JPH09207289A - Film structural material and its manufacture - Google Patents
Film structural material and its manufactureInfo
- Publication number
- JPH09207289A JPH09207289A JP2109196A JP2109196A JPH09207289A JP H09207289 A JPH09207289 A JP H09207289A JP 2109196 A JP2109196 A JP 2109196A JP 2109196 A JP2109196 A JP 2109196A JP H09207289 A JPH09207289 A JP H09207289A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- titanium oxide
- oxide fine
- photocatalytic titanium
- fluororesin
- 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.)
- Granted
Links
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は巨大建築物の屋根材
等に使用されるガラス繊維等を構成材料とする繊維布を
基材とする膜構造材及びその製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a membrane structure material having a base material of a fiber cloth made of glass fiber or the like, which is used as a roof material of a huge building, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、体育館、競技場及び多目的ホール
等の巨大建築物の屋根材として、例えばガラス繊維（ガ
ラスクロス）等からなる繊維布を基材としこれをフッ素
樹脂層で被覆してなる膜構造材が使用されている。この
膜構造材は、不燃で機械的強度が高く、しかも、軽量か
つ柔軟性に富むという利点を有しており、建築材料とし
ての規模を拡大してきたものである。しかしながら、こ
の膜構造材は大気中のばい煙、ほこり、細砂等の物質が
膜表面に付着して外観が汚れるという問題を抱えてい
る。この原因はフッ素樹脂が非粘着性を有し、離型性に
優れるものではあるが、有機物をバインダーとするゴミ
等の付着を防止できるにはいたらず、かつ撥水性を有す
るために水洗い効率が悪いということにある。2. Description of the Related Art In recent years, as a roofing material for huge buildings such as gymnasiums, stadiums and multipurpose halls, a fiber cloth made of, for example, glass fiber (glass cloth) is used as a base material and coated with a fluororesin layer. Membrane structural material is used. This membrane structural material has the advantages of being non-combustible, having high mechanical strength, being lightweight and rich in flexibility, and has expanded in scale as a building material. However, this membrane structure material has a problem that substances such as dust, dust, and fine sand in the atmosphere adhere to the membrane surface to stain the appearance. The reason for this is that the fluororesin has non-adhesiveness and is excellent in releasability, but it cannot prevent the adhesion of dust or the like using an organic substance as a binder, and since it has water repellency, the washing efficiency is low. It's bad.
【０００３】[0003]
【発明が解決しようとする課題】このため前記膜構造材
の表面を清浄化するための種々のクリーニング方法も検
討されてきたが、膜構造材が大面積で、高所といった場
所に配置されることが多いものであることから、クリー
ニングには大がかりな人件費と材料が必要であるばかり
でなく危険性を伴うため、クリーニングを必要としな
い、すなわち、表面汚染が生じにくい膜構造材の開発が
強く要望されている。For this reason, various cleaning methods for cleaning the surface of the membrane structure material have been investigated, but the membrane structure material has a large area and is arranged at a high place. Since cleaning often requires a large labor cost and materials as well as risks, it is necessary to develop a membrane structure material that does not require cleaning, that is, does not easily cause surface contamination. There is a strong demand.
【０００４】本発明は前記課題に鑑みてなされたもので
あり、表面汚染が生じにくい膜構造材及びその製造方法
を提供することを目的とするものである。The present invention has been made in view of the above problems, and an object of the present invention is to provide a film structure material which is less likely to cause surface contamination and a method for manufacturing the same.
【０００５】[0005]
【課題を解決するための手段】前記目的を達成するため
に、本発明の膜構造材は、ガラス繊維、金属繊維、及び
鉱物繊維から選ばれる少くとも１つを構成材料とする繊
維布とフッ素樹脂とを主材とする膜構造材であって、そ
の少くとも一方の最外表面層が光触媒酸化チタン微粒子
を含むフッ素樹脂層からなることを特徴とする。このよ
うな構成にしたことにより膜構造材表面が汚染しにくく
なり、かつ、膜構造材表面に微量の汚れが生じたとして
も光触媒酸化チタン微粒子の光分解触媒反応によって微
量の汚れは分解または洗浄される。[Means for Solving the Problems] In order to achieve the above object, the membrane structure material of the present invention comprises a fiber cloth and a fluorine containing at least one selected from glass fiber, metal fiber and mineral fiber as a constituent material. A film structure material mainly composed of a resin, characterized in that at least one outermost surface layer thereof comprises a fluororesin layer containing photocatalytic titanium oxide fine particles. With such a structure, the surface of the membrane structure material is less likely to be contaminated, and even if a small amount of dirt is generated on the surface of the membrane structure material, a minute amount of dirt is decomposed or washed by the photolytic catalytic reaction of the photocatalytic titanium oxide fine particles. To be done.
【０００６】前記構成からなる本発明の膜構造材におい
ては、光触媒酸化チタン微粒子を含むフッ素樹脂層が非
多孔性であるのが好ましい。このような構成にしたこと
により、膜構造材表面の耐汚染性が一層向上し、しか
も、膜構造材の強度も向上する。ここで、「非多孔性」
とは、層内に孔が実質的に存在せず（孔が存在したとし
ても層全体での気孔率が１％以下の極微量）、層を構成
する材料（光触媒酸化チタン微粒子、フッ素樹脂）が緻
密に詰まった状態であって、ばい煙、ほこり、細砂等の
空気中の浮遊物と層表面との接触面積をできる限り小さ
くした状態である。In the film structure material of the present invention having the above structure, it is preferable that the fluororesin layer containing the photocatalytic titanium oxide fine particles is non-porous. With such a structure, the stain resistance of the surface of the film structure material is further improved, and the strength of the film structure material is also improved. Where "non-porous"
Means that there are substantially no pores in the layer (even if there are pores, the porosity of the layer as a whole is 1% or less), the materials constituting the layer (photocatalytic titanium oxide fine particles, fluororesin) Is a densely packed state in which the contact area between airborne matter such as soot, dust and fine sand and the layer surface is made as small as possible.
【０００７】また前記構成からなる本発明の膜構造材に
おいては、光触媒酸化チタン微粒子を含むフッ素樹脂層
の前記光触媒酸化チタン微粒子が層表面から露出してい
るのが好ましい。このような構成にすることにより、層
表面にて光触媒酸化チタン微粒子の光分解触媒反応が積
極的に起こり、汚れの分解または洗浄が効率良く行われ
る。In the film structure material of the present invention having the above-mentioned constitution, it is preferable that the photocatalytic titanium oxide fine particles of the fluororesin layer containing the photocatalytic titanium oxide fine particles are exposed from the layer surface. With such a structure, the photodecomposition catalytic reaction of the photocatalytic titanium oxide fine particles positively takes place on the surface of the layer, and the decomposition or cleaning of the dirt is efficiently performed.
【０００８】また前記構成からなる本発明の膜構造材に
おいては、光触媒酸化チタン微粒子を含むフッ素樹脂層
の下にガラスビーズを含有するフッ素樹脂層が形成され
ているのが好ましい。このような構成にしたことによ
り、膜構造材の光透過性を向上させることができる。Further, in the film structure material of the present invention having the above-mentioned constitution, it is preferable that a fluororesin layer containing glass beads is formed below the fluororesin layer containing photocatalytic titanium oxide fine particles. With such a structure, the light transmittance of the film structure material can be improved.
【０００９】本発明の膜構造材の製造方法は、ガラス繊
維、金属繊維、及び鉱物繊維から選ばれる少くとも１つ
を構成材料とする繊維布の表面を光触媒酸化チタン微粒
子とフッ素樹脂粉を含有する液状物の塗膜で被覆し、こ
の塗膜を前記フッ素樹脂粉の融点以上の温度で焼成して
光触媒酸化チタン微粒子を含むフッ素樹脂層を形成する
ようにした。このような構成にしたことにより、前記し
た本発明の耐表面汚染性に優れた膜構造材を合理的に製
造することができる。また、光触媒酸化チタン微粒子を
露出させたフッ素樹脂層を非多孔性の樹脂層に形成する
ことができる。In the method for producing a membrane structure material of the present invention, the surface of a fiber cloth made of at least one selected from glass fiber, metal fiber, and mineral fiber contains photocatalytic titanium oxide fine particles and fluororesin powder. Then, the coating film was coated with a liquid coating film, and the coating film was baked at a temperature equal to or higher than the melting point of the fluororesin powder to form a fluororesin layer containing photocatalytic titanium oxide fine particles. With such a structure, it is possible to rationally manufacture the above-mentioned film structure material having excellent surface contamination resistance of the present invention. Further, the fluororesin layer in which the photocatalytic titanium oxide fine particles are exposed can be formed as a non-porous resin layer.
【００１０】また、本発明の膜構造材の製造方法は、ガ
ラス繊維、金属繊維、及び鉱物繊維から選ばれる少くと
も１つを構成材料とする繊維布の表面をガラスビーズと
フッ素樹脂粉を含有する第１の液状物の塗膜で被覆し、
この塗膜を前記フッ素樹脂粉の融点以上の温度で焼成し
てガラスビーズが分散したフッ素樹脂層を形成し、次に
前記ガラスビーズが分散したフッ素樹脂層上に光触媒酸
化チタン微粒子とフッ素樹脂粉を含有する第２の液状物
の塗膜を形成し、この塗膜を前記フッ素樹脂粉の融点以
上の温度で焼成して光触媒酸化チタン微粒子を露出させ
たフッ素樹脂層を形成する。このような構成にしたこと
により、前記した耐表面汚染性及び光透過性に優れた本
発明の膜構造材を合理的に製造することができる。Further, in the method for producing a membrane structure material of the present invention, the surface of a fiber cloth composed of at least one selected from glass fiber, metal fiber and mineral fiber contains glass beads and fluororesin powder. Coating with the first liquid coating film
This coating film is baked at a temperature not lower than the melting point of the fluororesin powder to form a fluororesin layer in which glass beads are dispersed, and then photocatalytic titanium oxide fine particles and fluororesin powder are formed on the fluororesin layer in which the glass beads are dispersed. A coating film of a second liquid material containing is formed, and the coating film is baked at a temperature equal to or higher than the melting point of the fluororesin powder to form a fluororesin layer in which the photocatalytic titanium oxide fine particles are exposed. With such a structure, it is possible to rationally manufacture the above-mentioned film structure material of the present invention having excellent resistance to surface contamination and light transmission.
【００１１】[0011]
【発明の実施の形態】本発明の膜構造材はガラス繊維、
金属繊維、及び鉱物繊維から選ばれる少くとも１つを構
成材料とする繊維布を基材とするが、この繊維布として
は市販されているものを使用することができる。金属繊
維の具体例としてはステンレス、チタン合金等の繊維を
挙げることができ、鉱物繊維の具体例としてはアスベス
トを挙げることができる。取り扱いが容易である点及び
軽量である点等から、ガラス繊維からなる繊維布（ガラ
スクロス）を用いるのが一般的である。BEST MODE FOR CARRYING OUT THE INVENTION The membrane structure material of the present invention is glass fiber,
A fiber cloth having at least one selected from metal fibers and mineral fibers as a constituent material is used as a base material, and commercially available fiber cloth can be used. Specific examples of the metal fibers include fibers such as stainless steel and titanium alloys, and specific examples of the mineral fibers include asbestos. A fiber cloth (glass cloth) made of glass fibers is generally used because it is easy to handle and lightweight.
【００１２】膜構造材の強度及び耐水性を向上させる観
点からは、繊維布の繊維間に撥水性物質を（含浸）充填
するのが好ましい。この撥水性物質としては、シリコー
ンオイル、シリコーン樹脂、ステアリン酸等の飽和炭化
水素部分のある化合物、フッ素樹脂等を挙げることがで
き、このうちシリコーンオイルまたはシリコーン樹脂を
用いるのが好ましい。市販されているガラス繊維布（ガ
ラスクロス）は、通常コーンスターチ等のサイジング剤
が付着しており、このサイジング剤が撥水性物質の含浸
を疎外するため、繊維布の繊維間に撥水性物質を（含
浸）充填させるに先立ち、ガラス繊維布を約３５０℃以
上の温度に曝してサイジング剤を揮散除去するのが好ま
しい。From the viewpoint of improving the strength and water resistance of the membrane structural material, it is preferable to fill (impregnate) a water-repellent substance between the fibers of the fiber cloth. Examples of the water-repellent substance include silicone oil, silicone resin, compounds having a saturated hydrocarbon moiety such as stearic acid, and fluororesin. Of these, it is preferable to use silicone oil or silicone resin. Commercially available glass fiber cloth (glass cloth) usually has a sizing agent such as cornstarch attached thereto, and this sizing agent disperses the impregnation of the water-repellent substance. Prior to (impregnation) filling, the glass fiber cloth is preferably exposed to a temperature of about 350 ° C. or higher to volatilize and remove the sizing agent.
【００１３】光触媒酸化チタン微粒子を露出させたフッ
素樹脂層に使用される光触媒酸化チタン微粒子として
は、アナターゼ型、ルチル型、含水型等の各種光触媒酸
化チタン微粒子を挙げることができるが、光活性の点か
らアナターゼ型光触媒酸化チタン微粒子を使用するのが
好ましい。また、光触媒酸化チタン微粒子の平均粒子径
は０．００７〜０．５μｍの範囲にあるのが好ましい。
これは、光触媒酸化チタン微粒子の平均粒子径が０．０
０７μｍより小さくなると、微粒子をフッ素樹脂層表面
に充分に露出させることが困難になる傾向を示し、０．
５μｍより大きくなると比表面積が小さくなることによ
り光触媒効果が減少する傾向を示すためでる。また、フ
ッ素樹脂としては、ポリテトラフルオロエチレン（ＰＴ
ＦＥ）、テトラフルオロエチレン−ヘキサフルオロプロ
ピレン共重合体（ＦＥＰ）、テトラフルオロエチレン−
パーフルオロアルキルビニルエーテル共重合体（ＰＦ
Ａ）、ポリクロロトリフルオロエチレン（ＰＣＴＦ
Ｅ）、ポリビニリデンフルオライド（ＰＶＤＦ）、ポリ
ビニルフルオライド（ＰＶＦ）、テトラフルオロエチレ
ン−エチレン共重合体（ＰＥＴＦＥ）等が使用される。
光触媒酸化チタン微粒子を露出させたフッ素樹脂層の形
成は、例えば撥水性樹脂層表面に光触媒酸化チタン微粒
子とフッ素樹脂粉を含有する液状物（エマルジョン、デ
ィスパージョン）の塗膜を形成し、この塗膜をフッ素樹
脂粉の融点以上の温度で加熱して焼成することにより行
われる。光触媒酸化チタン微粒子とフッ素樹脂の配合量
は、光触媒酸化チタン微粒子の層表面への露出や下層の
撥水性樹脂層への密着性の点から、重量比（光触媒酸化
チタン微粒子：フッ素樹脂）で一般に１：９〜６：４、
好ましくは３：７〜５：５にするのがよい。この範囲を
越えて光触媒酸化チタン微粒子の配合量が多くなると下
層の撥水性樹脂層への密着性が低下する傾向を示し、少
くなると光触媒酸化チタン微粒子を層表面に充分に露出
させることが困難になる傾向を示す。As the photocatalytic titanium oxide fine particles used in the fluororesin layer in which the photocatalytic titanium oxide fine particles are exposed, various photocatalytic titanium oxide fine particles such as anatase type, rutile type and hydrous type can be mentioned. From this point, it is preferable to use the anatase type photocatalytic titanium oxide fine particles. The average particle size of the photocatalytic titanium oxide fine particles is preferably in the range of 0.007 to 0.5 μm.
This is because the average particle size of the photocatalytic titanium oxide fine particles is 0.0
If it is smaller than 07 μm, it tends to be difficult to sufficiently expose the fine particles to the surface of the fluororesin layer.
This is because if it is larger than 5 μm, the specific surface area becomes smaller and the photocatalytic effect tends to decrease. Further, as the fluororesin, polytetrafluoroethylene (PT
FE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-
Perfluoroalkyl vinyl ether copolymer (PF
A), polychlorotrifluoroethylene (PCTF
E), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-ethylene copolymer (PETFE) and the like are used.
The formation of the fluororesin layer in which the photocatalytic titanium oxide fine particles are exposed is performed, for example, by forming a coating film of a liquid substance (emulsion, dispersion) containing the photocatalytic titanium oxide fine particles and the fluororesin powder on the surface of the water-repellent resin layer, and applying the coating. It is performed by heating the film at a temperature equal to or higher than the melting point of the fluororesin powder and baking the film. The photocatalytic titanium oxide fine particles and the fluororesin are generally mixed in a weight ratio (photocatalytic titanium oxide fine particles: fluororesin) in terms of the exposure of the photocatalytic titanium oxide fine particles to the layer surface and the adhesion to the lower water-repellent resin layer. 1: 9 to 6: 4,
Preferably, it is 3: 7 to 5: 5. If the content of the photocatalytic titanium oxide fine particles exceeds this range, the adhesion to the lower water-repellent resin layer tends to decrease, and if it is too small, it becomes difficult to sufficiently expose the photocatalytic titanium oxide fine particles to the layer surface. Shows a tendency to become.
【００１４】図１は本発明の好適な実施形態を示す膜構
造材の断面図であり、図において、１は基材としてのガ
ラス繊維布、２はシリコーン樹脂層、３はＰＴＦＥ層、
４はガラスビーズを含有するＰＴＦＥ層、５は光触媒酸
化チタン微粒子を露出させたフッ素樹脂層である。以
下、この膜構造材の構成及び製造工程を詳しく説明す
る。FIG. 1 is a sectional view of a membrane structure material showing a preferred embodiment of the present invention. In the figure, 1 is a glass fiber cloth as a base material, 2 is a silicone resin layer, 3 is a PTFE layer,
Reference numeral 4 is a PTFE layer containing glass beads, and 5 is a fluororesin layer exposing the photocatalytic titanium oxide fine particles. Hereinafter, the configuration and manufacturing process of this membrane structure material will be described in detail.
【００１５】ガラス繊維布１は加熱処理によりサイジン
グ剤が揮散除去されたもので、通常厚みが０．３〜０．
８ｍｍであり、この表面にシリコーン樹脂層２が薄層状
に形成されている。シリコーン樹脂の量が少な過ぎると
膜構造材の柔軟性が低下する傾向となり、多すぎるとＰ
ＴＦＥ層３との密着性が低下する傾向となるため、シリ
コーン樹脂の付着量は１〜１０ｇ／ｍ2 、好ましくは４
〜６ｇ／ｍ2 である。このシリコーン樹脂層２は、例え
ばガラス繊維布１をシリコーン樹脂を含有するエマルジ
ョン中に浸漬して引き上げ、これを加熱することによ
り、シリコーン樹脂がガラス繊維布に含浸すると同時
に、ガラス繊維布の表面に薄層状に付着することにより
形成される。The glass fiber cloth 1 has a sizing agent volatilized and removed by heat treatment, and usually has a thickness of 0.3 to 0.
The thickness is 8 mm, and the silicone resin layer 2 is formed in a thin layer on this surface. If the amount of silicone resin is too small, the flexibility of the membrane structural material tends to decrease, and if it is too large, P
Since the adhesion with the TFE layer 3 tends to decrease, the adhesion amount of the silicone resin is 1 to 10 g / m 2 , preferably 4
~ 6 g / m 2 . The silicone resin layer 2 is obtained by, for example, immersing the glass fiber cloth 1 in an emulsion containing the silicone resin, pulling it up, and heating it to impregnate the glass fiber cloth with the silicone resin and, at the same time, to the surface of the glass fiber cloth. It is formed by depositing in a thin layer.
【００１６】ＰＴＦＥ層３は通常その付着量が約１００
〜５００ｇ／ｍ2 であり、これは例えばシリコーン樹脂
層２表面にＰＴＦＥ粉末（粒径０．１〜０．４μｍ）を
３０〜６０重量％含有するディスパージョンを塗布し、
得られた塗膜を乾燥、焼成する工程を繰り返し行うこと
により形成される。The PTFE layer 3 usually has an adhesion amount of about 100.
˜500 g / m 2 , which is applied, for example, to the surface of the silicone resin layer 2 by applying a dispersion containing 30 to 60% by weight of PTFE powder (particle size 0.1 to 0.4 μm),
It is formed by repeating the steps of drying and baking the obtained coating film.
【００１７】ガラスビーズを含有するＰＴＦＥ層４は膜
構造材の光透過性を向上させるため層で、通常その付着
量が約１００〜５００ｇ／ｍ2 である。これは例えばＰ
ＴＦＥ層３表面に前記したＰＴＦＥ粉末（粒径０．１〜
０．４μｍ）を３０〜６０重量％含有するディスパージ
ョンに更にガラスビーズを混合分散したものを塗布し、
得られた塗膜を乾燥、焼成する工程を繰り返し行うこと
により形成される。ここで、ガラスビーズは中空または
中身の詰まったもののいずれでもよく、その粒径は通常
１〜１００μｍであり、また、配合量はＰＴＦＥの固形
分に対して１〜１０重量％、好ましくは３〜５重量％で
ある。The PTFE layer 4 containing glass beads is a layer for improving the light-transmitting property of the membrane structure material, and the adhesion amount thereof is usually about 100 to 500 g / m 2 . This is for example P
On the surface of the TFE layer 3, the above-mentioned PTFE powder (particle size 0.1 to 0.1
0.4 μm) is added to a dispersion containing 30 to 60% by weight of glass beads and further mixed and dispersed with glass beads,
It is formed by repeating the steps of drying and baking the obtained coating film. Here, the glass beads may be hollow or packed, and their particle size is usually 1 to 100 μm, and the compounding amount is 1 to 10% by weight, preferably 3 to 10% based on the solid content of PTFE. It is 5% by weight.
【００１８】光触媒酸化チタン微粒子を露出させたフッ
素樹脂層５は、通常その付着量が約１〜５０ｇ／ｍ2 、
好ましくは１０〜３０ｇ／ｍ2 であり、これはガラスビ
ーズを含むＰＴＦＥ層４表面に、前記したＰＴＦＥ粉末
（粒径０．１〜０．４μｍ）を３０〜６０重量％含有す
るディスパージョンに更に光触媒酸化チタン微粒子を混
合分散したものを塗布し、得られた塗膜を乾燥、焼成す
る工程を繰り返し行うことにより形成される。ここで焼
成温度をＰＴＦＥの融点（３２７℃）よりも高い温度に
すると、ＰＴＦＥ粉末及び光触媒酸化チタン微粒子の各
粉（粒子）間の空隙が充分に埋め尽くされるようにＰＴ
ＦＥ粉末が溶融する過程を経て塗膜が焼成されることと
なり、得られる層は孔が殆どなく、樹脂成分と光触媒酸
化チタン微粒子が緻密に詰まったものとなる。The fluororesin layer 5 on which the photocatalytic titanium oxide fine particles are exposed usually has an adhesion amount of about 1 to 50 g / m 2 ,
It is preferably 10 to 30 g / m 2 , which is further added to the dispersion containing 30 to 60% by weight of the above-mentioned PTFE powder (particle size 0.1 to 0.4 μm) on the surface of the PTFE layer 4 containing glass beads. The photocatalytic titanium oxide fine particles are mixed and dispersed, and the resulting coating film is formed by repeating the steps of drying and baking. Here, if the firing temperature is set to a temperature higher than the melting point of PTFE (327 ° C.), the PT will be filled so that the voids between the PTFE powder and the photocatalytic titanium oxide fine particles (particles) are sufficiently filled.
The coating film is fired through the process in which the FE powder is melted, and the obtained layer has almost no pores, and the resin component and the photocatalyst titanium oxide fine particles are densely packed.
【００１９】このような構成の膜構造材は、表面に太陽
光が当たると光触媒酸化チタンの光分解触媒反応による
強い酸化力によって、表面に付着した有機物からなる汚
染物質が分解され脱色されるだけでなく、有機物を含む
バインダーを失った無機物からなる汚染物質が容易に洗
い流されるため、半永久的にきれいな外観が保たれる。
また、図１では膜構造材の両側の表面層を光触媒酸化チ
タン微粒子を露出させたフッ素樹脂層にしたが、膜構造
材の片側の表面の耐汚染性だけを向上させる場合には、
片側の表面層だけを光触媒酸化チタン微粒子を露出させ
たフッ素樹脂層にしてもよい。When the surface of the film structure material having such a structure is exposed to sunlight, the strong oxidizing power of the photocatalytic titanium oxide photocatalytic reaction causes decomposition and decolorization of pollutants consisting of organic substances adhering to the surface. Not only that, but contaminants made of inorganic substances that have lost the binder containing organic substances are easily washed away, so that a semi-permanently clean appearance is maintained.
Further, in FIG. 1, the surface layers on both sides of the membrane structure material are fluororesin layers in which the photocatalytic titanium oxide fine particles are exposed, but in the case of improving only the stain resistance of the surface on one side of the membrane structure material,
Only one surface layer may be a fluororesin layer in which the photocatalytic titanium oxide fine particles are exposed.
【００２０】[0020]
（実施例１）厚み０．５ｍｍのガラス繊維布（米国ケミ
カルファブリック社製、商品名ガラスクロス＃１５３）
を３７０℃にて１５０秒間加熱し、サイジング剤及び異
物の除去をした。この繊維布をシリコーン樹脂濃度３重
量％のエマルジョン（ダウコーニング社製、商品名ＥＴ
−４３２７）中に浸漬して引き上げ、２９０℃で１５０
秒間加熱し、該繊維布にシリコーン樹脂を含浸させると
ともにその表面にシリコーン樹脂層を形成した。なお、
この時、シリコーン樹脂の繊維布に対する付着量は５ｇ
／ｍ2 にした。(Example 1) Glass fiber cloth having a thickness of 0.5 mm (trade name: glass cloth # 153, manufactured by US Chemical Fabric Co.)
Was heated at 370 ° C. for 150 seconds to remove the sizing agent and foreign matters. An emulsion of this fiber cloth with a silicone resin concentration of 3% by weight (made by Dow Corning, trade name ET
-4327) soaked in and pulled up at 290 ° C for 150
The fiber cloth was heated for 2 seconds to impregnate the fiber cloth with a silicone resin, and a silicone resin layer was formed on the surface. In addition,
At this time, the amount of silicone resin attached to the fiber cloth is 5 g
/ M 2 .
【００２１】次に、ＰＴＦＥ粉末濃度４０重量％のディ
スパージョン（三井デュポンフロロケミカル社製、商品
名ＴＥ−３３１３Ｊ）をシリコーン樹脂層上に塗布し、
３７０℃で３時間加熱した。更に、ディスパージョンの
塗布及び加熱をもう一度繰り返し、ＰＴＦＥの付着量３
５０ｇ／ｍ2 のＰＴＦＥ層を形成した。Next, a dispersion having a PTFE powder concentration of 40% by weight (TE-3313J, trade name, manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was applied on the silicone resin layer,
Heated at 370 ° C. for 3 hours. Furthermore, the application of the dispersion and the heating are repeated once more, and the amount of PTFE attached 3
A 50 g / m 2 PTFE layer was formed.
【００２２】その後、ＰＴＦＥ粉末１００重量部に対し
てガラスビーズ（球径１０〜１５μｍ）３重量部を含む
ディスパージョン（三井デュポンフロロケミカル社製、
商品名ＴＥ−３４８１Ｊ）をＰＴＦＥ層上に塗布し、３
７０℃で３分間加熱した。この塗布及び加熱を更に２回
繰り返し、付着量３９０ｇ／ｍ2 のガラスビーズを含む
ＰＴＦＥ層を形成した。Thereafter, a dispersion (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) containing 3 parts by weight of glass beads (spherical diameter: 10 to 15 μm) relative to 100 parts by weight of PTFE powder.
Apply the product name TE-3481J) on the PTFE layer and apply 3
Heated at 70 ° C. for 3 minutes. This coating and heating were repeated twice more to form a PTFE layer containing glass beads having an adhesion amount of 390 g / m 2 .
【００２３】次に、ＰＴＦＥ粉末及びアナターゼ型光触
媒酸化チタン微粒子を含むディスパージョンをガラスビ
ーズを含むＰＴＦＥ層上に塗布し、３７０℃で３分間加
熱した。この塗布及び加熱をもう一度繰り返し、表面に
付着量２０ｇ／ｍ2 の光触媒酸化チタン微粒子を含むＰ
ＴＦＥ層をもつ目的の膜構造材を得た。Next, a dispersion containing PTFE powder and anatase type photocatalytic titanium oxide fine particles was applied onto the PTFE layer containing glass beads, and heated at 370 ° C. for 3 minutes. This coating and heating are repeated once more, and P containing photocatalytic titanium oxide fine particles with an adhesion amount of 20 g / m 2 is formed on the surface.
A target film structure material having a TFE layer was obtained.
【００２４】上記酸化チタンを含むＰＴＦＥ層形成用の
ディスパージョンはＰＴＦＥ粉末濃度６０重量％のディ
スパージョン（三井デュポンフロロケミカル社製、商品
名ＴＥ−３３１３Ｊ）１００重量部中にアナターゼ型光
触媒酸化チタン微粒子（石原産業社製、商品名ＳＴ−４
１）４０重量部及び蒸留水４０重量部を攪拌しながら分
散せしめ、さらに全重量に対して１重量％のシリコーン
系界面活性剤（日本ユニカー社製、商品名Ｌ−７７）を
攪拌しながら加えることによって調整した。なお、この
光触媒酸化チタン微粒子を含むＰＴＦＥ層の光触媒酸化
チタン微粒子とＰＴＦＥ粉末との重量比（光触媒酸化チ
タン微粒子：ＰＴＦＥ粉末）は４：６であった。The dispersion for forming the PTFE layer containing titanium oxide is anatase-type photocatalytic titanium oxide fine particles in 100 parts by weight of a PTFE powder concentration dispersion of 60% by weight (manufactured by Mitsui DuPont Fluorochemical Co., Ltd., trade name TE-3313J). (Product name ST-4 manufactured by Ishihara Sangyo Co., Ltd.
1) 40 parts by weight and 40 parts by weight of distilled water are dispersed with stirring, and 1% by weight of the total weight of a silicone-based surfactant (manufactured by Nippon Unicar, trade name L-77) is added with stirring. Adjusted by The weight ratio of the photocatalytic titanium oxide fine particles to the PTFE powder in the PTFE layer containing the photocatalytic titanium oxide fine particles (photocatalytic titanium oxide fine particles: PTFE powder) was 4: 6.
【００２５】このようにして得られた膜構造材の最外層
の表面を走査式電子顕微鏡で観察すると、光触媒酸化チ
タン微粒子が表面に露出した孔のない緻密な膜構造をし
ており、この膜構造を屋外にて３か月暴露試験を行った
ところ、表面には汚染が認めらず、島津製作所製の分光
分析装置ＵＶ−２４０を用いて光波長５５５ｎｍにおけ
る表面の反射率を測定したところ８８％で良好であっ
た。When the surface of the outermost layer of the film structure material thus obtained is observed with a scanning electron microscope, it has a dense film structure with no holes in which the photocatalytic titanium oxide fine particles are exposed on the surface. When the structure was subjected to an exposure test for 3 months outdoors, no contamination was found on the surface, and the reflectance of the surface at a light wavelength of 555 nm was measured using a spectroscopic analyzer UV-240 manufactured by Shimadzu. 88 % Was good.
【００２６】（実施例２）光触媒酸化チタン微粒子の配
合量を６．７重量部とした以外は実施例１と同様にして
膜構造材を得た。なお、この光触媒酸化チタン微粒子を
含むＰＴＦＥ層の光触媒酸化チタン微粒子とＰＴＦＥ粉
末との重量比（光触媒酸化チタン微粒子：ＰＴＦＥ粉
末）は１：９であった。このようにして得られた膜構造
材を屋外にて３か月暴露試験を行ったところ、表面には
汚染がやや認められたが、表面の反射率は７５％で良好
であった。(Example 2) A film structure material was obtained in the same manner as in Example 1 except that the amount of the fine particles of photocatalytic titanium oxide was 6.7 parts by weight. The weight ratio of the photocatalytic titanium oxide fine particles to the PTFE powder in the PTFE layer containing the photocatalytic titanium oxide fine particles (photocatalytic titanium oxide fine particles: PTFE powder) was 1: 9. When the film structural material thus obtained was subjected to an outdoor exposure test for 3 months, the surface was found to be slightly contaminated, but the surface reflectance was 75%, which was good.
【００２７】（実施例３）光触媒酸化チタン微粒子の配
合量を９０重量部とした以外は実施例１と同様にして膜
構造材を得た。なお、この光触媒酸化チタン微粒子を含
むＰＴＦＥ層の光触媒酸化チタン微粒子とＰＴＦＥ粉末
との重量比（光触媒酸化チタン微粒子：ＰＴＦＥ粉末）
は６：４であった。このようにして得られた膜構造材は
酸化チタン微粒子が少し脱落しやすい表面であったが、
屋外にて３か月暴露試験を行ったところ、表面には汚染
が認めらず、表面の反射率は８７％で良好であった。Example 3 A film structure material was obtained in the same manner as in Example 1 except that the amount of the photocatalyst titanium oxide fine particles was 90 parts by weight. The weight ratio of the photocatalytic titanium oxide fine particles and the PTFE powder in the PTFE layer containing the photocatalytic titanium oxide fine particles (photocatalytic titanium oxide fine particles: PTFE powder)
Was 6: 4. The film structure material thus obtained had a surface on which the titanium oxide fine particles were a little likely to fall off,
When an exposure test was conducted outdoors for 3 months, no contamination was found on the surface and the surface reflectance was good at 87%.
【００２８】（実施例４）光触媒酸化チタン微粒子の配
合量を３．２重量部とした以外は実施例１と同様にして
膜構造材を得た。なお、この光触媒酸化チタン微粒子を
含むＰＴＦＥ層の光触媒酸化チタン微粒子とＰＴＦＥ粉
末との重量比（光触媒酸化チタン微粒子：ＰＴＦＥ粉
末）は０．５：９．５であった。このようにして得られ
た膜構造材を屋外にて３か月暴露試験を行ったところ、
表面には汚染が認めらたが、表面の反射率は５０％であ
った。Example 4 A film structure material was obtained in the same manner as in Example 1 except that the amount of the photocatalytic titanium oxide fine particles was 3.2 parts by weight. The weight ratio of the photocatalytic titanium oxide fine particles to the PTFE powder in the PTFE layer containing the photocatalytic titanium oxide fine particles (photocatalytic titanium oxide fine particles: PTFE powder) was 0.5: 9.5. When the membrane structure material thus obtained was subjected to an outdoor exposure test for 3 months,
Contamination was observed on the surface, but the reflectance on the surface was 50%.
【００２９】（実施例５）光触媒酸化チタン微粒子の配
合量を１４０重量部とした以外は実施例１と同様にして
膜構造材を得た。なお、この光触媒酸化チタン微粒子を
含むＰＴＦＥ層の光触媒酸化チタン微粒子とＰＴＦＥ粉
末との重量比（光触媒酸化チタン微粒子：ＰＴＦＥ粉
末）は７：３であった。このようにして得られた膜構造
材は酸化チタン微粒子がかなり脱落しやすい表面であっ
たが、屋外にて３か月暴露試験を行ったところ、表面に
は汚染が認めらず、表面の反射率は８８％で良好であっ
た。Example 5 A film structure material was obtained in the same manner as in Example 1 except that the amount of the photocatalyst titanium oxide fine particles was 140 parts by weight. The weight ratio of the photocatalytic titanium oxide fine particles to the PTFE powder in the PTFE layer containing the photocatalytic titanium oxide fine particles (photocatalytic titanium oxide fine particles: PTFE powder) was 7: 3. The film structure material thus obtained had a surface on which the titanium oxide fine particles were quite likely to fall off, but when subjected to an outdoor exposure test for 3 months, no contamination was found on the surface and the surface reflection The rate was 88%, which was good.
【００３０】（比較例１）実施例１の光触媒酸化チタン
微粒子を含むＰＴＦＥ層の代わりにＦＥＰ層を設けた以
外は実施例と同様に膜構造材を得た。Comparative Example 1 A film structure material was obtained in the same manner as in Example 1 except that an FEP layer was provided instead of the PTFE layer containing the photocatalytic titanium oxide fine particles of Example 1.
【００３１】ＦＥＰ層はガラスビーズを含むＰＴＦＥ上
にＦＥＰ粉末濃度４０重量％のディスパージョン（三井
デュポンフロロケミカル社製、商品名ＴＥ−９５０３
Ｊ）を塗布し、３５０℃で２分間加熱し、この塗布及び
加熱をもう一度繰り返して、ＦＥＰの付着量５０ｇ／ｍ
2 となるようにして設けた。The FEP layer is a dispersion containing 40% by weight of FEP powder (made by Mitsui DuPont Fluorochemicals, trade name TE-9503) on PTFE containing glass beads.
J) is applied and heated at 350 ° C. for 2 minutes, and this application and heating are repeated once more, and the amount of FEP deposited is 50 g / m 2.
It was set to be 2 .
【００３２】このようにして得られた膜構造材を屋外に
て３か月暴露試験を行ったところ、表面には汚染が顕著
に認められ、表面の反射率は４５％であった。When the film structure material thus obtained was subjected to an outdoor exposure test for 3 months, the surface was markedly contaminated and the surface reflectance was 45%.
【００３３】これらの結果を以下の表１に示す。なお、
表中の密着性は光触媒酸化チタン微粒子を含むＰＴＦＥ
層のガラスビーズを含むＰＴＦＥ層への密着性である。The results are shown in Table 1 below. In addition,
The adhesion in the table is PTFE containing photocatalytic titanium oxide fine particles.
The adhesion of the layer to the PTFE layer containing the glass beads.
【００３４】[0034]
【表１】 [Table 1]
【００３５】本実施例及び比較例により、膜構造材の最
外層に光触媒酸化チタン微粒子を露出させたフッ素樹脂
層を形成することにより、膜構造材表面の耐汚染性を大
きく向上させることを確認できた。According to the present example and the comparative example, it was confirmed that the contamination resistance of the surface of the membrane structure material is greatly improved by forming the fluororesin layer exposing the photocatalytic titanium oxide fine particles on the outermost layer of the membrane structure material. did it.
【００３６】[0036]
【発明の効果】以上説明したように、本発明の膜構造材
によれば、ガラス繊維、金属繊維、及び鉱物繊維から選
ばれる少くとも１つを構成材料とする繊維布とフッ素樹
脂とを主材とする膜構造材であって、その少くとも一方
の最外表面層を光触媒酸化チタン微粒子を含むフッ素樹
脂層からなるものとすることにより、柔軟性、耐候性及
び機械的強度に優れるだけでなく、耐表面汚染性に優
れ、長期間きれいな外観を保つことができる膜構造材を
提供することができる。また、本発明の膜構造材の製造
方法によれば、ガラス繊維、金属繊維、及び鉱物繊維か
ら選ばれる少くとも１つを構成材料とする繊維布の表面
を光触媒酸化チタン微粒子とフッ素樹脂粉を含有する液
状物の塗膜で被覆し、この塗膜を前記フッ素樹脂粉の融
点以上の温度で焼成して光触媒酸化チタン微粒子を含む
フッ素樹脂層を形成することにより、優れた諸特性を有
する膜構造材を合理的に製造することができる。As described above, according to the membrane structure material of the present invention, a fiber cloth mainly composed of at least one selected from glass fiber, metal fiber, and mineral fiber and a fluororesin are mainly used. A film structure material as a material, and at least one of the outermost surface layers is made of a fluororesin layer containing photocatalytic titanium oxide fine particles, so that it is excellent in flexibility, weather resistance and mechanical strength. In addition, it is possible to provide a film structure material having excellent surface contamination resistance and capable of maintaining a clean appearance for a long period of time. Further, according to the method for producing a membrane structure material of the present invention, the surface of a fiber cloth made of at least one selected from glass fiber, metal fiber, and mineral fiber is treated with photocatalytic titanium oxide fine particles and fluororesin powder. A film having excellent properties by coating with a coating film of a liquid containing and baking the coating film at a temperature equal to or higher than the melting point of the fluororesin powder to form a fluororesin layer containing photocatalytic titanium oxide fine particles. The structural material can be reasonably manufactured.
【図１】 本発明の好適な実施形態を示す膜構造材の概
念断面図である。FIG. 1 is a conceptual cross-sectional view of a membrane structure material showing a preferred embodiment of the present invention.
１ ガラス繊維布 ２ シリコーン樹脂層 ３ ＰＴＦＥ層 ４ ガラスビーズを含むＰＴＦＥ層 ５ 光触媒酸化チタン微粒子を含むＰＴＦＥ層 1 glass fiber cloth 2 silicone resin layer 3 PTFE layer 4 PTFE layer containing glass beads 5 PTFE layer containing photocatalytic titanium oxide fine particles
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ３２Ｂ 27/04 Ｂ３２Ｂ 27/04 Ｚ 27/30 27/30 Ｄ (72)発明者 道本 忠憲 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (72)発明者 大西 伸夫 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (72)発明者 鳥居 晃 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内 (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Ｄ213号─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Reference number within the agency FI Technical display area B32B 27/04 B32B 27/04 Z 27/30 27/30 D (72) Inventor Tadanori Michimoto Osaka 1-1-2 Shimohozumi, Ibaraki, Ibaraki Prefecture Nitto Denko Corporation (72) Inventor Nobuo Ohnishi 1-2-1 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denko Corporation (72) Inventor Akira Torii Ibaraki, Osaka Prefecture Hozumi Ichimo 1-2-2 Nitto Denko Corporation (72) Inventor Akira Fujishima 710 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa 5 (72) Kazuhito Hashimoto 2073 Iijima-cho, Sakae-ku, Yokohama, Kanagawa Prefecture 2 New City Hongodai D213
Claims (9)
ら選ばれる少くとも１つを構成材料とする繊維布とフッ
素樹脂とを主材とする膜構造材であって、その少くとも
一方の最外表面層が光触媒酸化チタン微粒子を含むフッ
素樹脂層からなることを特徴とする膜構造材。1. A membrane structure material mainly composed of a fiber cloth and a fluororesin, which comprises at least one selected from glass fiber, metal fiber and mineral fiber as a constituent material, and at least one of A film structural material, wherein the outer surface layer is composed of a fluororesin layer containing photocatalytic titanium oxide fine particles.
脂層が非多孔性である請求項１に記載の膜構造材。2. The film structure material according to claim 1, wherein the fluororesin layer containing the photocatalytic titanium oxide fine particles is non-porous.
脂層の前記光触媒酸化チタン微粒子が層表面から露出し
ている請求項１に記載の膜構造材。3. The film structure material according to claim 1, wherein the photocatalytic titanium oxide fine particles of the fluororesin layer containing the photocatalytic titanium oxide fine particles are exposed from the layer surface.
脂層における光触媒酸化チタン微粒子とフッ素樹脂との
配合比（重量比）が光触媒酸化チタン微粒子：フッ素樹
脂で１：９〜６：４の範囲にある請求項１に記載の膜構
造材。4. The compounding ratio (weight ratio) of the photocatalytic titanium oxide fine particles to the fluororesin in the fluororesin layer containing the photocatalytic titanium oxide fine particles is in the range of 1: 9 to 6: 4 for the photocatalytic titanium oxide fine particles: the fluororesin. The membrane structure material according to claim 1.
０７〜０．５μｍである請求項１に記載の膜構造材。5. The photocatalytic titanium oxide fine particles have a particle size of 0.0.
The film structure material according to claim 1, having a thickness of 07 to 0.5 μm.
酸化チタン微粒子である請求項１に記載の膜構造材。6. The film structure material according to claim 1, wherein the photocatalytic titanium oxide fine particles are anatase type titanium oxide fine particles.
脂層の下にガラスビーズを含有するフッ素樹脂層が形成
されている請求項１に記載の膜構造材。7. The film structure material according to claim 1, wherein a fluororesin layer containing glass beads is formed below the fluororesin layer containing photocatalytic titanium oxide fine particles.
ら選ばれる少くとも１つを構成材料とする繊維布の表面
を光触媒酸化チタン微粒子とフッ素樹脂粉を含有する液
状物の塗膜で被覆し、この塗膜を前記フッ素樹脂粉の融
点以上の温度で焼成して光触媒酸化チタン微粒子を含む
フッ素樹脂層を形成する膜構造材の製造方法。8. A surface of a fiber cloth having at least one selected from glass fiber, metal fiber and mineral fiber as a constituent material is coated with a coating film of a liquid containing fine particles of photocatalytic titanium oxide and fluororesin powder. A method for producing a film structure material, wherein the coating film is baked at a temperature not lower than the melting point of the fluororesin powder to form a fluororesin layer containing photocatalytic titanium oxide fine particles.
ら選ばれる少くとも１つを構成材料とする繊維布の表面
をガラスビーズとフッ素樹脂粉を含有する第１の液状物
の塗膜で被覆し、この塗膜を前記フッ素樹脂粉の融点以
上の温度で焼成してガラスビーズが分散したフッ素樹脂
層を形成し、次に、前記ガラスビーズが分散したフッ素
樹脂層上に光触媒酸化チタン微粒子とフッ素樹脂粉を含
有する第２の液状物の塗膜を形成し、この塗膜を前記フ
ッ素樹脂粉の融点以上の温度で焼成して光触媒酸化チタ
ン微粒子を含むフッ素樹脂層を形成する膜構造材の製造
方法。9. A surface of a fiber cloth having at least one selected from glass fiber, metal fiber and mineral fiber as a constituent material is coated with a coating film of a first liquid containing glass beads and fluororesin powder. Then, this coating film is baked at a temperature equal to or higher than the melting point of the fluororesin powder to form a fluororesin layer in which glass beads are dispersed, and then photocatalytic titanium oxide fine particles are formed on the fluororesin layer in which the glass beads are dispersed. A film structure material for forming a coating film of a second liquid material containing fluororesin powder and firing the coating film at a temperature equal to or higher than the melting point of the fluororesin powder to form a fluororesin layer containing photocatalytic titanium oxide fine particles. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02109196A JP3540884B2 (en) | 1996-02-07 | 1996-02-07 | Manufacturing method of membrane structural material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02109196A JP3540884B2 (en) | 1996-02-07 | 1996-02-07 | Manufacturing method of membrane structural material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09207289A true JPH09207289A (en) | 1997-08-12 |
| JP3540884B2 JP3540884B2 (en) | 2004-07-07 |
Family
ID=12045207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02109196A Expired - Lifetime JP3540884B2 (en) | 1996-02-07 | 1996-02-07 | Manufacturing method of membrane structural material |
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| Country | Link |
|---|---|
| JP (1) | JP3540884B2 (en) |
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