at least one surface of which is subjected to hydrophilic treatment, and a water-based antifouling agent is applied to the treated surface (second coating layer). ) Antifouling glass characterized by being.
触媒体である請求項１記載の防汚性ガラス。2. The antifouling glass according to claim 1, wherein the water-based antifouling agent is a photocatalyst having photocatalytic activity.
ーゼ型酸化チタンである請求項２記載の防汚性ガラス。3. The antifouling glass according to claim 2, wherein the photocatalyst having photocatalytic activity is anatase type titanium oxide.
タンを含有する請求項３記載の防汚性ガラス。4. The antifouling glass according to claim 3, wherein the photocatalyst contains amorphous titanium peroxide.
防汚剤（第２塗膜層）との間に中間層（第１塗膜層）を
設けた請求項１乃至４いずれか１項記載の防汚性ガラ
ス。5. An intermediate layer (first coating layer) is provided between the surface of the glass subjected to the hydrophilic treatment and the antifouling agent (second coating layer). Antifouling glass as described in the item.
有さないアモルフアス型過酸化チタンである請求項１乃
至５いずれか１項記載の防汚性ガラス。6. The antifouling glass according to claim 1, wherein the intermediate layer (first coating layer) is amorphous titanium peroxide having no photocatalytic activity.
及び／又は親水剤を含有する請求項５又は６記載の防汚
性ガラス。7. The antifouling glass according to claim 5, wherein the intermediate layer (first coating layer) contains a surfactant and / or a hydrophilic agent.
０．０２〜４．０〃ｍである請求項１乃至７いずれか１
項記載の防汚性ガラス。8. The layer of the antifouling agent (second coating layer) has a thickness of 0.02 to 4.0 .mu.m.
Antifouling glass as described in the item.
０２〜４．０〃ｍである請求項１乃至８いずれか１項記
載の防汚性ガラス。9. The intermediate layer (first coating layer) has a thickness of 0.
The antifouling glass according to any one of claims 1 to 8, which has a thickness of 02 to 4.0 m.
請求項１乃至９いずれか１項記載の防汚性ガラス。10. The antifouling glass according to claim 1, wherein the hydrophilic treatment is corona discharge treatment.
る請求項１乃至９いずれか１項記載の防汚性ガラス。11. The antifouling glass according to claim 1, wherein the hydrophilic treatment is plasma discharge treatment.
項１乃至９いずれか１項記載の防汚性ガラス。12. The antifouling glass according to claim 1, wherein the hydrophilic treatment is an ultraviolet treatment.
項１乃至９いずれか１項記載の防汚性ガラス。13. The antifouling glass according to claim 1, wherein the hydrophilic treatment is ozone treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002111523A JP2003306347A (en) | 2002-04-15 | 2002-04-15 | Stain-proofing glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002111523A JP2003306347A (en) | 2002-04-15 | 2002-04-15 | Stain-proofing glass |
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| Publication Number | Publication Date |
|---|---|
| JP2003306347A true JP2003306347A (en) | 2003-10-28 |
Family
ID=29394286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108056A1 (en) * | 2004-05-06 | 2005-11-17 | Sustainable Titania Technology Inc. | Base protection method |
| WO2005110938A1 (en) * | 2004-05-19 | 2005-11-24 | Murakami Corporation | Anticlouding device, anticlouding mirror and electrochromic mirror |
| JP2007247011A (en) * | 2006-03-17 | 2007-09-27 | Okayama Prefecture | Method for hydrophilizing narrow channel |
| CN105254186A (en) * | 2015-10-29 | 2016-01-20 | 苏州市灵通玻璃制品有限公司 | Preparation method of self-cleaning glass |
-
2002
- 2002-04-15 JP JP2002111523A patent/JP2003306347A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005108056A1 (en) * | 2004-05-06 | 2005-11-17 | Sustainable Titania Technology Inc. | Base protection method |
| KR100849150B1 (en) * | 2004-05-06 | 2008-07-31 | 사스티나부르 . 테크노로지 가부시키가이샤 | Base protection method |
| WO2005110938A1 (en) * | 2004-05-19 | 2005-11-24 | Murakami Corporation | Anticlouding device, anticlouding mirror and electrochromic mirror |
| JP2007247011A (en) * | 2006-03-17 | 2007-09-27 | Okayama Prefecture | Method for hydrophilizing narrow channel |
| CN105254186A (en) * | 2015-10-29 | 2016-01-20 | 苏州市灵通玻璃制品有限公司 | Preparation method of self-cleaning glass |
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