JPH11256134A - Anti staining structure - Google Patents
Anti staining structureInfo
- Publication number
- JPH11256134A JPH11256134A JP10071188A JP7118898A JPH11256134A JP H11256134 A JPH11256134 A JP H11256134A JP 10071188 A JP10071188 A JP 10071188A JP 7118898 A JP7118898 A JP 7118898A JP H11256134 A JPH11256134 A JP H11256134A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- dirt
- matrix
- resin
- antifouling
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、屋外や屋内で付着
する種々物品に付着する汚れを防止する光触媒と樹脂を
用いた被覆構造体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating structure using a resin and a photocatalyst for preventing dirt from adhering to various articles adhering outdoors or indoors.
【０００２】[0002]
【従来の技術】光触媒を用いた防汚材料に関しては、光
触媒性酸化チタンを焼き付けたタイルやガラスが最近商
品化され、良好な防汚性が報告されている。このような
光触媒作用のある酸化チタンは、励起波長以下の紫外線
照射により、その表面に活性酸素を生成し、これによっ
て表面に付着した有機物質を分解し、汚れを防止するこ
とができる。しかしガラスやタイルのような耐熱性無機
物では光触媒の焼き付け加工が可能であるため、物品の
表面全面に酸化チタンで被覆することが可能であるが、
樹脂や金属等への応用の際には、光触媒粒子を樹脂バイ
ンダーと混合した塗料を用いて表面にコーティングする
必要がある。この場合バインダーも光触媒の有機物分解
作用を受けるため、光触媒分解を受けにくい難分解性の
樹脂を用いることが必要になる。特開平７−１７１４０
８号公報には、このような塗料として、光触媒とシリコ
ン系ポリマーやフッ素系ポリマーを光触媒と混合したも
のが開示されており、良好な脱臭性能を発現している。
しかし汚れ防止を目的とした場合では、塗料表面にバイ
ンダーの樹脂成分と光触媒が共に露出していることか
ら、光触媒粒子にたまたま付着した汚れは分解除去され
るが、バインダー上に付着堆積した汚れは分解されず残
存する問題点がある。このためバインダーの添加量は極
力少量に抑える必要があった。バインダーの添加量を減
らすことは、粒子状の光触媒が大部分を占めることにつ
ながり、塗膜が可とう性を失い、厚膜化が困難になった
り、耐久性信頼性に欠ける等の難点を引き起こす。現在
までのところ、このような問題を解決する防汚性の表面
構造は見出されていない。2. Description of the Related Art As for an antifouling material using a photocatalyst, tiles and glass baked with photocatalytic titanium oxide have recently been commercialized, and good antifouling properties have been reported. Such a photocatalytic titanium oxide generates active oxygen on the surface thereof by irradiation with ultraviolet light of an excitation wavelength or less, thereby decomposing an organic substance attached to the surface and preventing dirt. However, heat-resistant inorganic substances such as glass and tiles can be baked with a photocatalyst, so the entire surface of the article can be coated with titanium oxide.
In the case of application to a resin, a metal, or the like, it is necessary to coat the surface with a paint in which photocatalyst particles are mixed with a resin binder. In this case, since the binder also undergoes an organic substance decomposing action of the photocatalyst, it is necessary to use a hardly decomposable resin which is not easily subjected to photocatalytic decomposition. JP-A-7-17140
No. 8 discloses such a paint in which a photocatalyst and a silicon-based polymer or a fluorine-based polymer are mixed with a photocatalyst, and exhibits good deodorizing performance.
However, when the purpose is to prevent contamination, since the resin component of the binder and the photocatalyst are both exposed on the surface of the paint, the contamination that happens to adhere to the photocatalyst particles is decomposed and removed. There is a problem that remains without being decomposed. For this reason, it was necessary to suppress the addition amount of the binder as small as possible. Reducing the amount of binder added leads to a large portion of the particulate photocatalyst, which causes problems such as loss of flexibility of the coating film, difficulty in thickening the film, and lack of durability and reliability. cause. Until now, no antifouling surface structure has been found to solve such problems.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、必要
最小限の光触媒の添加量で、効率よく防汚効果を発現す
る表面構造を有する防汚構造体を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an antifouling structure having a surface structure capable of efficiently exhibiting an antifouling effect with a minimum necessary amount of a photocatalyst.
【０００４】[0004]
【課題を解決するための手段】本発明を概説すれば、本
発明は、表面がマトリックスと光触媒性半導体材料から
構成される構造体であって、前記構造体表面を構成する
マトリックスは、汚れをはじく性質を有し、且つ前記構
造体表面を構成する光触媒性半導体材料は、汚れを吸着
する性質を有し、前記構造体表面において、汚れが可動
な範囲に、光触媒が少量露出していることを特徴とする
防汚構造体に関する。SUMMARY OF THE INVENTION In general, the present invention is directed to a structure having a surface composed of a matrix and a photocatalytic semiconductor material, wherein the matrix constituting the surface of the structure is free of dirt. It has a repelling property, and the photocatalytic semiconductor material constituting the surface of the structure has a property of adsorbing dirt. On the surface of the structure, a small amount of the photocatalyst is exposed in a movable range of the dirt. The present invention relates to an antifouling structure characterized by the following.
【０００５】本発明者らは、防汚構造体の表面の大部分
を、防止したい汚れ成分をはじく性質のあるマトリック
スとすることにより、汚れ成分を構造体表面において移
動可能な状態とし、汚れ成分が移動可能な範囲に、汚れ
成分を吸着する性質のある光触媒を最小限配置すること
により、移動してきた汚れを吸着分解することで、効率
よく汚れを防止することができることを見出した。[0005] The present inventors have made most of the surface of an antifouling structure a matrix having a property of repelling a dirt component to be prevented, thereby making the dirt component movable on the surface of the structure, It has been found that, by disposing the photocatalyst having the property of adsorbing the dirt component at a minimum in the range in which the dirt can move, the dirt that has moved can be adsorbed and decomposed, thereby efficiently preventing the dirt.
【０００６】[0006]
【発明の実施の形態】以下、本発明を具体的に説明す
る。以下、本発明における好適な構成要件を列挙すると
下記のとおりである。 （１）前記構造体表面を構成するマトリックスが、はっ
水・はつ油性樹脂を含むものである。 （２）前記はっ水・はつ油性樹脂が、フッ素樹脂を含む
ものである。 （３）前記構造体表面を構成する光触媒性半導体材料
が、ＴｉＯ2 、ＺｎＯ、ＳｎＯ2 、ＳｒＴｉＯ3 、ＷＯ
3 、ＢｉＯ3 及びＦｅ2 Ｏ3 よりなる群から選択した１
種又は複数種組合せの酸化物を含むものである。 （４）前記構造体が５ｗｔ％以下の光触媒を含むもので
ある。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. Hereinafter, preferred constituent elements in the present invention are listed as follows. (1) The matrix constituting the surface of the structure contains a water-repellent / oil-repellent resin. (2) The water-repellent / oil-repellent resin contains a fluorine resin. (3) The photocatalytic semiconductor material constituting the surface of the structure is made of TiO 2 , ZnO, SnO 2 , SrTiO 3 , WO
3 , selected from the group consisting of BiO 3 and Fe 2 O 3
It contains a species or a combination of species. (4) The structure contains a photocatalyst of 5 wt% or less.
【０００７】例えば、建造物の表面に付着する油汚れ
は、降雨等と共に構造体表面に一様に付着する。この構
造物表面をはつ油性のフッ素樹脂で被覆することによっ
て、付着した油汚れは、使用環境下での風雨や重力によ
って表面を徐々に移動できる。しかしはつ油性の樹脂の
みの構造体では、汚れは構造体上を移動するのみで経時
と共に構造物表面全体が汚染していく。しかしこの時、
汚れが移動する範囲内に油汚れを吸着する性質のある光
触媒を最小限配置すれば、移動してきた油汚れを分解除
去することができる。この方法によれば、構造体の表面
の多くを光触媒で被覆する必要が無く、むしろ構造体の
大部分を可とう性などが優れる樹脂等を用いることがで
きる。このため粒子状の光触媒を高い比率で含有してい
る構造体に比べて、耐久性や信頼性に優れる構造体を提
供することができる。For example, oil stains adhering to the surface of a building uniformly adhere to the surface of a structure together with rainfall or the like. By coating the surface of the structure with an oily fluororesin, the attached oil stains can gradually move on the surface due to wind, rain and gravity in the use environment. However, in a structure made of only oil-based resin, dirt only moves on the structure, and the entire structure surface is contaminated with time. But at this time,
If a photocatalyst having the property of adsorbing oily dirt is arranged at a minimum within the range in which dirt moves, the oily dirt that has moved can be decomposed and removed. According to this method, it is not necessary to cover much of the surface of the structure with the photocatalyst, and rather, a resin or the like having excellent flexibility and the like can be used for most of the structure. For this reason, a structure excellent in durability and reliability can be provided as compared with a structure containing a high ratio of the particulate photocatalyst.
【０００８】構造体に付着する汚れの種類は、その構造
体が使用される環境によって異なり、建築外装材では土
や粘土等の親水性の汚れや、都市部では煤煙などに由来
する疎水性の汚れが問題となる。また建築内装材では、
浴室や浴槽で問題となるバクテリアや人の垢などに由来
するタンパク質の汚れが問題になる。親水性の汚れはは
っ水性の表面でははじかれて可動となり、また疎水性
（油性）の汚れでははつ油性の表面上で可動となる。ま
たタンパク質などの両性の汚れでは、親水性及び疎水性
の数十ｎｍ程度の間隔で交互に配置するミクロドメイン
構造の表面では可動となることが知られている。このよ
うな対象汚れに合せて汚れが可動となる種類のマトリッ
クスを選択し、これに少量の光触媒粒子を添加し露出さ
せることにより、種々の対象とする汚れを防止すること
ができる。The type of dirt adhering to a structure depends on the environment in which the structure is used. For building exterior materials, hydrophilic dirt such as soil and clay, and in urban areas, hydrophobic dirt derived from soot and the like. Dirt is a problem. In building interior materials,
Protein stains originating from bacteria and human dirt, which are problematic in bathrooms and bathtubs, pose a problem. Hydrophilic dirt is repelled and mobile on a water-repellent surface, and is mobile on hydrophobic (oil-based) dirt. It is known that amphoteric stains such as proteins become movable on the surface of a microdomain structure in which hydrophilicity and hydrophobicity are alternately arranged at intervals of about several tens nm. By selecting a type of matrix in which dirt is movable according to such target dirt and adding a small amount of photocatalyst particles to the matrix to expose it, various types of target dirt can be prevented.
【０００９】光耐食性で且つはっ水・はつ油性の樹脂と
してはフッ素樹脂が好適である。特に四フッ化エチレン
樹脂、四フッ化エチレン−六フッ化プロピレン共重合体
樹脂等は高度なはっ水・はつ油性を発現する。更にはマ
トリックス樹脂は必ずしも難分解性（光耐食性）である
必要はなく、対象汚れが可動なように表面処理を行え
ば、安価なアクリル系樹脂等も用いることが可能であ
る。Fluororesin is preferred as the light-corrosion-resistant, water-repellent and oil-repellent resin. In particular, ethylene tetrafluoride resin, ethylene tetrafluoride-propylene hexafluoride copolymer resin and the like exhibit high water repellency and oiliness. Furthermore, the matrix resin does not necessarily need to be hardly decomposable (light corrosion resistance), and if a surface treatment is performed so that the target dirt is movable, an inexpensive acrylic resin or the like can be used.
【００１０】はっ水・はつ油性表面処理の例としては、
表面に−ＣＦ3 、−ＣＦ2 −ＣＦ3、−（ＣＦ2 ）ｎ
−、ＣＦ3 −、ＣＨ3 等の官能基を固体表面に配向させ
ることなどが有効である。その他カップリング剤を用い
たり、プラズマ反応を利用する方法がある。Examples of the water-repellent and oil-based surface treatment include:
-CF 3 , -CF 2 -CF 3 ,-(CF 2 ) n on the surface
It is effective to orient functional groups such as —, CF 3 — and CH 3 on the solid surface. Other methods include the use of a coupling agent and the use of a plasma reaction.
【００１１】光耐食性でないマトリックスを用いる場合
は、含有する光触媒粒子を、対象汚れが吸着可能な光耐
食性の吸着剤で被覆することでマトリックスと光触媒界
面の劣化が防止できると共に、移動してきた汚れの分解
が可能になる。この場合の汚れ吸着剤は、多孔質なアル
ミナ、ゼオライト等の親水性物質や、カーボンブラック
等の親油性物質などが利用できる。When a non-corrosion resistant matrix is used, deterioration of the interface between the matrix and the photocatalyst can be prevented by coating the contained photocatalyst particles with a photocorrosion-resistant adsorbent capable of adsorbing the target dirt, and the transferred dirt can be prevented. Decomposition becomes possible. In this case, as the soil adsorbent, a hydrophilic substance such as porous alumina or zeolite, or a lipophilic substance such as carbon black can be used.
【００１２】はっ水・はつ油性とは表面の性質であるた
め、表面組成のみでなく、表面の組織によっても影響さ
れる。表面粗さが大きくなるとはっ水・はつ油性は強調
されることから、表面粗さを制御することによって汚れ
の可動性を高めることは有効である。Water repellency and oiliness are properties of the surface and are affected not only by the surface composition but also by the surface texture. Since water repellency and oiliness are emphasized when the surface roughness increases, it is effective to control the surface roughness to increase the mobility of dirt.
【００１３】本発明で用いられる光触媒としては酸化チ
タン（ＴｉＯ2 ）が最も望ましい。酸化チタンにはアナ
ターゼ、ルチル、ブルッカイトの三種の結晶形態がある
が、いずれも光触媒性酸化チタンとして用いることがで
きることに加え、光照射によって親水・親油性となる特
性が知られており、汚れの吸着効率が高い。特にアナタ
ーゼ型酸化チタンは、光触媒活性の高い微粒子の粉体や
水に分散したコロイド等が市場で容易に入手できるため
原料として好適である。The most preferred photocatalyst used in the present invention is titanium oxide (TiO 2 ). Titanium oxide has three crystal forms: anatase, rutile, and brookite.In addition to being able to be used as a photocatalytic titanium oxide, it is known that it becomes hydrophilic and lipophilic by light irradiation. High adsorption efficiency. In particular, anatase-type titanium oxide is suitable as a raw material because fine powder having high photocatalytic activity, a colloid dispersed in water, and the like can be easily obtained on the market.
【００１４】以上の方法により、光触媒の添加量は、５
ｗｔ％以下、更には驚くべきことに０．５ｗｔ％以下で
も防汚効果を発現することが可能となる。この場合は汚
れの可能な範囲内に必要最小限配置することが重要であ
るから、微細な光触媒粒子が均一に分散している必要が
ある。光触媒粒子は平均粒径１００ｎｍ以下のものを用
いるのが望ましい。同じ添加量で粒径を大きくするにつ
れて分散がまばらになることから汚れが移動しなくては
ならない距離が増し、汚れ防止効果が低下する関係とな
る。According to the above method, the addition amount of the photocatalyst is 5
The antifouling effect can be exhibited even when the amount is not more than 0.5% by weight, and even more surprisingly, not more than 0.5% by weight. In this case, it is important to dispose the photocatalysts in a minimum possible range within a possible range of dirt, so that fine photocatalyst particles need to be uniformly dispersed. It is desirable to use photocatalyst particles having an average particle size of 100 nm or less. As the particle size is increased with the same addition amount, the dispersion becomes sparser, so that the distance over which the stain must move increases, and the stain prevention effect decreases.
【００１５】光触媒粉末の添加量や粒径は、マトリック
スの汚れのはじき易さとも関係がある。汚れに対するマ
トリックスのはじきが十分大きいときは汚れの可動距離
は大きく添加量は少なくてもすむと考えられるが、マト
リックスの汚れはじきが小さいときは、添加量がより多
く必要になる。親水性汚れに対する防汚を目的とした場
合のマトリックスのはっ水性及び油汚れを防止する場合
のはつ油性は接触角度で９０°以上、より望ましくは１
２０°以上が好適である。The addition amount and particle size of the photocatalyst powder are also related to the ease with which the matrix is repelled. When the repelling of the matrix to the stain is sufficiently large, it is considered that the movable distance of the stain is large and the addition amount may be small, but when the repelling of the matrix is small, a larger amount of addition is required. The matrix has a contact angle of 90 ° or more, and more preferably 1 or more, in terms of the water repellency and the oil repellency for preventing oil stains in the case of preventing stains on hydrophilic stains.
20 ° or more is preferred.
【００１６】本発明の防汚構造体は、物品表面の塗膜の
形態により金属、セラミックス、ガラス、プラスチッ
ク、木、石、セメント、コンクリートそれらの組合せや
積層体、又はそれらの材料で形成された建築物の外装
材、屋根材、窓枠、窓ガラス、及び浴室壁材等の内装材
や住宅設備機器、自動車、鉄道車両、航空機、船舶のよ
うな乗り物の外装塗装や内装部材の汚れ防止に広く用い
ることができる。The antifouling structure of the present invention is made of metal, ceramics, glass, plastic, wood, stone, cement, concrete, combinations or laminates thereof, or materials thereof, depending on the form of the coating film on the surface of the article. For exterior coating of building exterior materials, roofing materials, window frames, window glass, bathroom wall materials, etc., housing equipment, exterior coating of vehicles such as automobiles, railway vehicles, aircraft, ships, and prevention of stains on interior components. Can be widely used.
【００１７】[0017]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明はこれら実施例に限定されない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
【００１８】実施例１ 平均分子量８５００、平均粒径１μｍの四フッ化エチレ
ン樹脂粉末８０ｗｔ％とフッ化ビニリデン樹脂にフッ化
オイル（パーフルオロポリエーテル）を２ｗｔ％を加え
た樹脂成分に、平均粒径５０μｍのアナターゼ型酸化チ
タン粉末をそれぞれ０．５、２．０、５．０ｗｔ％加え
て酢酸ブチルで希釈し、ボールミルを用いてかくはん作
製した。これらのフッ素樹脂塗料をエポキシ樹脂を主材
料とするＦＲＰ板にスプレー塗装した。Example 1 A resin component obtained by adding 80 wt% of a tetrafluoroethylene resin powder having an average molecular weight of 8500 and an average particle size of 1 μm and 2 wt% of a vinylidene fluoride resin to 2 wt% of a fluorinated oil (perfluoropolyether) was added. 0.5, 2.0, and 5.0 wt% of anatase-type titanium oxide powder having a diameter of 50 μm were added, respectively, diluted with butyl acetate, and stirred using a ball mill. These fluororesin paints were spray-coated on an FRP plate mainly composed of an epoxy resin.
【００１９】比較例１ 実施例１と同様の樹脂成分に酸化チタンを添加しないで
混合し塗料を作製し、ＦＲＰ板にスプレー塗装した。上
記のサンプルについて初期接触角を測定したところ、実
施例１、比較例１共に１５０°であった。またサラダオ
イルの接触角を計ったところ、いずれも１３９°であ
り、初期状態においては酸化チタンの添加の有無や添加
量に関わらず、いずれのサンプルもはっ水・はつ油性を
発現していることがわかった。次に実施例１、比較例１
の屋外暴露による表面の汚れの評価を行った。サンプル
の暴露場所はビル屋上（東京都武蔵野市）で南面傾斜角
４５°で行った。屋外暴露後３００日経過後、サンプル
を目視観察すると酸化チタン無添加の比較例１のサンプ
ルは、縦方向の雨筋や水垢が認められたが、実施例１の
サンプルでは酸化チタンの添加量の多少によらず汚れが
全く観測されなかった。Comparative Example 1 A coating material was prepared by mixing the same resin components as in Example 1 without adding titanium oxide, and spray-coated on an FRP plate. When the initial contact angle of the above sample was measured, it was 150 ° in both Example 1 and Comparative Example 1. When the contact angle of the salad oil was measured, all were 139 °, and in the initial state, regardless of the presence or absence and the amount of titanium oxide added, all samples exhibited water repellency and oil repellency. I knew it was there. Next, Example 1 and Comparative Example 1
Was evaluated for surface contamination due to outdoor exposure. The sample was exposed on the roof of a building (Musashino City, Tokyo) at an inclination of 45 ° on the south side. After 300 days from the outdoor exposure, when the sample was visually observed, the sample of Comparative Example 1 to which no titanium oxide was added was found to have vertical rain streaks and water scale, but the sample of Example 1 had a small amount of titanium oxide added. No contamination was observed at all.
【００２０】[0020]
【発明の効果】本発明によれば、少量の光触媒の添加に
より長期にわたって高い汚れ防止効果を有する防汚構造
体を提供することができる。本発明は屋外の種々の建築
物の内外装材、更には自動車、車両等の移動体の内外装
材への適用に際しても高い防汚効果を奏することができ
る。According to the present invention, an antifouling structure having a high antifouling effect for a long time can be provided by adding a small amount of a photocatalyst. INDUSTRIAL APPLICABILITY The present invention can exhibit a high antifouling effect when applied to the interior and exterior materials of various outdoor buildings and also to the interior and exterior materials of moving objects such as automobiles and vehicles.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山内 五郎 東京都新宿区西新宿三丁目19番２号 日本 電信電話株式会社内 (72)発明者 高井 健一 東京都新宿区西新宿三丁目19番２号 日本 電信電話株式会社内 (72)発明者 藤嶋 昭 神奈川県川崎市中原区中丸子710番地５ (72)発明者 橋本 和仁 神奈川県横浜市栄区飯島町2073番地２ ニ ューシティ本郷台Ｄ棟213号 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Goro Yamauchi 3-chome 192-1 Nishishinjuku, Shinjuku-ku, Tokyo Japan Telegraph and Telephone Corporation (72) Inventor Kenichi Takai 3-chome 192-1 Nishishinjuku, Shinjuku-ku, Tokyo No. Nippon Telegraph and Telephone Corporation (72) Inventor Akira Fujishima 710-5 Nakamaruko, Nakahara-ku, Kawasaki City, Kanagawa Prefecture
Claims (5)
料から構成される構造体であって、前記構造体表面を構
成するマトリックスは、汚れをはじく性質を有し、且つ
前記構造体表面を構成する光触媒性半導体材料は、汚れ
を吸着する性質を有し、前記構造体表面において、汚れ
が可動な範囲に、光触媒が少量露出していることを特徴
とする防汚構造体。1. A structure whose surface is composed of a matrix and a photocatalytic semiconductor material, wherein the matrix constituting the surface of the structure has a property of repelling dirt and the photocatalyst constituting the surface of the structure An antifouling structure, wherein the conductive semiconductor material has a property of adsorbing dirt, and a small amount of a photocatalyst is exposed in a range in which dirt is movable on the surface of the structure.
は、はっ水・はつ油性樹脂を含むものである請求項１に
記載の防汚構造体。2. The antifouling structure according to claim 1, wherein the matrix constituting the surface of the structure includes a water-repellent / oil-repellent resin.
脂を含むものである請求項２に記載の防汚構造体。3. The antifouling structure according to claim 2, wherein the water-repellent / oil-repellent resin contains a fluorine resin.
体材料は、ＴｉＯ2、ＺｎＯ、ＳｎＯ2 、ＳｒＴｉ
Ｏ3 、ＷＯ3 、ＢｉＯ3 及びＦｅ2 Ｏ3 よりなる群から
選択した１種又は複数種組合せの酸化物を含むものであ
る請求項１に記載の防汚構造体。4. The photocatalytic semiconductor material constituting the surface of the structure is made of TiO 2 , ZnO, SnO 2 , SrTi.
O 3, WO 3, BiO 3 and antifouling structure according to claim 1 from the group consisting of Fe 2 O 3 is intended to include an oxide of one or more combinations selected.
むものである請求項１に記載の防汚構造体。5. The antifouling structure according to claim 1, wherein the structure contains a photocatalyst of 5 wt% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10071188A JPH11256134A (en) | 1998-03-06 | 1998-03-06 | Anti staining structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10071188A JPH11256134A (en) | 1998-03-06 | 1998-03-06 | Anti staining structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11256134A true JPH11256134A (en) | 1999-09-21 |
Family
ID=13453447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10071188A Pending JPH11256134A (en) | 1998-03-06 | 1998-03-06 | Anti staining structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11256134A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006200325A (en) * | 2005-01-24 | 2006-08-03 | Toyo Kawara Kogyo Kk | Composition of coating agent for tile |
| EP1873218A1 (en) * | 2005-04-22 | 2008-01-02 | Dow Corning Toray Silicone Company, Ltd. | Solution or dispersion for base surface treatment containing titanium oxide doped with metal element, method of treating base surface with the liquid, and surface-treated material obtained by the method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08218029A (en) * | 1995-02-16 | 1996-08-27 | Matsushita Electric Ind Co Ltd | Stain-proofing resin and stain-proofing resin part |
| JPH09164091A (en) * | 1995-12-15 | 1997-06-24 | Matsushita Electric Ind Co Ltd | Bottomed container with photocatalyst and molding thereof |
| WO1997045502A1 (en) * | 1996-05-31 | 1997-12-04 | Toto Ltd. | Antifouling member and antifouling coating composition |
| JPH09316214A (en) * | 1996-05-27 | 1997-12-09 | Nitto Denko Corp | Anti-staining sheet |
| JPH1030030A (en) * | 1996-07-16 | 1998-02-03 | Nitto Denko Corp | Surface protecting material for solar cell |
| JPH1045428A (en) * | 1996-05-31 | 1998-02-17 | Toto Ltd | Window glass for construction |
| JPH1088061A (en) * | 1996-09-10 | 1998-04-07 | Nippon Telegr & Teleph Corp <Ntt> | Fluororesin coating material and its coating film |
| JPH10130540A (en) * | 1996-10-28 | 1998-05-19 | Nippon Telegr & Teleph Corp <Ntt> | Powdered paint and coated layer and coating method |
-
1998
- 1998-03-06 JP JP10071188A patent/JPH11256134A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08218029A (en) * | 1995-02-16 | 1996-08-27 | Matsushita Electric Ind Co Ltd | Stain-proofing resin and stain-proofing resin part |
| JPH09164091A (en) * | 1995-12-15 | 1997-06-24 | Matsushita Electric Ind Co Ltd | Bottomed container with photocatalyst and molding thereof |
| JPH09316214A (en) * | 1996-05-27 | 1997-12-09 | Nitto Denko Corp | Anti-staining sheet |
| WO1997045502A1 (en) * | 1996-05-31 | 1997-12-04 | Toto Ltd. | Antifouling member and antifouling coating composition |
| JPH1045428A (en) * | 1996-05-31 | 1998-02-17 | Toto Ltd | Window glass for construction |
| JPH1030030A (en) * | 1996-07-16 | 1998-02-03 | Nitto Denko Corp | Surface protecting material for solar cell |
| JPH1088061A (en) * | 1996-09-10 | 1998-04-07 | Nippon Telegr & Teleph Corp <Ntt> | Fluororesin coating material and its coating film |
| JPH10130540A (en) * | 1996-10-28 | 1998-05-19 | Nippon Telegr & Teleph Corp <Ntt> | Powdered paint and coated layer and coating method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006200325A (en) * | 2005-01-24 | 2006-08-03 | Toyo Kawara Kogyo Kk | Composition of coating agent for tile |
| JP4643997B2 (en) * | 2005-01-24 | 2011-03-02 | 東洋瓦株式会社 | Tile coating composition |
| EP1873218A1 (en) * | 2005-04-22 | 2008-01-02 | Dow Corning Toray Silicone Company, Ltd. | Solution or dispersion for base surface treatment containing titanium oxide doped with metal element, method of treating base surface with the liquid, and surface-treated material obtained by the method |
| EP1873218A4 (en) * | 2005-04-22 | 2010-03-24 | Dow Corning Toray Silicone | Solution or dispersion for base surface treatment containing titanium oxide doped with metal element, method of treating base surface with the liquid, and surface-treated material obtained by the method |
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