JP4470198B2 - Photocatalyst sheet, film structure, and method for producing photocatalyst sheet - Google Patents
Photocatalyst sheet, film structure, and method for producing photocatalyst sheet Download PDFInfo
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- JP4470198B2 JP4470198B2 JP2003278672A JP2003278672A JP4470198B2 JP 4470198 B2 JP4470198 B2 JP 4470198B2 JP 2003278672 A JP2003278672 A JP 2003278672A JP 2003278672 A JP2003278672 A JP 2003278672A JP 4470198 B2 JP4470198 B2 JP 4470198B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 39
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 29
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
本発明は、基材最表面が光触媒を含むフッ素樹脂層で被覆された光触媒シート及びその製造方法に関する。 The present invention relates to a photocatalyst sheet whose outermost surface is coated with a fluororesin layer containing a photocatalyst and a method for producing the photocatalyst sheet.
野球場，催し場などのドームやサッカースタジアム，テント倉庫，体育館，商業施設などの膜構造物や、軒出テント，トラック幌，養生シートなどに使用される基材や、防雨服，カバン，椅子などに使用される防水布、ベルトコンベア，タイミングベルトなど機械用の繊維補強樹脂の基材には、透光性や防汚性を確保するために、ほぼ透明または無色透明な表面処理剤で被覆されている。なお本明細書で基材とは、上記各種の製品自体又はこれらの製品に用いられる材料を含む概念であり、材料（素材）の表面に表面処理剤を被覆した状態又は被覆する前の状態のものを含む概念として用いている。
従来にあっては、基材の表面に、防汚や耐久性の向上や接合など目的に応じた表面膜が形成されており、この表面膜としては、基材となる膜や繊維の彩色や透光性能を損なわないように、また、防汚性などを確保するために、ほぼ透明または無色透明な表面膜を使用していた。上記膜構造材として、例えば、ガラス繊維等からなる繊維布を基材とし、この基材をフッ素樹脂層で被覆した膜構造材が知られている。この膜構造材は、はっ水性（水との接触角は１１５°〜１２５°）があり、不燃性で機械強度が高く、しかも、軽量かつ柔軟性に富むという利点を有している。しかしながら、フッ素樹脂層で被覆した膜構造材においては、大気中の煤煙、粉塵、黄砂などの細い砂等の物質が膜表面に付着して汚れるという問題がある。
Domes such as baseball stadiums and event halls, soccer stadiums, tent warehouses, gymnasiums, commercial structures, membrane structures such as eaves tents, track hoods, curing sheets, rainproof clothing, bags, In order to ensure translucency and antifouling properties, the base material of fiber reinforced resin for machinery such as waterproof cloth used for chairs, belt conveyors, timing belts, etc. is almost transparent or colorless and transparent surface treatment agent. It is covered. In addition, in this specification, a base material is a concept including the above-mentioned various products themselves or materials used in these products, and is a state in which the surface of the material (raw material) is coated with a surface treatment agent or a state before coating. It is used as a concept including things.
Conventionally, a surface film according to the purpose such as antifouling, durability improvement and bonding is formed on the surface of the base material. In order not to impair the light transmission performance and to ensure antifouling properties, a surface film that is almost transparent or colorless and transparent has been used. As the membrane structure material, for example, a membrane structure material in which a fiber cloth made of glass fiber or the like is used as a base material and the base material is covered with a fluororesin layer is known. This membrane structure material has water repellency (contact angle with water is 115 ° to 125 °), has non-flammability, high mechanical strength, and is advantageous in that it is lightweight and flexible. However, a membrane structure material coated with a fluororesin layer has a problem that substances such as fine smoke such as smoke, dust, and yellow sand in the atmosphere adhere to the membrane surface and become dirty.
近年、光触媒はガラス基板などの各種の材料の表面に被覆されている。日光に含まれる紫外線が光触媒に照射されたとき、光触媒の酸化還元反応を利用して、材料の表面に付着した有機物などによる汚れを分解する、所謂、防汚に利用されつつある。
光触媒をガラス基板に付着させる方法としては、光触媒を含んだバインダ（結合剤）を用いる方法があり、例えば、溶媒中に、バインダとなる非酸化性高分子材料及び酸化チタン微粒子を混合した組成が知られている（特許文献１参照）。上記文献においては、バインダーとして、シリコーン樹脂などの非酸化性ポリマー、多孔質材のアルミナ及びシリカ、コロイド状酸化錫やこれらの材料の混合物を使用している。このバインダは、従来のプラスティックや繊維のように、加熱による熱処理（シンター）により被覆するための熱工程が必要であった材料にも、乾燥や、低温加熱（キュア）だけで、材料の表面に被覆できることが開示されているが、光触媒を含有させたフッ素樹脂層をフッ素樹脂層上に被覆する方法は開示されていない。
In recent years, the photocatalyst is coated on the surface of various materials such as a glass substrate. When the photocatalyst is irradiated with ultraviolet rays contained in sunlight, the photocatalyst is being used for so-called antifouling, in which the redox reaction of the photocatalyst is used to decompose dirt due to organic substances adhering to the surface of the material.
As a method for attaching a photocatalyst to a glass substrate, there is a method using a binder (binder) containing a photocatalyst. For example, a composition in which a non-oxidizing polymer material and titanium oxide fine particles serving as a binder are mixed in a solvent. It is known (see Patent Document 1). In the above documents, non-oxidizing polymers such as silicone resins, porous materials such as alumina and silica, colloidal tin oxide, and mixtures of these materials are used as binders. This binder can be applied to the surface of the material only by drying or low-temperature heating (cure), even for materials that require a heat treatment to be coated by heat treatment (sinter) by heating, such as conventional plastics and fibers. Although it is disclosed that it can be coated, a method of coating a fluororesin layer containing a photocatalyst on the fluororesin layer is not disclosed.
また、基材に光触媒を含有させたフッ素樹脂層を被覆する方法として、特許文献２及び３には、フッ素樹脂であるＰＴＦＥ層（ポリテトラフルオロエチレン）上に、光触媒酸化チタン微粒子を含有するディスパージョン（分散剤）を塗布して乾燥し、焼成する工程を繰り返して光触媒酸化チタン微粒子を露出させたＰＴＦＥ層を形成することが開示されている。 As a method for coating a fluororesin layer containing a photocatalyst on a substrate, Patent Documents 2 and 3 disclose a disperser containing photocatalytic titanium oxide fine particles on a PTFE layer (polytetrafluoroethylene) which is a fluororesin. It is disclosed that a PTFE layer in which photocatalytic titanium oxide fine particles are exposed is formed by repeating the steps of applying John (dispersing agent), drying, and baking.
また、特許文献４及び５には、膜構造材の補強層や支持体となるＰＴＦＥ層上に、ＰＴＦＥ粉末と光触媒微粒子とを含有するディスパージョンの塗布と焼成により、光触媒層を形成することが開示されている。 In Patent Documents 4 and 5, a photocatalyst layer is formed by applying and baking a dispersion containing PTFE powder and photocatalyst fine particles on a reinforcing layer of a membrane structure material or a PTFE layer as a support. It is disclosed.
また、特許文献６には、表面が平坦なアルミニウム合金基材を光触媒を含有させたフッ素樹脂で被覆したフッ素樹脂部材表面の親水化方法が開示されている。上記特許文献６においては、フッ素樹脂中にフッ化アルミニウムなどのセラミック成分を導入することにより親水化をはかった場合、再び疎水性を発現し防汚性を十分に発揮できない欠点（非特許文献１参照）を解決するためになされたものである。上記特許文献６においては、親水性を水に対する接触角が９０未満の材料としている。 Patent Document 6 discloses a method for hydrophilizing the surface of a fluororesin member in which an aluminum alloy substrate having a flat surface is coated with a fluororesin containing a photocatalyst. In the above-mentioned Patent Document 6, when a hydrophilic component is introduced by introducing a ceramic component such as aluminum fluoride into the fluororesin, the hydrophobicity is developed again and the antifouling property cannot be sufficiently exhibited (Non-Patent Document 1). Reference) was made. In the above-mentioned Patent Document 6, the hydrophilic property is a material having a contact angle with water of less than 90.
膜構造物が大面積の場合には、膜構造物用基材を多数枚使用して組み立てる。この場合には、膜構造物への漏水や空気漏れなどを防止するために、各膜構造物用基材同士を接合させる必要がある。従来、表面がフッ素樹脂で被覆されている基材の場合には、重ね合わせた部分よりも幅の広い同じフッ素樹脂のテープを熱溶着させることで、膜構造物用基材同士の熱接合を行っていた。
しかしながら、表面がフッ素樹脂で被覆されている基材の場合には、基材同士の熱接合はできるものの、フッ素樹脂の表面が汚れ易く、その洗浄は、屋外スタジアムのような大規模膜構造建築物においては、洗浄に要するコストが高いという課題がある。
When the membrane structure has a large area, it is assembled using a large number of membrane structure substrates. In this case, in order to prevent water leakage or air leakage to the membrane structure, it is necessary to join the membrane structure substrates together. Conventionally, in the case of a base material whose surface is coated with a fluororesin, the same fluororesin tape having a width wider than the overlapped portion is thermally welded so that the thermal bonding between the base materials for the membrane structure can be performed. I was going.
However, in the case of a base material whose surface is coated with a fluororesin, the base materials can be thermally bonded to each other, but the surface of the fluororesin is easily contaminated, and the cleaning is performed on a large-scale membrane structure such as an outdoor stadium. In a thing, there exists a subject that the cost required for washing | cleaning is high.
また、上記特許文献６のように、平滑なアルミニウム合金基材上のフッ素樹脂部材表面の親水化方法においては、紫外線を照射し光触媒の作用により親水化させているので、部材表面の十分な親水化には日数を要し、その間に汚れが付着したり、紫外線照射前は疎水性である表面領域（接触角が約９０°）における親水化による洗浄作用では十分な防汚性を発揮し難いという課題がある。 Further, as in the above-mentioned Patent Document 6, in the method for hydrophilizing the surface of the fluororesin member on the smooth aluminum alloy substrate, the surface of the member is sufficiently hydrophilic because it is made hydrophilic by the action of a photocatalyst by irradiating ultraviolet rays. It takes several days to make it clean, and dirt is attached between them, and it is difficult to exert sufficient antifouling property by the cleaning action by hydrophilization in the surface area (contact angle is about 90 °) that is hydrophobic before UV irradiation. There is a problem.
一方、光触媒をフッ素樹脂層に含有させた光触媒シートにおいては、フッ素樹脂層に酸化チタンのような光触媒となる無機物を含有させると熱接合が困難となるので、熱接合ができると共に、防汚性に優れた光触媒シートは、未だ実現されていない。 On the other hand, in a photocatalyst sheet containing a photocatalyst in a fluororesin layer, if an inorganic substance that becomes a photocatalyst such as titanium oxide is contained in the fluororesin layer, thermal joining becomes difficult, so that thermal joining is possible and antifouling properties are achieved. An excellent photocatalytic sheet has not been realized yet.
本発明は、上記課題に鑑み、基材の最表面が光触媒を含むフッ素樹脂層で被覆された光触媒シートにおいて、最表面がはっ水性を有し、この最表面に紫外線が照射されたときに高い防汚性を有する新規な光触媒シート及びその製造方法を提供することを目的としている。 In view of the above problems, the present invention provides a photocatalytic sheet in which the outermost surface of the substrate is coated with a fluororesin layer containing a photocatalyst, the outermost surface has water repellency, and the outermost surface is irradiated with ultraviolet rays. It aims at providing the novel photocatalyst sheet which has high antifouling property, and its manufacturing method.
上記目的を達成するため、本発明の光触媒シートの第１の構成は、基材にフッ素樹脂層が被覆され、該フッ素樹脂層のフッ素樹脂を溶融させてシート同士を互いに熱接合する光触媒シートであって、上記フッ素樹脂層は、上記基材上に被覆される第１のフッ素樹脂層と、該第１のフッ素樹脂層上に被覆される第２のフッ素樹脂層と、該第２のフッ素樹脂層上に被覆され、光触媒を含有させた第３のフッ素樹脂層と、からなり、上記第１のフッ素樹脂層のフッ素樹脂はＰＴＦＥで、上記第３のフッ素樹脂層のフッ素樹脂はＦＥＰであり、上記第３のフッ素樹脂層中の上記光触媒は１０〜６０重量％で、上記基材の表面粗さ（Ｒａ）が１０μｍ以上であり、上記第２のフッ素樹脂層は、上記基材の表面粗さの値より小さい値を有する厚さとし、上記第３のフッ素樹脂層は、１μｍ以上で上記基材の表面粗さの値より小さい値を有する厚さとし、上記第３のフッ素樹脂層表面が、水との接触角９０°以上のはっ水性を有すると共に、表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上であることを特徴とする。
本発明の光触媒シートの第２の構成は、基材にフッ素樹脂層が被覆され、該フッ素樹脂層のフッ素樹脂を溶融させてシート同士を互いに熱接合する光触媒シートであって、上記フッ素樹脂層は、上記基材上に被覆される第１のフッ素樹脂層と、該第１のフッ素樹脂層上に被覆され、光触媒を含有させた第２のフッ素樹脂層と、該第２のフッ素樹脂層上に被覆され、光触媒を含有させた第３のフッ素樹脂層と、からなり、上記第１のフッ素樹脂層のフッ素樹脂はＰＴＦＥで、上記第３のフッ素樹脂層のフッ素樹脂はＦＥＰであり、上記第３のフッ素樹脂層中の上記光触媒は１０〜６０重量％で、上記基材の表面粗さ（Ｒａ）が１０μｍ以上であり、上記第２のフッ素樹脂層の厚さは、上記基材の表面粗さの値より小さい値を有し、上記第３のフッ素樹脂層の厚さは、１μｍ以上で上記基材の表面粗さの値より小さい値を有し、上記第３のフッ素樹脂層表面が、水との接触角９０°以上のはっ水性を有すると共に、表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上であることを特徴とする。
上記何れの構成によっても、光触媒シートの最上層に含有される光触媒を含有したフッ素樹脂層表面がはっ水性を有し、光触媒に紫外線照射されたときの酸化還元作用により、表面の防汚性が高い光触媒シートを提供することができる。
Order to achieve the above object, the first construction of a photocatalytic sheet of the present invention, the fluorine resin layer is coated on a substrate, the photocatalyst sheet is melted fluororesin of the fluororesin layer is thermally bonded to each other to seat together with The fluororesin layer includes a first fluororesin layer that is coated on the substrate, a second fluororesin layer that is coated on the first fluororesin layer, and the second fluororesin layer. coated on a fluorine resin layer, and a third fluorine resin layer containing a photocatalyst made, a fluorine resin PTFE of the first fluororesin layer, a fluororesin of the third fluororesin layer FEP The photocatalyst in the third fluororesin layer is 10 to 60% by weight, the surface roughness (Ra) of the substrate is 10 μm or more, and the second fluororesin layer is composed of the substrate A thickness having a value smaller than the surface roughness value of The third fluororesin layer, thickness precepts have values less than value of the surface roughness of the substrate by 1μm or more, the third fluororesin layer surface, the contact angle of 90 ° or more water-repellent with water And the decomposition rate of the oleic glyceride is 0.4 mg / cm 2 · day or more when the surface is coated with oleic glyceride and irradiated with 1 mW / cm 2 ultraviolet rays. And
The second construction of a photocatalytic sheet of the present invention, the fluorine resin layer is coated on a substrate, the fluorine fluorine resin of the resin layer is melted by a photocatalyst sheet of thermally bonded together sheets together, the fluororesin layer a first fluororesin layer coated on the substrate and, coated on the first fluororesin layer, a second fluorine resin layer containing a photocatalyst, the second fluororesin layer coated on a third fluorine resin layer containing a photocatalyst made of fluororesin of the first fluororesin layer is PTFE, fluorocarbon resin of the third fluorocarbon resin layer is FEP, The photocatalyst in the third fluororesin layer is 10 to 60% by weight, the surface roughness (Ra) of the base material is 10 μm or more, and the thickness of the second fluororesin layer is the base material. Having a value smaller than the value of the surface roughness of The thickness of the fluororesin layer has a value less than the value of the surface roughness of the substrate by 1μm or more, the third fluororesin layer surface, the contact angle 90 ° or more water-repellent with water And the decomposition rate of the oleic glyceride is 0.4 mg / cm 2 · day or more when oleic glyceride is applied to the surface and the surface is irradiated with 1 mW / cm 2 ultraviolet rays. To do.
In any of the above structures, the surface of the fluororesin layer containing the photocatalyst contained in the uppermost layer of the photocatalyst sheet has water repellency, and the antifouling property of the surface by the oxidation-reduction action when the photocatalyst is irradiated with ultraviolet rays. Can provide a high photocatalytic sheet.
上記構成において、光触媒は、好ましくは、少なくとも酸化チタン（ＴｉＯ2 又はＴｉＯ3 ）からなる。光触媒は最上層となるフッ素樹脂上または第３のフッ素樹脂層上に露出している部分を有している。
光触媒を含有するフッ素樹脂層表面の光還元機能は、０．１Ｎ（規定）の硝酸銀水溶液中に前記光触媒シートを浸漬させ、その光触媒を含有させたフッ素樹脂層表面に１ｍＷ／ｃｍ2 の紫外線で１分照射したときの色差変化がΔＥ* ≧１であることが好ましい。
上記構成によれば、光触媒に光触媒の禁制帯幅以上のエネルギーを有する太陽や蛍光灯などに含まれる紫外線が照射されると、光触媒の酸化還元反応により、光触媒シートの表面に付着した有機物などの分解が行われることで、高い防汚性が付与される。
In the above configuration, the photocatalyst is preferably made of at least titanium oxide (TiO 2 or TiO 3 ). Photocatalysts that have a portion exposed on or third fluororesin layer fluororesin as a top layer.
The photoreduction function on the surface of the fluororesin layer containing a photocatalyst is obtained by immersing the photocatalyst sheet in a 0.1 N (regular) silver nitrate aqueous solution and applying 1 mW / cm 2 of ultraviolet light to the surface of the fluororesin layer containing the photocatalyst. it is preferred color difference change when irradiated one minute is Delta] E * ≧ 1.
According to the above configuration, when the photocatalyst is irradiated with ultraviolet rays contained in the sun or fluorescent lamp having energy greater than the forbidden band width of the photocatalyst, the organic catalyst attached to the surface of the photocatalyst sheet is caused by the oxidation-reduction reaction of the photocatalyst. By performing the decomposition, high antifouling property is imparted.
上記構成において、基材は繊維からなり、その表面形状が平坦でない凹凸面、メッシュ状のいずれかである。また、好ましくは、基材はガラス繊維であり、第２のフッ素樹脂層がＦＥＰまたはＰＦＡであるか、或いは、第２のフッ素樹脂層がＰＴＦＥ，ＦＥＰ，ＰＦＡの何れか一つの樹脂層であってもよい。
上記構成によれば、基材が繊維からなりその表面が適度な表面粗さを有しているので、平滑面に比較して、単位面積当たりの光触媒の表面積を大きくできることから、高い防汚性を得ることができる。したがって、光触媒を含有させたフッ素樹脂層に汚れが付着しても、表面粗さによりその周囲の三次元方向にある光触媒の酸化還元作用により高い防汚性を得ることができる。また、光触媒シート同士の熱接合特性を良好にできる。
The arrangement smell Te, the substrate is made of fibers, uneven surface the surface shape is not flat, is either meshed. Also preferably, the substrate is Ri fiberglass der, or the second fluororesin layer is FEP or PFA, walk the PTFE a second fluororesin layer, FEP, any one resin of PFA it may be a layer.
According to the above configuration, since the base material is made of fibers and the surface thereof has an appropriate surface roughness, the surface area of the photocatalyst per unit area can be increased compared to a smooth surface, thus providing high antifouling properties. Can be obtained. Therefore, even if dirt adheres to the fluororesin layer containing the photocatalyst, high antifouling properties can be obtained by the oxidation-reduction action of the photocatalyst in the three-dimensional direction around it due to the surface roughness. Moreover, the thermal joining characteristic between photocatalyst sheets can be made favorable.
次に、本発明の光触媒シートの製造方法は、基材にフッ素樹脂層が被覆され、該フッ素樹脂層のフッ素樹脂を溶融させてシート同士を互いに熱接合する光触媒シートの製造方法であって、上記基材の表面粗さ（Ｒａ）を１０μｍ以上とし、上記基材上に第１のフッ素樹脂層を被覆する工程と、該第１のフッ素樹脂層上に第２のフッ素樹脂層を被覆する工程と、該第２のフッ素樹脂層上に光触媒を１０〜６０重量％含有させた第３のフッ素樹脂層を被覆する工程と、からなり、上記第１のフッ素樹脂層のフッ素樹脂をＰＴＦＥとすると共に上記第３のフッ素樹脂層のフッ素樹脂をＦＥＰとし、上記第２のフッ素樹脂層の厚さを、上記基材の表面粗さの値より小さい値にすると共に、上記第３のフッ素樹脂層の厚さを、１μｍ以上で上記基材の表面粗さの値より小さい値にし、上記光触媒を含有させたフッ素樹脂層表面を、水との接触角が９０°以上のはっ水性とすると共に、上記フッ素樹脂層表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上にすることを特徴とする。
また、本発明の光触媒シートの製造方法は、基材にフッ素樹脂層が被覆され、該フッ素樹脂層のフッ素樹脂を溶融させてシート同士を互いに熱接合する光触媒シートの製造方法であって、上記基材の表面粗さ（Ｒａ）を１０μｍ以上とし、上記基材上に第１のフッ素樹脂層を被覆する工程と、該第１のフッ素樹脂層上に光触媒を含有させた第２のフッ素樹脂層を被覆する工程と、該第２のフッ素樹脂層上に光触媒を１０〜６０重量％含有させた第３のフッ素樹脂層を被覆する工程と、からなり、上記第１のフッ素樹脂層のフッ素樹脂をＰＴＦＥとすると共に上記第３のフッ素樹脂層のフッ素樹脂をＦＥＰとし、上記第２のフッ素樹脂層の厚さを、上記基材の表面粗さの値より小さい値にすると共に、上記第３のフッ素樹脂層の厚さを、１μｍ以上で上記基材の表面粗さの値より小さい値にし、上記光触媒を含有させたフッ素樹脂層表面を、水との接触角が９０°以上のはっ水性とすると共に、上記フッ素樹脂層表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上にすることを特徴とすることを特徴とする。
上記の製造方法によれば、基材の最表面が光触媒を含有したフッ素樹脂層で被覆されることで、最上層がはっ水性を有し、防汚性が高く、かつ、熱接合が容易にできる光触媒シートを低コストで製造することができる。
Next, the photocatalyst sheet manufacturing method of the present invention is a photocatalyst sheet manufacturing method in which a base material is coated with a fluororesin layer, the fluororesin layer is melted and the sheets are thermally bonded to each other, The surface roughness (Ra) of the substrate is set to 10 μm or more, and the first fluororesin layer is coated on the substrate, and the second fluororesin layer is coated on the first fluororesin layer. And a step of coating a third fluororesin layer containing 10 to 60% by weight of a photocatalyst on the second fluororesin layer, wherein the fluororesin of the first fluororesin layer is PTFE. In addition, the fluororesin of the third fluororesin layer is FEP, the thickness of the second fluororesin layer is set to a value smaller than the surface roughness value of the substrate, and the third fluororesin The surface of the base material with a layer thickness of 1 μm or more The fluororesin layer surface containing the photocatalyst having a value smaller than the roughness value is made water-repellent with a contact angle with water of 90 ° or more, and oleic glyceride is applied to the fluororesin layer surface. When the surface is irradiated with 1 mW / cm 2 of ultraviolet rays, the degradation rate of the oleic acid glyceride is 0.4 mg / cm 2 · day or more.
The photocatalyst sheet production method of the present invention is a photocatalyst sheet production method in which a base material is coated with a fluororesin layer, the fluororesin of the fluororesin layer is melted, and the sheets are thermally bonded to each other. A step of coating the first fluororesin layer on the base material with a surface roughness (Ra) of the base material of 10 μm or more, and a second fluororesin containing a photocatalyst on the first fluororesin layer And a step of coating a third fluororesin layer containing 10 to 60% by weight of a photocatalyst on the second fluororesin layer, and the fluorine of the first fluororesin layer. The resin is PTFE, the fluororesin of the third fluororesin layer is FEP, the thickness of the second fluororesin layer is set to a value smaller than the surface roughness value of the substrate, and the first The thickness of the fluororesin layer 3 is 1 μm or less The fluororesin layer surface containing the photocatalyst having a value smaller than the surface roughness value of the substrate is made water repellent with a contact angle with water of 90 ° or more, and the fluororesin layer surface characterized when illuminated with ultraviolet rays of 1 mW / cm 2 on the surface by applying oleic acid glyceride, the degradation rate of the oleic acid glyceride is characterized in that more than 2 day 0.4 mg / cm And
According to the above manufacturing method, the outermost surface of the base material is coated with a fluororesin layer containing a photocatalyst, so that the uppermost layer has water repellency, high antifouling property, and easy thermal bonding. The photocatalyst sheet which can be made can be manufactured at low cost.
上記構成において、第１のフッ素樹脂層と、第２のフッ素樹脂層または光触媒を含有させた第２のフッ素樹脂層と、光触媒とを含有させた第３のフッ素樹脂層と、を形成する被覆工程が連続して行われることを特徴とする。この構成によれば、基材上に、第１〜第３のフッ素樹脂層を連続的に被覆して、最上層が光触媒を含有させた第３のフッ素樹脂層とした光触媒シートを効率よく製造することができる。 In the above configuration, a coating that forms the first fluororesin layer, the second fluororesin layer containing the second fluororesin layer or the photocatalyst, and the third fluororesin layer containing the photocatalyst The process is performed continuously. According to this structure, the photocatalyst sheet | seat used as the 3rd fluororesin layer which covered the 1st-3rd fluororesin layer continuously on the base material and made the uppermost layer contain the photocatalyst efficiently is manufactured. can do.
上記構成において、予め第１のフッ素樹脂層及び第２のフッ素樹脂層を被覆した基材に、光触媒を含有させた第３のフッ素樹脂層を被覆する工程を行うようにしてもよい。このようにすれば、予め第１のフッ素樹脂層及び第２のフッ素樹脂層を被覆した基材を製造した後で、何時でも、光触媒を含有させた第３のフッ素樹脂層を被覆させることで、光触媒シートを製造することができる。 In the above-described configuration, a step of covering the base material previously coated with the first fluororesin layer and the second fluororesin layer with the third fluororesin layer containing the photocatalyst may be performed. In this way, after manufacturing the base material previously coated with the first fluororesin layer and the second fluororesin layer, the third fluororesin layer containing the photocatalyst can be coated at any time. A photocatalytic sheet can be produced.
また、光触媒を含有させた第３のフッ素樹脂層が、光触媒となる酸化チタン微粒子を含有させたフッ素樹脂用分散剤を第２のフッ素樹脂層上に塗布する工程と、乾燥する工程と、第３のフッ素樹脂層に用いるフッ素樹脂の融点よりも高い温度で焼結すると共に光触媒を第３のフッ素樹脂層の表面に露出させる工程と、を含むようにしてもよい。この構成によれば、光触媒を含有させた第３のフッ素樹脂層を基材上の第１及び第２のフッ素樹脂層に焼結でき、防汚性が高く、かつ、熱接合特性が良好な光触媒シートを製造することができる。 A third fluororesin layer containing a photocatalyst, a step of applying a fluororesin dispersant containing titanium oxide fine particles to be a photocatalyst onto the second fluororesin layer, a step of drying, And a step of sintering at a temperature higher than the melting point of the fluororesin used for the third fluororesin layer and exposing the photocatalyst to the surface of the third fluororesin layer. According to this configuration, the third fluororesin layer containing the photocatalyst can be sintered into the first and second fluororesin layers on the substrate, has high antifouling properties, and good thermal bonding characteristics. A photocatalytic sheet can be produced.
本発明の光触媒シートによれば、従来の最上層をフッ素樹脂層としたシートが有していた熱接合性を阻害することなく、はっ水性を有しかつ、高い防汚性を付与することができる。したがって、従来のシートに代えて、本発明の光触媒シートを膜構造物に使用すれば、シート同士の熱接合ができると共に、高い防汚性を発揮でき、シートに施した彩色の美観を損なうことなく長期間使用することができる。 According to the photocatalyst sheet of the present invention, it has water repellency and imparts high antifouling properties without impairing the thermal bondability of the conventional sheet having a fluororesin layer as the uppermost layer. Can do. Therefore, if the photocatalyst sheet of the present invention is used for the membrane structure instead of the conventional sheet, the sheets can be thermally bonded to each other, can exhibit high antifouling properties, and impair the color appearance applied to the sheet. And can be used for a long time.
また、本発明の光触媒シートの製造方法によれば、はっ水性を有し、防汚性が高く、かつ、光触媒シート同士の熱接合を容易に行うことができる光触媒シートを、低コストで製造し得る。 Moreover, according to the method for producing a photocatalyst sheet of the present invention, a photocatalyst sheet having water repellency, high antifouling properties, and capable of easily performing thermal bonding between the photocatalyst sheets is produced at low cost. Can do.
以下、この発明の実施の形態を図面により詳細に説明する。
本発明の光触媒シートの構造を図１〜図４を参照して説明する。図１及び図２は、本発明の光触媒シートの構造を模式的に示す断面図である。図に示すように、本発明の光触媒シート１は、ガラス繊維や繊維補強樹脂などからなる基材２の両面に、第１のフッ素樹脂層３と、第２のフッ素樹脂層４と、光触媒を含有させた第３のフッ素樹脂層５が順次積層された構造を有している。図１の場合には、一例として、基材２の両表面に多層のフッ素樹脂層３，４，５が被覆された構造を示しているが、図２に示すように、使用目的などに応じて、本発明の光触媒シート１０は基材２の片面又は表面の所定の領域だけに、光触媒を含有させた第３のフッ素樹脂層５を被覆するようにしても勿論構わない。
基材２は、ガラス繊維，カーボン繊維，ポリイミド繊維，ポリイミド繊維，ＰＢＯ繊維，シリカ繊維，バサルト繊維，ポリエステル繊維，ナイロン繊維，綿，麻，ケナフなどの繊維の織布又は不織布である。
ここで、基材２の表面形状は、後述するが、防汚性を高めるために、表面粗さ（Ｒａ）が粗い平坦でない凹凸面またはメッシュ状のいずれかであればよい。表面粗さは、平滑なアルミニウムやガラスの基材の表面粗さの１．４μｍ〜２．７μｍ程度の数倍以上の粗さであればよい。例えば、表面粗さが１０μｍ以上であればよい。
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The structure of the photocatalytic sheet of the present invention will be described with reference to FIGS. FIG.1 and FIG.2 is sectional drawing which shows typically the structure of the photocatalyst sheet | seat of this invention. As shown in the figure, the photocatalyst sheet 1 of the present invention has a first fluororesin layer 3, a second fluororesin layer 4, and a photocatalyst on both surfaces of a substrate 2 made of glass fiber, fiber reinforced resin, or the like. It has a structure in which the contained third fluororesin layer 5 is sequentially laminated. In the case of FIG. 1, as an example, a structure in which multilayer fluororesin layers 3, 4, and 5 are coated on both surfaces of the base material 2 is shown. However, as shown in FIG. Of course, the photocatalyst sheet 10 of the present invention may cover the third fluororesin layer 5 containing the photocatalyst only on a predetermined region of one side or the surface of the substrate 2.
The substrate 2 is a woven or non-woven fabric of fibers such as glass fiber, carbon fiber, polyimide fiber, polyimide fiber, PBO fiber, silica fiber, basalt fiber, polyester fiber, nylon fiber, cotton, hemp, and kenaf.
Here, although the surface shape of the base material 2 is mentioned later, in order to improve antifouling property, what is necessary is just a rough surface or a mesh shape with a rough surface roughness (Ra). The surface roughness may be a roughness several times or more of about 1.4 μm to 2.7 μm of the surface roughness of a smooth aluminum or glass substrate. For example, the surface roughness may be 10 μm or more.
上記第１〜第３のフッ素樹脂層３，４，５において、一例として、第１のフッ素樹脂層３の融点が第２のフッ素樹脂層４及び第３のフッ素樹脂層５の融点よりも高く、第２のフッ素樹脂層４の融点が第３のフッ素樹脂層５の融点と同じか、または、高くしてもよい。この場合には、第２のフッ素樹脂層４と第３のフッ素樹脂層５が同じフッ素樹脂からなっていてもよい。
この例に限らず、第１〜第３のフッ素樹脂層３，４，５のフッ素樹脂の材料を適宜選定すれば、光触媒シート同士の熱接合特性を良好とすることができる。これにより、光触媒シート同士の熱接合特性を良好とする第１〜第３のフッ素樹脂層の組合わせを容易に得ることができる。
In the first to third fluororesin layers 3, 4, and 5, as an example, the melting point of the first fluororesin layer 3 is higher than the melting points of the second fluororesin layer 4 and the third fluororesin layer 5. The melting point of the second fluororesin layer 4 may be the same as or higher than the melting point of the third fluororesin layer 5. In this case, the second fluororesin layer 4 and the third fluororesin layer 5 may be made of the same fluororesin.
Not only this example but the material of the fluororesin of the first to third fluororesin layers 3, 4, 5 can be appropriately selected, the thermal bonding characteristics between the photocatalyst sheets can be improved. Thereby, the combination of the 1st-3rd fluororesin layer which makes the heat joining characteristic of photocatalyst sheets favorable can be obtained easily.
フッ素樹脂としては、ポリテトラフルオロエチレン（ＰＴＦＥ、融点３２７℃），ポリビニリデンフルオライド（ＰＶＤＦ、融点１５６〜１７８℃），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（ＰＦＡ、融点＝３１０℃）、テトラフルオロエチレン−へキサフルオロプロピレン共重合体（ＦＥＰ、融点＝２７５℃）などのフッ素を含むモノマーの重合体、または、共重合体を用いることができる。なお、各材料の融点については、日本弗素樹脂工業会編、「フッ素樹脂ハンドブック」、改訂７版、日本弗素樹脂工業会、平成１０年（１９９８年）６月、ｐ．１８を参照されたい。
本発明の光触媒シート１は、一例として、基材２はガラス繊維、フッ素樹脂層として、第１のフッ素樹脂層３はＰＴＦＥ（融点Ｔ１＝３２７℃）、第２のフッ素樹脂層４はＦＥＰ（融点Ｔ２＝２７５℃）またはＰＦＡ（融点Ｔ２＝３１０℃）及び光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰ（融点Ｔ３＝２７５℃）で構成することができる。
As fluororesins, polytetrafluoroethylene (PTFE, melting point 327 ° C.), polyvinylidene fluoride (PVDF, melting point 156 to 178 ° C.), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA, melting point = 310 ° C.) , A polymer of a monomer containing fluorine such as tetrafluoroethylene-hexafluoropropylene copolymer (FEP, melting point = 275 ° C.), or a copolymer can be used. The melting point of each material is described in Japan Fluoropolymer Industry Association, edited by “Fluorine Resin Handbook”, 7th edition, Japan Fluoropolymer Industry Association, June 1998, p. See 18.
As an example, the photocatalyst sheet 1 of the present invention has a base material 2 as glass fiber, a fluororesin layer, a first fluororesin layer 3 as PTFE (melting point T1 = 327 ° C.), and a second fluororesin layer 4 as FEP ( The third fluororesin layer 5 containing a melting point T2 = 275 ° C. or PFA (melting point T2 = 310 ° C.) and a photocatalyst can be composed of FEP (melting point T3 = 275 ° C.).
図３は本発明の光触媒シート２０の別の構造を模式的に示す断面図である。図に示すように、本発明の光触媒シート２０が上記の光触媒シート１０と異なるのは、第２のフッ素樹脂層４’にも光触媒を含有させた点である。この第２のフッ素樹脂層４’は、第１のフッ素樹脂層と同じフッ素樹脂層、または、融点の低いフッ素樹脂層とすることができる。光触媒を含有させた第３のフッ素樹脂層５の融点（Ｔ３）は、光触媒を含有させた第２のフッ素樹脂層４’の融点（Ｔ２）と同じかより低い、即ち、Ｔ３≦Ｔ２というフッ素樹脂層としてもよい。他の構成は、光触媒シート１０と同じであるので、説明は省略する。
本発明の光触媒シート２０は、一例として、基材２はガラス繊維、第１のフッ素樹脂層３はＰＴＦＥ（融点Ｔ１＝３２７℃）、光触媒を含有させた第２のフッ素樹脂層４’としてＰＴＦＥ（融点Ｔ２＝３２７℃），ＦＥＰ（融点Ｔ２＝２７５℃）、ＰＦＡ（融点Ｔ２＝３１０℃）の何れか一つのフッ素樹脂、光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰ（融点Ｔ３＝２７５℃）で構成することができる。
この構成によれば、後述するが、光触媒を含む第２のフッ素樹脂層４’も光触媒を含むので、光触媒シート１同士を焼結により熱接合（以下、適宜、熱溶着とも呼ぶ）する際に、熱接合部における光触媒の作用による防汚性を損なうことがなく、防汚性を長期間に亘り維持することができる。
FIG. 3 is a cross-sectional view schematically showing another structure of the photocatalyst sheet 20 of the present invention. As shown in the figure, the photocatalyst sheet 20 of the present invention is different from the photocatalyst sheet 10 in that the photocatalyst is also contained in the second fluororesin layer 4 ′. The second fluororesin layer 4 ′ can be the same fluororesin layer as the first fluororesin layer or a fluororesin layer having a low melting point. The melting point (T3) of the third fluororesin layer 5 containing the photocatalyst is the same as or lower than the melting point (T2) of the second fluororesin layer 4 ′ containing the photocatalyst, ie, T3 ≦ T2. It is good also as a resin layer. Since the other structure is the same as the photocatalyst sheet 10, description is abbreviate | omitted.
As an example, the photocatalyst sheet 20 of the present invention is made of PTFE as the second fluororesin layer 4 ′ containing the glass fiber, the first fluororesin layer 3 as PTFE (melting point T1 = 327 ° C.), and the photocatalyst as an example. (Melting point T2 = 327 ° C.), FEP (melting point T2 = 275 ° C.), PFA (melting point T2 = 310 ° C.), FEP (melting point T3) as the third fluororesin layer 5 containing a photocatalyst. = 275 ° C.).
According to this configuration, as will be described later, since the second fluororesin layer 4 ′ containing the photocatalyst also contains the photocatalyst, when the photocatalyst sheets 1 are thermally bonded to each other by sintering (hereinafter also referred to as thermal welding as appropriate). In addition, the antifouling property due to the action of the photocatalyst in the heat bonding portion is not impaired, and the antifouling property can be maintained for a long period of time.
図４は、本発明の光触媒を含む第３のフッ素樹脂層を被覆した基材の表面側の構造を示す拡大断面図である。光触媒を含む第３のフッ素樹脂層５は、例えば、ＦＥＰなどのフッ素樹脂を使用し、さらに、光触媒７，８が添加されている。
ここで光触媒７，８は、直径が例えば１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 （二酸化チタン）などの光触媒微粒子であり、それぞれ、第３のフッ素樹脂層５内にある光触媒微粒子と、その表面５ａに露出した光触媒微粒子を示している。光触媒効果を高めるためには、表面５ａに露出した光触媒８の表面積を大きくするために、光触媒７，８の粒子径は、適度に小さいことが望ましい。
FIG. 4 is an enlarged cross-sectional view showing the structure on the surface side of the base material coated with the third fluororesin layer containing the photocatalyst of the present invention. For the third fluororesin layer 5 containing a photocatalyst, for example, a fluororesin such as FEP is used, and photocatalysts 7 and 8 are further added.
Here, the photocatalysts 7 and 8 are photocatalyst fine particles such as anatase type TiO 2 (titanium dioxide) having a diameter of, for example, 1 nm to 100 nm, and the photocatalyst fine particles in the third fluororesin layer 5 and the surface 5a thereof. The exposed photocatalyst fine particles are shown. In order to increase the photocatalytic effect, it is desirable that the particle diameters of the photocatalysts 7 and 8 are appropriately small in order to increase the surface area of the photocatalyst 8 exposed on the surface 5a.
ここで、光触媒７，８は光半導体とも呼ばれる材料である。光触媒７，８は、アナターゼ型ＴｉＯ2 （禁制帯幅３．２ｅＶ、波長３８８ｎｍ）のほかには、ルチル型ＴｉＯ2 （禁制帯幅３．０ｅＶ、波長４１４ｎｍ）、三酸化チタン（ＴｉＯ3 ）などが使用できる。これらのチタン酸化物を総称して酸化チタンと呼ぶ。光触媒は、酸化チタン以外には、酸化亜鉛（ＺｎＯ、禁制帯幅３．２ｅＶ、波長３８８ｎｍ）、チタン酸ストロンチウム（ＳｒＴｉＯ2 、禁制帯幅３．２ｅＶ、波長３８８ｎｍ）、三酸化タングステン（ＷＯ3 、禁制帯幅３．２ｅＶ、波長３８８ｎｍ）などが使用できる。 Here, the photocatalysts 7 and 8 are materials also called optical semiconductors. The photocatalysts 7 and 8 include anatase TiO 2 (forbidden band width 3.2 eV, wavelength 388 nm), rutile TiO 2 (forbidden band width 3.0 eV, wavelength 414 nm), titanium trioxide (TiO 3 ), etc. Can be used. These titanium oxides are collectively referred to as titanium oxide. In addition to titanium oxide, the photocatalyst includes zinc oxide (ZnO, forbidden band width 3.2 eV, wavelength 388 nm), strontium titanate (SrTiO 2 , forbidden band width 3.2 eV, wavelength 388 nm), tungsten trioxide (WO 3 , Forbidden band width 3.2 eV, wavelength 388 nm) and the like can be used.
また、上記光触媒を含む第３のフッ素樹脂層５中に含まれる光触媒の配合量は任意であるが、用途、性能、塗布方法により溶液の粘度を適宜調製すればよい。光触媒シート１，１０，２０の防汚性を高めると共に、光触媒シート同士の熱接合（以下、適宜、熱溶着とも呼ぶ）特性を良好とするためには、光触媒の配合量は、フッ素樹脂５中の固形濃度成分量として、好ましくは、１０〜６０重量％とすればよい。
光触媒を含有するフッ素樹脂層５表面の光酸化機能としては、フッ素樹脂層表面にオレイン酸グリセリドを塗布して表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、オレイン酸グリセリドの分解速度が０．１ｍｇ／ｃｍ2 ・日以上とすることが好ましい。また、光触媒を含有するフッ素樹脂層５表面の光還元機能としては、０．１Ｎ（規定）の硝酸銀水溶液中に前記光触媒シートを浸漬させ、その光触媒を含有させたフッ素樹脂層表面に１ｍＷ／ｃｍ2 で１分照射したときの色差変化がΔＥ* ≧１とすることが好ましい。
Moreover, the compounding quantity of the photocatalyst contained in the 3rd fluororesin layer 5 containing the said photocatalyst is arbitrary, What is necessary is just to adjust the viscosity of a solution suitably with a use, a performance, and the coating method. In order to improve the antifouling properties of the photocatalyst sheets 1, 10 and 20 and to improve the thermal bonding (hereinafter also referred to as heat welding as appropriate) characteristics between the photocatalyst sheets, the blending amount of the photocatalyst is The solid concentration component amount is preferably 10 to 60% by weight.
As the photo-oxidation function of the surface of the fluororesin layer 5 containing a photocatalyst, when the oleic acid glyceride is applied to the surface of the fluororesin layer and the surface is irradiated with 1 mW / cm 2 of ultraviolet rays, the degradation rate of the oleic acid glyceride is 0. .1 mg / cm 2 · day or more is preferable. Further, as a photoreduction function of the surface of the fluororesin layer 5 containing a photocatalyst, the photocatalyst sheet is immersed in an aqueous solution of 0.1N (normal) silver nitrate and 1 mW / cm on the surface of the fluororesin layer containing the photocatalyst. it is preferred that the color difference change when irradiated 1 minute 2 is a Delta] E * ≧ 1.
また、本発明の光触媒シートの表面は、紫外線照射の有無によらず、はっ水性を有している。この際、光触媒を含有するフッ素樹脂層５表面の水との接触角としては、おおよそ９０°以上のはっ水性とすることができる。
ここで、はっ水性の定義は、水との接触角が９０°以上であり、疎水性はその接触角が６０°〜９０°、親水性はその接触角が３０°以下である。なお、これらの接触角の定義は、藤嶋 昭、橋本 和仁、渡部 俊也著、「光触媒のしくみ」、第３版、株式会社日本実業出版社、２００１年３月２０日発行、ｐｐ．９６−９７参照）を参照されたい。
In addition, the surface of the photocatalyst sheet of the present invention has water repellency regardless of the presence or absence of ultraviolet irradiation. At this time, the contact angle with water on the surface of the fluororesin layer 5 containing the photocatalyst can be approximately 90 ° or more water repellency.
Here, the definition of water repellency is that the contact angle with water is 90 ° or more, the hydrophobicity has a contact angle of 60 ° to 90 °, and the hydrophilic property has a contact angle of 30 ° or less. These contact angles are defined by Akira Fujishima, Kazuhito Hashimoto, Toshiya Watanabe, “Mechanism of Photocatalyst”, 3rd edition, Nihon Jitsugyo Publishing Co., Ltd., published on March 20, 2001, pp. 96-97).
また、光触媒シート１，１０，２０を膜構造建築物に用い、光触媒シート同士を熱接合する場合には、最上層となる光触媒を含有するフッ素樹脂層５の厚さを１μｍ以上とすれば、光触媒シート１，１０，２０の熱接合特性を良好にすることができる。光触媒を含有させる第３のフッ素樹脂層５の厚さが１μｍ以下では、防汚性はあるものの、光触媒シート同士の摩擦や磨耗により熱接合した場合に剥離や亀裂などが生じやすく好ましくない。なお、光触媒シート同士に熱接合をしない場合には、光触媒を含有するフッ素樹脂層３の厚さを１μｍ以下としてもよい。
さらに、上記光触媒を含む第３のフッ素樹脂層５に、導電性や光触媒効果の増強効果をさらに付与するためには、金属材料や光触媒機能補助物質を添加すればよい。金属材料としては、Ａｇ，Ａｌ，Ａｕ，Ｃｕ，Ｆｅ，Ｉｎ，Ｉｒ，Ｎｉ，Ｏｓ，Ｐｄ，Ｐｔ，Ｒｈ，Ｒｕ，Ｓｂ，Ｓｎ，Ｚｎ，Ｚｒ等が使用できる。
Moreover, when using photocatalyst sheet | seat 1,10,20 for a film structure building and heat-joining photocatalyst sheets, if the thickness of the fluororesin layer 5 containing the photocatalyst used as the uppermost layer shall be 1 micrometer or more, The thermal bonding characteristics of the photocatalyst sheets 1, 10, and 20 can be improved. When the thickness of the third fluororesin layer 5 containing the photocatalyst is 1 μm or less, although there is antifouling property, it is not preferable because peeling or cracking is likely to occur when thermally bonded by friction or wear between the photocatalyst sheets. In addition, when not thermally bonding between photocatalyst sheets, it is good also considering the thickness of the fluororesin layer 3 containing a photocatalyst as 1 micrometer or less.
Furthermore, a metal material or a photocatalyst function auxiliary substance may be added to the third fluororesin layer 5 containing the photocatalyst to further enhance the conductivity and the photocatalytic effect. As the metal material, Ag, Al, Au, Cu, Fe, In, Ir, Ni, Os, Pd, Pt, Rh, Ru, Sb, Sn, Zn, Zr, or the like can be used.
本発明の光触媒シートは以上のように構成されており、その作用と効果について説明する。
本発明の光触媒シートの基材最上層に被覆された光触媒を含むフッ素樹脂層の表面粗さは平滑なアルミニウムやガラスの基材の表面粗さよりも粗く、光触媒の作用に係らず、最上層表面はフッ素樹脂の有するはっ水性が発現して、おおよそ、９０°以上のはっ水性を有している。
また、本発明の光触媒シートは、最上層のフッ素樹脂層に含まれる光触媒の量を適宜に調整することにより、光触媒同士の熱接合を容易に行うことができる。
このような本発明の光触媒シートに、光触媒の禁制帯幅以上のエネルギーを有し、太陽光や蛍光灯に含まれている、例えば、約４００ｎｍ以下の紫外線が照射されると、光触媒の酸化還元反応により、光触媒シートに付着する有機物などが分解することにより防汚性が付与される。この際、最上層のフッ素樹脂層が適度な粗さを有しているので、この最上層に露出する光触媒の表面積が大きくできることから、さらに高い防汚性を得ることができる。したがって、光触媒を含有させたフッ素樹脂層に汚れが付着しても、表面粗さによりその周囲の三次元方向にある光触媒の酸化還元作用により高い防汚性を得ることができる。
これにより、本発明の光触媒シートを、例えば、膜構造建築物に用いれば、従来の基材にフッ素樹脂を被覆したシートと同様に、光触媒シート同士の熱接合を容易に行うことができる。また、構造建築物の施工後において、光触媒シートの最上層に露出した酸化チタンなどの光触媒の酸化還元反応による高い防汚性により、長期間に亘り、シートの彩色の美観を損なうことがない。
The photocatalyst sheet of the present invention is configured as described above, and its operation and effect will be described.
The surface roughness of the fluororesin layer containing the photocatalyst coated on the base material uppermost layer of the photocatalyst sheet of the present invention is rougher than the surface roughness of the smooth aluminum or glass base material, regardless of the action of the photocatalyst. Exhibits the water repellency possessed by the fluororesin and has a water repellency of approximately 90 ° or more.
Moreover, the photocatalyst sheet of this invention can perform thermal joining of photocatalysts easily by adjusting suitably the quantity of the photocatalyst contained in the uppermost fluororesin layer.
When such a photocatalyst sheet of the present invention is irradiated with ultraviolet rays of, for example, about 400 nm or less, which has energy exceeding the band gap of the photocatalyst and is contained in sunlight or fluorescent lamps, for example, Antifouling properties are imparted by the decomposition of organic substances adhering to the photocatalyst sheet by the reaction. At this time, since the uppermost fluororesin layer has an appropriate roughness, the surface area of the photocatalyst exposed on the uppermost layer can be increased, so that higher antifouling properties can be obtained. Therefore, even if dirt adheres to the fluororesin layer containing the photocatalyst, high antifouling properties can be obtained by the oxidation-reduction action of the photocatalyst in the three-dimensional direction around it due to the surface roughness.
Thereby, if the photocatalyst sheet | seat of this invention is used for a film structure building, for example, the heat joining of photocatalyst sheets can be easily performed similarly to the sheet | seat which coat | covered the fluororesin to the conventional base material. In addition, after the construction of the structure building, the high antifouling property due to the oxidation-reduction reaction of the photocatalyst such as titanium oxide exposed on the uppermost layer of the photocatalyst sheet does not impair the aesthetic appearance of the color of the sheet for a long period of time.
次に、本発明の光触媒シートの製造方法を図５を参照して説明する。図５は、本発明の光触媒シートを製造する場合の工程を順次示すフロー図である。最初に、図５（Ａ）に示すように、ガラス繊維からなる基材２にディッピングコート法を用いて、第１のフッ素樹脂層３となるフッ素樹脂分散剤を塗布する。なお、本発明において、フッ素樹脂を形成するときに用いる塗布液や分散剤、または、塗布剤などを総称して分散剤と呼ぶ。 Next, the manufacturing method of the photocatalyst sheet of this invention is demonstrated with reference to FIG. FIG. 5 is a flow chart sequentially showing the steps in producing the photocatalytic sheet of the present invention. First, as shown in FIG. 5A, a fluororesin dispersant to be the first fluororesin layer 3 is applied to the base material 2 made of glass fibers by using a dipping coating method. In the present invention, the coating liquid, dispersant, or coating agent used when forming the fluororesin is generically called a dispersant.
続いて、図５（Ｂ）に示すように、フッ素樹脂分散剤の塗膜の均一性を良くするために、基材に塗布したフッ素樹脂分散剤を乾燥させる。この乾燥工程においては、乾燥温度を２０℃〜１００℃程度とし、乾燥時間を３分から６０分程度とすればよい。乾燥工程は、フッ素樹脂分散剤の組成に応じて、室温放置による自然乾燥または風または熱源を用いた強制乾燥法で行うことができる。強制乾燥法においては、抵抗加熱などの電気炉、赤外線や遠赤外加熱などの熱源と送風機を組み合わせた装置で行うことができる。 Subsequently, as shown in FIG. 5B, in order to improve the uniformity of the coating film of the fluororesin dispersant, the fluororesin dispersant applied to the substrate is dried. In this drying step, the drying temperature may be about 20 ° C. to 100 ° C., and the drying time may be about 3 to 60 minutes. Depending on the composition of the fluororesin dispersant, the drying step can be performed by natural drying by standing at room temperature or by a forced drying method using wind or a heat source. In the forced drying method, it can be performed with an electric furnace such as resistance heating, a heat source such as infrared or far-infrared heating, and an apparatus that combines a blower.
次に、図５（Ｃ）に示すように焼結工程を施して、基材２に第１のフッ素樹脂層３を被膜として形成する。この焼結工程の処理温度は、基材２に被覆させる第１のフッ素樹脂層３の融点に応じて設定すればよい。焼成温度として、第１のフッ素樹脂の融点よりも高くすることにより、フッ素樹脂が溶融し、フッ素樹脂粉末及び光触媒粉末の各粉末間の隙間がなくなる。この焼結工程は、例えば、第１のフッ素樹脂の融点よりもおおよそ５０℃高い程度の温度で３分〜３０分程度行えばよい。なお、焼結温度はフッ素樹脂の融点よりも５０℃以上の高温にすると、フッ素樹脂の分解温度に達し、フッ素樹脂の分解とそれに伴う基材の損傷を招く恐れがあるので好ましくない。
焼結後、冷却工程により室温に冷却される。この時点で、基材２は第１のフッ素樹脂層３の被膜で覆われる。冷却工程は第１のフッ素樹脂層３となる分散剤により形成される被膜を曇り（ヘイズ）がなく緻密で強靭な膜とするために、第１のフッ素樹脂層３を非結晶化させるために急冷することが好ましい。冷却工程は、焼結の後で第１のフッ素樹脂層３を被覆した基材２を、電気炉から取り出して室温である雰囲気において自然冷却で行うことができる。
なお、第１のフッ素樹脂層３を所定の膜厚とするために、上記の分散剤の塗布、乾燥、焼結工程を繰り替えし行ってもよい（図５（Ａ）と図５（Ｃ）に示した点線参照）。
Next, as shown in FIG. 5C, a sintering process is performed to form the first fluororesin layer 3 on the substrate 2 as a coating. What is necessary is just to set the processing temperature of this sintering process according to melting | fusing point of the 1st fluororesin layer 3 coat | covered with the base material 2. FIG. By setting the firing temperature to be higher than the melting point of the first fluororesin, the fluororesin melts and there is no gap between the fluororesin powder and the photocatalyst powder. This sintering step may be performed, for example, at a temperature of about 50 ° C. higher than the melting point of the first fluororesin for about 3 minutes to 30 minutes. If the sintering temperature is higher than the melting point of the fluororesin by 50 ° C. or more, the temperature reaches the decomposition temperature of the fluororesin, which may cause decomposition of the fluororesin and accompanying damage to the base material.
After sintering, it is cooled to room temperature by a cooling process. At this point, the base material 2 is covered with a coating of the first fluororesin layer 3. In order to make the first fluororesin layer 3 non-crystallized in order that the cooling process is a dense and tough film with no haze, the film formed by the dispersant that becomes the first fluororesin layer 3 Rapid cooling is preferred. The cooling step can be performed by natural cooling in an atmosphere at room temperature after taking out the substrate 2 coated with the first fluororesin layer 3 after sintering from the electric furnace.
In addition, in order to make the 1st fluororesin layer 3 into a predetermined film thickness, you may repeat and perform the application | coating of a dispersing agent, drying, and a sintering process (FIG. 5 (A) and FIG. 5 (C)). See dotted line).
次に、図５（Ｄ）に示すように、第１のフッ素樹脂層３上にディッピングコート法を用いて、第２のフッ素樹脂層４となるフッ素樹脂分散剤を塗布する。 Next, as shown in FIG. 5 (D), a fluororesin dispersant to be the second fluororesin layer 4 is applied on the first fluororesin layer 3 by using a dipping coating method.
続いて、図５（Ｅ）に示すように、第２のフッ素樹脂層４となるフッ素樹脂分散剤の塗膜の均一性を良くするために、第１のフッ素樹脂層３に塗布した第２のフッ素樹脂層４となるフッ素樹脂分散剤を乾燥させる。この乾燥工程においては、乾燥温度を２０℃〜１００℃程度とし、乾燥時間を３分から６０分程度とすればよい。 Subsequently, as shown in FIG. 5 (E), in order to improve the uniformity of the coating film of the fluororesin dispersant that becomes the second fluororesin layer 4, the second applied to the first fluororesin layer 3 is used. The fluororesin dispersant that becomes the fluororesin layer 4 is dried. In this drying step, the drying temperature may be about 20 ° C. to 100 ° C., and the drying time may be about 3 to 60 minutes.
次に、図５（Ｆ）に示すように焼結工程を施して、第１のフッ素樹脂層３上に第２のフッ素樹脂層４を被膜として形成する。この焼結工程の処理温度は、第１のフッ素樹脂層３に被覆させた第２のフッ素樹脂層４の融点に応じて設定すればよい。焼結後、冷却工程により室温に冷却される。この時点で、第１のフッ素樹脂層３は、第２のフッ素樹脂層４の被膜で覆われる。 Next, as shown in FIG. 5F, a sintering process is performed to form the second fluororesin layer 4 as a coating on the first fluororesin layer 3. What is necessary is just to set the processing temperature of this sintering process according to melting | fusing point of the 2nd fluororesin layer 4 coat | covered with the 1st fluororesin layer 3. FIG. After sintering, it is cooled to room temperature by a cooling process. At this point, the first fluororesin layer 3 is covered with the coating film of the second fluororesin layer 4.
その後、図５（Ｇ）に示すように、第２のフッ素樹脂層４上にディッピングコート法を用いて、光触媒を含有させた第３のフッ素樹脂層５となる、例えば、光触媒となる酸化チタン微粒子を含有させたフッ素樹脂用の分散剤を塗布する。 Thereafter, as shown in FIG. 5G, the third fluororesin layer 5 containing the photocatalyst is formed on the second fluororesin layer 4 by using a dipping coating method, for example, titanium oxide serving as a photocatalyst. A dispersant for fluororesin containing fine particles is applied.
そして、図５（Ｈ）に示すように、第２のフッ素樹脂層４上に塗布した光触媒を含有させたフッ素樹脂層５となる分散剤の塗膜の均一性を良くするために、乾燥させる。この乾燥工程においては、乾燥温度を２０℃〜１００℃程度とし、乾燥時間を３分から６０分程度とすればよい。 And as shown in FIG.5 (H), in order to improve the uniformity of the coating film of the dispersing agent used as the fluororesin layer 5 containing the photocatalyst apply | coated on the 2nd fluororesin layer 4, it is made to dry. . In this drying step, the drying temperature may be about 20 ° C. to 100 ° C., and the drying time may be about 3 to 60 minutes.
次に、図５（Ｉ）に示すように焼結工程を施して、第２のフッ素樹脂層４上に光触媒を含有させた第３のフッ素樹脂層５を被膜として形成する。この焼結工程の処理温度は、光触媒を含有させた第３のフッ素樹脂層５の融点に応じて設定すればよい。焼結後、冷却工程により室温に冷却される。この時点で、第２のフッ素樹脂層４は、光触媒を含有させた第３のフッ素樹脂層５の被膜で覆われる。
以上のようにして、本発明の光触媒シートを製造することができる。
Next, as shown in FIG. 5I, a sintering process is performed to form a third fluororesin layer 5 containing a photocatalyst on the second fluororesin layer 4 as a film. What is necessary is just to set the processing temperature of this sintering process according to melting | fusing point of the 3rd fluororesin layer 5 containing the photocatalyst. After sintering, it is cooled to room temperature by a cooling process. At this point, the second fluororesin layer 4 is covered with a film of the third fluororesin layer 5 containing a photocatalyst.
As described above, the photocatalytic sheet of the present invention can be produced.
ここで、上記各フッ素樹脂層に用いる分散剤を塗布する場合はディッピングコート法以外に、バーコート法、エアースプレーコート法，グラビアコート法，含浸法，スポンジ塗り法，静電スプレー法，刷毛塗り法，フローコート法，ロールコート法などが、好適に使用できる。 Here, when applying the dispersant used for each fluororesin layer, in addition to the dipping coating method, a bar coating method, an air spray coating method, a gravure coating method, an impregnation method, a sponge coating method, an electrostatic spray method, a brush coating method The method, the flow coat method, the roll coat method and the like can be suitably used.
なお、上記の製造工程は、ガラス繊維からなる基材２にディッピングコート法を用いて第１〜第３のフッ素樹脂層３，４，５を連続的に形成する方法の説明をした。別の方法として、ガラス繊維からなる基材２に第１及び第２のフッ素樹脂層３，４だけを形成した基材を先に製造し、後で、光触媒を含有させた第３のフッ素樹脂層５を被覆する工程により製造してもよい。 In addition, said manufacturing process demonstrated the method of forming the 1st-3rd fluororesin layers 3, 4, and 5 continuously in the base material 2 which consists of glass fiber using a dipping coat method. As another method, a base material in which only the first and second fluororesin layers 3 and 4 are formed on the base material 2 made of glass fiber is manufactured first, and a photocatalyst is added later. You may manufacture by the process of coat | covering the layer 5. FIG.
本発明の光触媒シートは、以上のように製造され、基材の最表面に光触媒を含有させた第３のフッ素樹脂層で被覆された光触媒シートを、低コストで製造することができる。 The photocatalyst sheet of this invention is manufactured as mentioned above, and can manufacture the photocatalyst sheet coat | covered with the 3rd fluororesin layer which made the outermost surface of a base material contain the photocatalyst at low cost.
以下、本発明の光触媒シートの実施例について説明する。
最初に、基材２として、平均厚さが０．４ｍｍのガラス繊維の両面に、第１のフッ素樹脂層３としてＰＴＦＥを約０．２ｍｍ、第２のフッ素樹脂層４としてＦＥＰを１０μｍ被膜した。最後に、光触媒を含有させた第３のフッ素樹脂層５であるＦＥＰ層を３μｍ被覆した。
図６は、実施例１において、光触媒を含有させた第３のフッ素樹脂層５の製造に用いた分散剤の組成を示す表である。分散剤は、ＦＥＰの水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を２１ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を６２．８ｋｇ、精製水を９４．４ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して、調製した。ＦＥＰと酸化チタン粉末の重量比率は４０：６０である。
光触媒を含有させた第３のフッ素樹脂層５は、次の製造工程で被覆した。
最初に、上記基材２に被覆された第２のフッ素樹脂層４であるＦＥＰを形成するための上記分散剤をディッピングコート法により両面に塗布し、自然乾燥し、次に６０℃で５分乾燥させた。そして、３２５℃で１０分間焼成した後、自然冷却させ、第２のフッ素樹脂層４であるＦＥＰを形成した。
第２のフッ素樹脂層４に上記分散剤をディッピングコート法により塗布した膜を常温で自然乾燥させた後で、６０℃で５分間乾燥した。さらに、３８０℃で１０分間加熱焼成してから自然冷却して、第２のフッ素樹脂層４上に光触媒を含有させた第３のフッ素樹脂層５であるＦＥＰ層を３μｍ被覆し、本発明の光触媒シート１を製造した。光触媒シート１の表面粗さは基材のガラス繊維２の表面粗さがフッ素樹脂層を塗布してもほとんど平坦化されないので、縦糸方向及び横糸方向の表面粗さ（Ｒａ）は、それぞれ、１４μｍ、１３μｍ程度であった。
Hereinafter, examples of the photocatalyst sheet of the present invention will be described.
First, as the substrate 2, on both sides of the glass textiles of average thickness of 0.4 mm, PTFE about 0.2mm as the first fluorocarbon resin layer 3, 10 [mu] m coating the FEP as a second fluororesin layer 4 did. Finally, the FEP layer which is the third fluororesin layer 5 containing the photocatalyst was coated with 3 μm.
FIG. 6 is a table showing the composition of the dispersant used in the production of the third fluororesin layer 5 containing the photocatalyst in Example 1. As the dispersant, an aqueous dispersion using an anatase type TiO 2 having an aqueous dispersion of FEP (solid content of 54% by weight, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and having a particle diameter of 1 nm to 100 nm is used. 62.8 kg of solid content (28% by weight, special order product), 94.4 kg of purified water, 1.8 kg of silicon surfactant (manufactured by Nihon Unicar Co., Ltd., L-77) (1 wt% of the total) are mixed and stirred And prepared. The weight ratio of FEP and titanium oxide powder is 40:60.
The 3rd fluororesin layer 5 containing the photocatalyst was coat | covered with the following manufacturing process.
First, the dispersant for forming the FEP which is the second fluororesin layer 4 coated on the base material 2 is applied to both sides by a dipping coat method, followed by natural drying, and then at 60 ° C. for 5 minutes. Dried. And after baking for 10 minutes at 325 degreeC, it was made to cool naturally and FEP which is the 2nd fluororesin layer 4 was formed.
After the film | membrane which apply | coated the said dispersing agent to the 2nd fluororesin layer 4 by the dipping coating method was naturally dried at normal temperature, it was dried at 60 degreeC for 5 minute (s). Furthermore, after heating and baking at 380 ° C. for 10 minutes, the film was naturally cooled, and the FEP layer as the third fluororesin layer 5 containing the photocatalyst was coated on the second fluororesin layer 4 by 3 μm. Photocatalyst sheet 1 was produced. Since the surface roughness of the photocatalyst sheet 1 is hardly flattened even if the surface roughness of the glass fiber 2 of the base material is coated with a fluororesin layer, the surface roughness (Ra) in the warp direction and the weft direction is 14 μm, respectively. About 13 μm.
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図７は、実施例２において、光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を４２．３ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を５４．４ｋｇ、精製水を８１．５ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は６０：４０である。そして、実施例１と同様の製造工程により、本発明の光触媒シート１を製造した。光触媒シート１の表面粗さは実施例１と同程度であった。
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 7 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Example 2. As the dispersant, 42.3 kg of FEP aqueous dispersion (solid content: 54% by weight, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and an aqueous dispersion using anatase TiO 2 having a particle diameter of 1 nm to 100 nm are used. (Solid content 28% by weight, custom-made product) 54.4 kg, purified water 81.5 kg, silicon surfactant (manufactured by Nihon Unicar Co., Ltd., L-77) 1.8 kg (1% by weight of the total), Prepared by stirring. The weight ratio of FEP and titanium oxide powder is 60:40. And the photocatalyst sheet 1 of this invention was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet 1 was almost the same as in Example 1.
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図８は、実施例３において、光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を５８．９ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を４８．６ｋｇ、精製水を７０．７ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は７０：３０である。そして、実施例１と同様の製造工程により、本発明の光触媒シート１を製造した。光触媒シート１の表面粗さは実施例１と同程度であった。
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 8 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Example 3. As the dispersant, an aqueous dispersion using 58.9 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and anatase TiO 2 having a particle diameter of 1 nm to 100 nm. (Solid content 28 wt%, custom-made product) 48.6 kg, purified water 70.7 kg, silicon surfactant (Nihon Unicar Co., Ltd., L-77) 1.8 kg (1 wt% of the total), Prepared by stirring. The weight ratio of FEP and titanium oxide powder is 70:30. And the photocatalyst sheet 1 of this invention was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet 1 was almost the same as in Example 1.
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図９は実施例４において光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を８０．９ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を３９ｋｇ、精製水を５８．３ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）を１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は８０：２０である。そして、実施例１と同様の製造工程により、本発明の光触媒シート１を製造した。光触媒シート１の表面粗さは実施例１と同程度であった。
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 9 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Example 4. The dispersant is an aqueous dispersion using 80.9 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and anatase TiO 2 having a particle diameter of 1 nm to 100 nm. (Solid content 28% by weight, custom-made product) 39 kg, purified water 58.3 kg, silicon surfactant (manufactured by Nippon Unicar Co., Ltd., L-77) 1.8 kg (1% by weight of the total) mixed and stirred Prepared. The weight ratio of FEP and titanium oxide powder is 80:20. And the photocatalyst sheet 1 of this invention was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet 1 was almost the same as in Example 1.
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図１０は、実施例５において光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を１１７．６ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を２５．２ｋｇ、精製水を３５．４ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は９０：１０である。そして、実施例１と同様の製造工程により、光触媒シート１を製造した。光触媒シート１の表面粗さは実施例１と同程度であった。
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 10 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Example 5. The dispersant is an aqueous dispersion using 117.6 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and anatase type TiO 2 having a particle diameter of 1 nm to 100 nm. (Solid content 28 wt%, custom-made product) 25.2 kg, purified water 35.4 kg, silicon surfactant (manufactured by Nihon Unicar Co., Ltd., L-77) 1.8 kg (1 wt% of the total), Prepared by stirring. The weight ratio of FEP and titanium oxide powder is 90:10. And the photocatalyst sheet 1 was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet 1 was almost the same as in Example 1.
次に、本発明の光触媒シート２０を製造した実施例６について説明する。
基材２として、平均厚さが０．４ｍｍのガラス繊維の両面に、第１のフッ素樹脂層３としてＰＴＦＥを約０．２ｍｍ被覆し、このＰＴＦＥ層の両面に、実施例１のＦＥＰの分散剤を使用して、光触媒を含有させた第２のフッ素樹脂層４’である厚さ１０μｍのＦＥＰ層と、光触媒を含有させた第３のフッ素樹脂層５である厚さＦＥＰ３μｍのＦＥＰ層と、を順次積層して、光触媒シート２０を製造した。光触媒を含有させたＦＥＰ層を形成する分散剤は、実施例２と同じであり、ＦＥＰと酸化チタン粉末の重量比率は６０：４０であった。光触媒シート１の表面粗さは実施例１と同程度であった。
Next, Example 6 which manufactured the photocatalyst sheet | seat 20 of this invention is demonstrated.
As the substrate 2, on both sides of the glass textiles of average thickness of 0.4 mm, PTFE and about 0.2mm coated as the first fluorocarbon resin layer 3, on both surfaces of the PTFE layer of Example 1 of FEP Using a dispersant, the FEP layer having a thickness of 10 μm that is the second fluororesin layer 4 ′ containing the photocatalyst and the FEP layer having a thickness of FEP of 3 μm that is the third fluororesin layer 5 containing the photocatalyst And the photocatalyst sheet 20 were manufactured. The dispersant for forming the FEP layer containing the photocatalyst was the same as in Example 2, and the weight ratio of FEP to titanium oxide powder was 60:40. The surface roughness of the photocatalyst sheet 1 was almost the same as in Example 1.
次に、比較例について説明する。
（比較例１）
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図１１は、比較例１において、光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤の組成は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を１４．６ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を６５．７ｋｇ、精製水を９７．９ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は３０：７０である。そして、実施例１と同様の製造工程により比較例１の光触媒シートを製造した。光触媒シートの表面粗さは実施例１と同程度であった。
Next, a comparative example will be described.
(Comparative Example 1)
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 11 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Comparative Example 1. The composition of the dispersant is an aqueous system using 14.6 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and anatase TiO 2 having a particle size of 1 nm to 100 nm. Dispersion (solid content 28 wt%, custom-made product) 65.7 kg, purified water 97.9 kg, silicon surfactant (Nihon Unicar Co., Ltd., L-77) 1.8 kg (1 wt% of the total) Prepared by mixing and stirring. The weight ratio of FEP and titanium oxide powder is 30:70. And the photocatalyst sheet of the comparative example 1 was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet was about the same as in Example 1.
（比較例２）
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図１２は、比較例２において、光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤の組成は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を８．８ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を６７．５ｋｇ、精製水を１０１．９ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は２０：８０である。そして、実施例１と同様の製造工程により比較例２の光触媒シートを製造した。光触媒シートの表面粗さは実施例１と同程度であった。
(Comparative Example 2)
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 12 is a table showing the composition of the dispersant used for the third fluororesin layer 5 containing a photocatalyst in Comparative Example 2. The composition of the dispersant is 8.8 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J), and an aqueous system using anatase TiO 2 having a particle diameter of 1 nm to 100 nm. Dispersion (solid content 28% by weight, custom-made product) 67.5 kg, purified water 101.9 kg, silicon surfactant (manufactured by Nippon Unicar Co., Ltd., L-77) 1.8 kg (1% by weight of the total) Prepared by mixing and stirring. The weight ratio of FEP to titanium oxide powder is 20:80. And the photocatalyst sheet of the comparative example 2 was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet was about the same as in Example 1.
（比較例３）
ＦＥＰの分散剤組成を変えた以外は、実施例１と同様に、基材の最上層に光触媒を含有させた第３のフッ素樹脂層５としてＦＥＰを形成した。
図１３は、比較例３において、光触媒を含有させた第３のフッ素樹脂層５に用いた分散剤の組成を示す表である。分散剤の組成は、ＦＥＰ水系ディスパージョン（固形分５４重量％、三井デュポンフロロケミカル（株）製、１２０−Ｊ）を４．１ｋｇ、粒径が１ｎｍ〜１００ｎｍのアナターゼ型ＴｉＯ2 を用いた水系ディスパージョン（固形分２８重量％、特注品）を７０．２ｋｇ、精製水を１０３．９ｋｇ、シリコン系界面活性剤（日本ユニカー社製、Ｌ−７７）１．８ｋｇ（全体の１重量％）を混合、攪拌して調製した。ＦＥＰと酸化チタン粉末の重量比率は１０：９０である。そして、実施例１と同様の製造工程により比較例３の光触媒シートを製造した。光触媒シートの表面粗さは実施例１と同程度であった。
(Comparative Example 3)
The FEP was formed as the third fluororesin layer 5 containing the photocatalyst in the uppermost layer of the substrate in the same manner as in Example 1 except that the dispersant composition of the FEP was changed.
FIG. 13 is a table showing the composition of the dispersant used in the third fluororesin layer 5 containing a photocatalyst in Comparative Example 3. The composition of the dispersant is 4.1 kg of FEP aqueous dispersion (solid content 54 wt%, manufactured by Mitsui DuPont Fluorochemical Co., Ltd., 120-J) and an aqueous system using anatase TiO 2 having a particle diameter of 1 nm to 100 nm. Dispersion (solid content 28% by weight, custom-made product) 70.2 kg, purified water 103.9 kg, silicon surfactant (Nihon Unicar, L-77) 1.8 kg (1% by weight of the total) Prepared by mixing and stirring. The weight ratio of FEP and titanium oxide powder is 10:90. And the photocatalyst sheet of the comparative example 3 was manufactured according to the manufacturing process similar to Example 1. FIG. The surface roughness of the photocatalyst sheet was about the same as in Example 1.
（比較例４）
最上層となる第３のフッ素樹脂層に光触媒を入れない以外は、実施例１と同様の製造方法により、従来構造のシートを製造した。光触媒シート１の表面粗さは実施例よりも若干大きい程度であった。
(Comparative Example 4)
A sheet having a conventional structure was produced by the same production method as in Example 1 except that the photocatalyst was not added to the third fluororesin layer as the uppermost layer. The surface roughness of the photocatalyst sheet 1 was slightly larger than that of the example.
実施例１〜６で製造した光触媒シート及び比較例１〜４で製造したシートを、膜構造建築物の施工に使用し、光触媒を含有させた最上層の光触媒機能と、はっ水性と、熱接合特性と、屋外暴露の汚れの評価を行った。
図１４及び図１５は、それぞれ、実施例と比較例との光触媒を含有させた最上層の光触媒機能と、接触角と、熱接合特性と、屋外暴露の汚れの評価結果を示す表である。表は、各実施例と各比較例における光触媒の第３のフッ素樹脂層中の重量％と、それに対応する最上層の光触媒機能と、はっ水性と、熱接合特性と、屋外暴露の汚れの評価結果を示している。
最上層の光触媒機能としては有機物（オレイン酸グリセリド）の分解特性を測定した。光触媒を含有させたフッ素樹脂層表面（２５ｃｍ2 ）にオレイン酸グリセリドを塗布して、紫外線照射を行ったときのオレイン酸グリセリドの分解量を測定した。紫外線照射は、紫外線源として１５Ｗのブラックライトランプ（ＦＬ１５ＢＬＢ：東芝ライテック製）を用いて、２４時間紫外線照射を行った。このときの紫外線強度は、日中の屋外の紫外線の強度と同等の１ｍＷ／ｃｍ2 であった。
図１４ら明らかなように、最上層のフッ素樹脂層５に含有される光触媒が２０重量％から６０重量％である実施例１〜６においては、オレイン酸グリセリドの分解速度は０．４ｍｇ／ｃｍ2 ・日以上が得られ、分解速度が速いことが分かった。
また、図１５から明らかなように、光触媒が７０重量％以上の比較例１〜３の場合にも、オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上であり分解速度が速い。比較例４の従来の光触媒触媒を含有させていないシートの場合には、オレイン酸グリセリドの分解作用がないので測定を行わなかった。
The photocatalyst sheet produced in Examples 1 to 6 and the sheet produced in Comparative Examples 1 to 4 were used for the construction of a membrane structure building, and the photocatalyst function of the uppermost layer containing the photocatalyst, water repellency, and heat We evaluated the bonding characteristics and contamination of outdoor exposure.
14 and 15 are tables showing the evaluation results of the photocatalyst function of the uppermost layer containing the photocatalyst of Example and Comparative Example, the contact angle, the thermal bonding characteristics, and the dirt of outdoor exposure, respectively. The table shows the weight% of the photocatalyst in the third fluororesin layer in each Example and each Comparative Example, the corresponding photocatalyst function of the uppermost layer, water repellency, thermal bonding characteristics, and contamination of outdoor exposure. The evaluation results are shown.
As the photocatalytic function of the uppermost layer, the decomposition characteristics of organic matter (oleic glyceride) were measured. An oleic glyceride was applied to the surface (25 cm 2 ) of the fluororesin layer containing a photocatalyst, and the amount of oleic glyceride decomposed when irradiated with ultraviolet rays was measured. Ultraviolet irradiation was performed for 24 hours using a 15 W black light lamp (FL15BLB: manufactured by Toshiba Lighting & Technology) as an ultraviolet source. The ultraviolet intensity at this time was 1 mW / cm 2 which is equivalent to the intensity of ultraviolet light outdoors in the daytime.
As apparent from FIG. 14, in Examples 1 to 6 in which the photocatalyst contained in the uppermost fluororesin layer 5 is 20 wt% to 60 wt%, the decomposition rate of oleic glyceride is 0.4 mg / cm 2. 2 days or more were obtained, and it was found that the degradation rate was fast.
As is clear from FIG. 15, also in Comparative Examples 1 to 3 in which the photocatalyst is 70% by weight or more, the degradation rate of oleic glyceride is 0.4 mg / cm 2 · day or more, and the degradation rate is fast. In the case of the sheet not containing the conventional photocatalyst catalyst of Comparative Example 4, no measurement was performed because there was no decomposition action of oleic glyceride.
また、最上層の光触媒機能としての還元作用は、光触媒シートを０．１Ｎ（規定）の硝酸銀水溶液中に浸漬し、その光触媒を含有させたフッ素樹脂層表面に上記紫外線源により、紫外線１ｍＷ／ｃｍ2 で１分照射した後の色差変化（ΔＥ* ）を調べた。色差変化の測定方法は、ＪＩＳ規格のＺ８７０１とＺ８７３０である。測定は、分光光度計（日立Ｕ−３４１０型）を使用して可視光領域（３８０ｎｍ〜７８０ｎｍ）で行った。
図１４から明らかなように、最上層のフッ素樹脂層５に含有される光触媒が２０重量％から６０重量％である実施例１〜６における、光触媒による硝酸銀水溶液中の銀の還元作用による色差変化（ΔＥ* ）は４．９４から２８となり、光触媒による還元作用が高い。色差変化は、光触媒の含有量が多くなると還元機能が増大するので大きくなっている。
また、図１５から明らかなように、光触媒が７０％重量以上の比較例１〜３の場合にも、光触媒による硝酸銀中の銀の還元作用による色差変化（ΔＥ* ）は２６〜２８あり、光触媒による還元作用が高い。比較例４の従来の光触媒触媒を含有させていないシートの場合には還元作用がないので測定を行わなかった。
Further, the reducing action as the photocatalytic function of the uppermost layer is that the photocatalyst sheet is immersed in a 0.1N (normal) silver nitrate aqueous solution, and the surface of the fluororesin layer containing the photocatalyst is irradiated with 1 mW / cm of ultraviolet light by the above ultraviolet light source. The change in color difference (ΔE * ) after 1 minute irradiation at 2 was examined. The measuring method of the color difference change is JIS standard Z8701 and Z8730. The measurement was performed in a visible light region (380 nm to 780 nm) using a spectrophotometer (Hitachi U-3410 type).
As apparent from FIG. 14, the color difference change due to the reducing action of silver in the aqueous silver nitrate solution by the photocatalyst in Examples 1 to 6 in which the photocatalyst contained in the uppermost fluororesin layer 5 is 20 wt% to 60 wt%. (Delta] E *) is next 28 from 4.94, the reduction action by the photocatalyst is high. The change in color difference increases because the reduction function increases as the photocatalyst content increases.
As is apparent from FIG. 15, even in Comparative Examples 1 to 3 in which the photocatalyst is 70% by weight or more, the color difference change (ΔE * ) due to the reducing action of silver in the silver nitrate by the photocatalyst is 26 to 28. Reduction effect by is high. In the case of the sheet of Comparative Example 4 which did not contain the conventional photocatalytic catalyst, no measurement was performed because there was no reducing action.
さらに、最上層の接触角は、実施例及び比較例の光触媒シートの製造直後と、紫外線照射後の測定を行った。紫外線照射は、キセノンウェザーメーター（１８ｍＷ／ｃｍ2 ）により２４時間照射した。接触角の測定は、協和界面科学社製の接触角計（ＣＡ−Ｘ型）を用い、試料表面に純水６μＬ（リットル）（６×１０-6Ｌ）を滴下して行った。
図１４から明らかなように、最上層のフッ素樹脂層５に含有される光触媒が２０重量％から６０重量％である実施例１〜６における製造直後の接触角は約１１０°から１２０°であり、はっ水性であった。また、各実施例１〜６において紫外線照射後の接触角は、約１０４°から１１１°であり、製造直後よりも若干低下したがはっ水性を示す。
また、図１５から明らかなように、光触媒が７０重量％と８０重量％の比較例１及び２の場合には、製造直後及び紫外線照射後において、接触角が１０５°以上ではっ水性であり、光触媒が９０重量％の比較例３の場合には、製造直後は接触角が約１０８°ではっ水性となり、紫外線照射後には８０°の疎水性となった。比較例４の従来の光触媒触媒を含有させていないシートの場合にはフッ素樹脂の接触角となるので測定を行わなかった。
Furthermore, the contact angle of the uppermost layer was measured immediately after the production of the photocatalyst sheets of Examples and Comparative Examples and after ultraviolet irradiation. Ultraviolet irradiation was performed for 24 hours using a xenon weather meter (18 mW / cm 2 ). The contact angle was measured by dropping 6 μL (liter) (6 × 10 −6 L) of pure water onto the sample surface using a contact angle meter (CA-X type) manufactured by Kyowa Interface Science Co., Ltd.
As is apparent from FIG. 14, the contact angle immediately after production in Examples 1 to 6 in which the photocatalyst contained in the uppermost fluororesin layer 5 is 20% to 60% by weight is about 110 ° to 120 °. It was water-repellent. Moreover, in each Example 1-6, the contact angle after ultraviolet irradiation is about 104 degrees to 111 degrees, and shows water repellency although it decreased a little from immediately after manufacture.
Further, as is clear from FIG. 15, in the case of Comparative Examples 1 and 2 in which the photocatalyst is 70% by weight and 80% by weight, immediately after production and after ultraviolet irradiation, the contact angle is 105 ° or more and water repellency. In the case of Comparative Example 3 in which the photocatalyst was 90% by weight, the contact angle was about 108 ° immediately after the production and the water became water repellent, and after the ultraviolet irradiation, the hydrophobicity was 80 °. In the case of the sheet of Comparative Example 4 that does not contain the conventional photocatalyst catalyst, the contact angle of the fluororesin was obtained, and measurement was not performed.
次に、光触媒シートの熱接合特性は、光触媒シート同士の熱接合部を試験機あるいは試験者の手により、おおよそ、２０ｍｍ／分の速度で剥離することにより行った。熱接合特性は、フッ素樹脂層同士が完全に溶融し、フッ素樹脂層全体が基材であるガラス繊維から完全に剥がれる場合を良好として○印で示し、その他のフッ素樹脂層間で剥離が生じる場合などの不良を×印で示している。
図１４及び図１５から明らかなように、光触媒を含有させた第３のフッ素樹脂層中の重量％（以下、適宜、光触媒の重量％と呼ぶ）が１０％から６０％である実施例１〜６及び光触媒を含有させていない比較例４の熱接合特性は良好である。一方、光触媒が７０重量％〜９０重量％である比較例１〜３においては、熱接合特性が不良となった。
このように、光触媒がおおよそ７０重量％以上で不良となるのは、第３のフッ素樹脂層５に含まれる光触媒が増加するために、第３のフッ素樹脂５とその下層にある第１のフッ素樹脂層３及び第２のフッ素樹脂４，４’との密着力が低下するためと推測される。
Next, the thermal bonding characteristics of the photocatalyst sheet were performed by peeling the thermal bonding portion between the photocatalyst sheets at a rate of approximately 20 mm / min by a tester or a tester's hand. The thermal bonding characteristics indicate that the fluororesin layers are completely melted and the entire fluororesin layer is completely peeled off from the glass fiber as the base material as indicated by a circle, and peeling occurs between other fluororesin layers Are indicated by crosses.
As is clear from FIGS. 14 and 15, the weight% (hereinafter referred to as the weight% of the photocatalyst as appropriate) in the third fluororesin layer containing the photocatalyst is 10% to 60%. No. 6 and Comparative Example 4 containing no photocatalyst have good thermal bonding characteristics. On the other hand, in Comparative Examples 1 to 3 in which the photocatalyst was 70% to 90% by weight, the thermal bonding characteristics were poor.
Thus, the reason why the photocatalyst becomes defective at about 70% by weight or more is that the photocatalyst contained in the third fluororesin layer 5 increases, so that the third fluororesin 5 and the first fluorine in the lower layer thereof. This is presumably because the adhesion between the resin layer 3 and the second fluororesins 4 and 4 ′ decreases.
次に、屋外暴露の汚れの評価は、上記実施例及び比較例のシートを屋外に１２カ月暴露した後、シート表面の汚れを評価した。汚れが付着していないシートを優良として○印で示し、汚れが殆ど付着していないシートを良として△印で示し、汚れが付着したシートを不良として×印で示している。屋外暴露は、本出願人の空間技術研究所（大阪府枚方市）屋上にて行った。
図１４から明らかなように、最上層のフッ素樹脂層５に含有される光触媒が２０重量％から６０重量％である実施例１〜４及び実施例６は防汚性が優れている。さらに、図１４及び図１５から明らかなように、光触媒が１０重量％である実施例５及び同７０重量％以上の比較例１〜３の場合には、汚れが付着し難いことが分かる。一方、比較例４の最上層に光触媒を含有させない従来のシートは防汚性がないことが分かる。
Next, the dirt on the outdoor exposure was evaluated by exposing the sheets of the above Examples and Comparative Examples to the outdoors for 12 months, and then evaluating the dirt on the sheet surface. A sheet with no dirt attached is indicated by a mark with good, a sheet with little dirt attached is indicated with a mark with Δ, and a sheet with dirt attached is indicated with a mark with a defect. Outdoor exposure was performed on the rooftop of the applicant's Spatial Technology Research Institute (Hirakata City, Osaka Prefecture).
As is apparent from FIG. 14, Examples 1-4 and Example 6 in which the photocatalyst contained in the uppermost fluororesin layer 5 is 20% by weight to 60% by weight are excellent in antifouling property. Further, as apparent from FIGS. 14 and 15, it can be seen that in Example 5 in which the photocatalyst is 10 wt% and Comparative Examples 1 to 3 in which the photocatalyst is 70 wt% or more, dirt is difficult to adhere. On the other hand, it turns out that the conventional sheet | seat which does not contain a photocatalyst in the uppermost layer of the comparative example 4 does not have antifouling property.
実施例５において、防汚性がやや悪くなるのは、フッ素樹脂層中の光触媒が少ない（１０重量％）ことに起因しているが、光触媒を含有させていない比較例４の防汚性がないのに比べると、はるかに防汚性が高く光触媒添加の効果が顕著である。
これに対して、比較例１〜３のように光触媒を多く含有している場合に防汚性が低下するのは、最上層の光触媒を含有させたフッ素樹脂層３とその下部のフッ素樹脂層３，４との熱接合性が悪いために、時間を経過すると光触媒を含有させたフッ素樹脂層３の欠落が生じ、光触媒を含有させていない下部のフッ素樹脂層４，５が直接外気に接触するためと推定される。しかし、実施例１〜６の熱接合部の防汚性に関しては、実施例６の光触媒シート２０が最も汚れが付着しないことが分かった。これは最上層の第３のフッ素樹脂層５と第２のフッ素樹脂層４’の両方に光触媒が含有されているので、光触媒を含有したフッ素樹脂層の厚さが厚いので、時間が経過しても、光触媒を含有させたフッ素樹脂層５の傷などによる欠陥が生じにくいからと推定される。
これにより、光触媒を含有させる第３のフッ素樹脂層のフッ素樹脂に対する酸化チタンが１０〜６０重量％の範囲において、良好な熱接合特性と共に、高い防汚性が得られることが分かる。
In Example 5, the antifouling property is slightly deteriorated because the photocatalyst in the fluororesin layer is small (10% by weight), but the antifouling property of Comparative Example 4 containing no photocatalyst is Compared with the case where no photocatalyst is added, the antifouling property is much higher and the effect of adding the photocatalyst is remarkable.
On the other hand, when the photocatalyst is contained in a large amount as in Comparative Examples 1 to 3, the antifouling property is reduced because the fluororesin layer 3 containing the uppermost photocatalyst and the fluororesin layer below the fluororesin layer 3 are contained. Due to poor thermal bonding properties with 3 and 4, the fluororesin layer 3 containing the photocatalyst is lost over time, and the lower fluororesin layers 4 and 5 not containing the photocatalyst are in direct contact with the outside air. Presumed to be. However, regarding the antifouling properties of the thermal bonding portions of Examples 1 to 6, it was found that the photocatalyst sheet 20 of Example 6 was the least contaminated. This is because the photocatalyst is contained in both the third fluororesin layer 5 and the second fluororesin layer 4 ′ as the uppermost layer, so that the time passes since the thickness of the fluororesin layer containing the photocatalyst is thick. However, it is presumed that defects due to scratches or the like of the fluororesin layer 5 containing the photocatalyst hardly occur.
Thereby, it turns out that high antifouling property is acquired with a favorable thermal-joining characteristic in the range whose titanium oxide with respect to the fluororesin of the 3rd fluororesin layer containing a photocatalyst is 10 to 60 weight%.
以上の実施例及び比較例の各項目の測定を総合評価すると、実施例１〜６において、高い防汚性と熱接合特性が得られた（図１４の総合評価において○）。また、比較例１〜４においては、高い防汚性と熱接合特性が同時に得られなかった（図１５の総合評価において×）。 When the measurement of each item of the above Examples and Comparative Examples was comprehensively evaluated, in Examples 1 to 6, high antifouling properties and thermal bonding characteristics were obtained (◯ in the comprehensive evaluation of FIG. 14). Further, in Comparative Examples 1 to 4, high antifouling properties and thermal bonding characteristics were not obtained at the same time (in the comprehensive evaluation of FIG. 15 x).
本発明は、上記実施例に限定されることなく、特許請求の範囲に記載した発明の範囲内で種々の変形が可能であり、それらも本発明の範囲内に含まれることはいうまでもない。例えば、上記実施の形態で説明した、基材やフッ素樹脂は目的に応じて適宜選択することができ、また、光触媒を含有させたフッ素樹脂の分散剤の組成も適宜に選択できることは勿論である。 The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the invention described in the claims, and it goes without saying that these are also included in the scope of the present invention. . For example, the substrate and the fluororesin described in the above embodiment can be appropriately selected according to the purpose, and the composition of the fluororesin dispersant containing the photocatalyst can be appropriately selected. .
１，１０，２０：光触媒シート
２：基材
３：第１のフッ素樹脂層
４：第２のフッ素樹脂層
４’：光触媒を含有させた第２のフッ素樹脂層
５：光触媒を含有させた第３のフッ素樹脂層
５ａ：光触媒を含有させた第３のフッ素樹脂層の表面
７：第３のフッ素樹脂層内の光触媒
８：第３のフッ素樹脂層の表面に露出した光触媒
DESCRIPTION OF SYMBOLS 1,10,20: Photocatalyst sheet 2: Base material 3: 1st fluororesin layer 4: 2nd fluororesin layer 4 ': The 2nd fluororesin layer 5 containing the photocatalyst 5: The photocatalyst containing 1st 3 fluororesin layer 5a: surface of third fluororesin layer containing photocatalyst 7: photocatalyst in third fluororesin layer 8: photocatalyst exposed on the surface of third fluororesin layer
Claims (16)
上記フッ素樹脂層は、
上記基材上に被覆される第１のフッ素樹脂層と、
該第１のフッ素樹脂層上に被覆される第２のフッ素樹脂層と、
該第２のフッ素樹脂層上に被覆され光触媒を含有させた第３のフッ素樹脂層と、からなり、
上記第１のフッ素樹脂層のフッ素樹脂はＰＴＦＥで、上記第３のフッ素樹脂層のフッ素樹脂はＦＥＰであり、
上記第３のフッ素樹脂層中の上記光触媒は１０〜６０重量％で、
上記基材の表面粗さ（Ｒａ）が１０μｍ以上であり、
上記第２のフッ素樹脂層は上記基材の表面粗さの値より小さい値の厚さでなり、上記第３のフッ素樹脂層は１μｍ以上で上記基材の表面粗さの値より小さい値の厚さでなり、
上記第３のフッ素樹脂層表面が、水との接触角９０°以上のはっ水性を有すると共に、表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上であることを特徴とする、光触媒シート。 A photocatalytic sheet in which a base material is coated with a fluororesin layer, the fluororesin of the fluororesin layer is melted, and the sheets are thermally bonded to each other,
The fluororesin layer,
A first fluororesin layer coated on the substrate;
A second fluororesin layer coated on the first fluororesin layer;
A third fluororesin layer coated on the second fluororesin layer and containing a photocatalyst,
The fluororesin of the first fluororesin layer is PTFE, the fluororesin of the third fluororesin layer is FEP,
The photocatalyst in the third fluororesin layer is 10 to 60% by weight,
The surface roughness (Ra) of the substrate is 10 μm or more,
The second fluororesin layer has a thickness smaller than the surface roughness value of the substrate, and the third fluororesin layer has a thickness of 1 μm or more and smaller than the surface roughness value of the substrate. With thickness,
When the surface of the third fluororesin layer has water repellency with a contact angle of 90 ° or more with water, oleic acid glyceride is applied to the surface and the surface is irradiated with ultraviolet rays of 1 mW / cm 2 , A photocatalytic sheet, wherein the degradation rate of the oleic acid glyceride is 0.4 mg / cm 2 · day or more.
上記フッ素樹脂層は、
上記基材上に被覆される第１のフッ素樹脂層と、
該第１のフッ素樹脂層上に被覆され、光触媒を含有させた第２のフッ素樹脂層と、
該第２のフッ素樹脂層上に被覆され、光触媒を含有させた第３のフッ素樹脂層と、からなり、
上記第１のフッ素樹脂層のフッ素樹脂はＰＴＦＥであると共に上記第３のフッ素樹脂層のフッ素樹脂はＦＥＰであり、
上記第３のフッ素樹脂層中の上記光触媒は１０〜６０重量％で、
上記基材の表面粗さ（Ｒａ）が１０μｍ以上であり、
上記第２のフッ素樹脂層は上記基材の表面粗さの値より小さい値の厚さでなり、上記第３のフッ素樹脂層は１μｍ以上で上記基材の表面粗さの値より小さい値の厚さでなり、
上記第３のフッ素樹脂層表面が、水との接触角９０°以上のはっ水性を有すると共に、表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上であることを特徴とする、光触媒シート。 A photocatalytic sheet in which a base material is coated with a fluororesin layer, the fluororesin of the fluororesin layer is melted, and the sheets are thermally bonded to each other,
The fluororesin layer,
A first fluororesin layer coated on the substrate;
Coated on the first fluororesin layer, a second fluorine resin layer containing a photocatalyst,
Coated onto the second fluororesin layer, and a third fluorine resin layer containing a photocatalyst made,
The fluororesin of the first fluororesin layer is PTFE and the fluororesin of the third fluororesin layer is FEP,
The photocatalyst in the third fluororesin layer is 10 to 60% by weight,
The surface roughness (Ra) of the substrate is 10 μm or more,
The second fluororesin layer has a thickness smaller than the surface roughness value of the substrate, and the third fluororesin layer has a thickness of 1 μm or more and smaller than the surface roughness value of the substrate. With thickness,
When the surface of the third fluororesin layer has water repellency with a contact angle of 90 ° or more with water, oleic acid glyceride is applied to the surface and the surface is irradiated with ultraviolet rays of 1 mW / cm 2 , A photocatalytic sheet, wherein the degradation rate of the oleic acid glyceride is 0.4 mg / cm 2 · day or more.
上記基材の表面粗さ（Ｒａ）を１０μｍ以上とし、
上記基材上に第１のフッ素樹脂層を被覆する工程と、
該第１のフッ素樹脂層上に第２のフッ素樹脂層を被覆する工程と、
該第２のフッ素樹脂層上に光触媒を１０〜６０重量％含有させた第３のフッ素樹脂層を被覆する工程と、からなり、
上記第１のフッ素樹脂層のフッ素樹脂をＰＴＦＥとすると共に上記第３のフッ素樹脂層のフッ素樹脂をＦＥＰとし、
上記第２のフッ素樹脂層を、上記基材の表面粗さの値より小さい値の厚さにすると共に、上記第３のフッ素樹脂層を、１μｍ以上で上記基材の表面粗さの値より小さい値の厚さにし、
上記光触媒を含有させたフッ素樹脂層表面を、水との接触角が９０°以上のはっ水性とすると共に、
上記フッ素樹脂層表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上にすることを特徴とする、光触媒シートの製造方法。 A method for producing a photocatalytic sheet in which a base material is coated with a fluororesin layer, the fluororesin of the fluororesin layer is melted, and the sheets are thermally bonded to each other,
The surface roughness (Ra) of the substrate is 10 μm or more,
Coating the first fluororesin layer on the substrate;
Coating the second fluororesin layer on the first fluororesin layer;
Coating a third fluororesin layer containing 10 to 60% by weight of a photocatalyst on the second fluororesin layer,
The fluororesin of the first fluororesin layer is PTFE and the fluororesin of the third fluororesin layer is FEP.
The second fluororesin layer has a thickness smaller than the surface roughness value of the substrate, and the third fluororesin layer has a thickness of 1 μm or more from the surface roughness value of the substrate. With a small thickness,
While making the fluororesin layer surface containing the photocatalyst water-repellent with a contact angle with water of 90 ° or more,
When oleic glyceride is applied to the surface of the fluororesin layer and the surface is irradiated with 1 mW / cm 2 of ultraviolet rays, the decomposition rate of the oleic glyceride is 0.4 mg / cm 2 · day or more. The manufacturing method of a photocatalyst sheet.
上記基材の表面粗さ（Ｒａ）を１０μｍ以上とし、
上記基材上に第１のフッ素樹脂層を被覆する工程と、
該第１のフッ素樹脂層上に光触媒を含有させた第２のフッ素樹脂層を被覆する工程と、
該第２のフッ素樹脂層上に光触媒を１０〜６０重量％含有させた第３のフッ素樹脂層を被覆する工程と、からなり、
上記第１のフッ素樹脂層のフッ素樹脂をＰＴＦＥとすると共に上記第３のフッ素樹脂層のフッ素樹脂をＦＥＰとし、
上記第２のフッ素樹脂層を、上記基材の表面粗さの値より小さい値の厚さにすると共に、上記第３のフッ素樹脂層を、１μｍ以上で上記基材の表面粗さの値より小さい値の厚さにし、
上記光触媒を含有させたフッ素樹脂層表面を、水との接触角が９０°以上のはっ水性とすると共に、
上記フッ素樹脂層表面にオレイン酸グリセリドを塗布して該表面に１ｍＷ／ｃｍ2 の紫外線を照射したときに、該オレイン酸グリセリドの分解速度が０．４ｍｇ／ｃｍ2 ・日以上にすることを特徴とすることを特徴とする、光触媒シートの製造方法。 A method for producing a photocatalytic sheet in which a base material is coated with a fluororesin layer, the fluororesin of the fluororesin layer is melted, and the sheets are thermally bonded to each other,
The surface roughness (Ra) of the substrate is 10 μm or more,
Coating the first fluororesin layer on the substrate;
Coating a second fluororesin layer containing a photocatalyst on the first fluororesin layer;
Coating a third fluororesin layer containing 10 to 60% by weight of a photocatalyst on the second fluororesin layer,
The fluororesin of the first fluororesin layer is PTFE and the fluororesin of the third fluororesin layer is FEP.
The second fluororesin layer has a thickness smaller than the surface roughness value of the substrate, and the third fluororesin layer has a thickness of 1 μm or more from the surface roughness value of the substrate. With a small thickness,
While making the fluororesin layer surface containing the photocatalyst water-repellent with a contact angle with water of 90 ° or more,
Characterized in that when irradiated with ultraviolet rays of 1 mW / cm 2 on the surface by applying oleic acid glyceride in the fluororesin layer surface, the degradation rate of the oleic acid glyceride is more than 2 · day 0.4 mg / cm The manufacturing method of the photocatalyst sheet characterized by these.
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| JP4990509B2 (en) * | 2005-06-15 | 2012-08-01 | 太陽工業株式会社 | Photocatalyst sheet manufacturing method |
| KR101472872B1 (en) | 2009-07-31 | 2014-12-15 | 칸보 프라스 가부시키가이샤 | Antifouling sheet |
| US20120225284A1 (en) * | 2011-03-04 | 2012-09-06 | Saint-Gobain Performance Plastics Corporation | Composite article for use as self-cleaning material |
| JP5159924B2 (en) * | 2011-07-19 | 2013-03-13 | 太陽工業株式会社 | Photocatalyst sheet manufacturing method |
| JP5854421B2 (en) * | 2011-11-07 | 2016-02-09 | 東ソー株式会社 | Water-repellent thin film and method for producing the same |
| JP5362070B2 (en) * | 2012-05-11 | 2013-12-11 | 太陽工業株式会社 | Photocatalyst sheet manufacturing method |
| JP5762471B2 (en) * | 2013-06-12 | 2015-08-12 | 太陽工業株式会社 | Photocatalyst sheet manufacturing method |
| JP5891552B2 (en) * | 2015-02-19 | 2016-03-23 | 平岡織染株式会社 | Flexible antifouling composite sheet and composite |
| JP6837706B2 (en) * | 2016-08-26 | 2021-03-03 | 太陽工業株式会社 | Fluororesin film material and its manufacturing method |
| JP7069814B2 (en) * | 2018-02-22 | 2022-05-18 | 富士フイルムビジネスイノベーション株式会社 | Structure |
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