JP2020000977A - Photocatalyst carried laminate - Google Patents
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- JP2020000977A JP2020000977A JP2018121466A JP2018121466A JP2020000977A JP 2020000977 A JP2020000977 A JP 2020000977A JP 2018121466 A JP2018121466 A JP 2018121466A JP 2018121466 A JP2018121466 A JP 2018121466A JP 2020000977 A JP2020000977 A JP 2020000977A
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- 239000011941 photocatalyst Substances 0.000 title abstract description 47
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims description 15
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 21
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 16
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 16
- 239000011800 void material Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004230 Fast Yellow AB Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、可視光応答型の光触媒材料を担持した積層体に関する。 The present invention relates to a laminate that supports a visible light responsive photocatalyst material.
光触媒は、消臭・抗菌・抗ウイルスなどの性能を有し、今後も注目される技術である。光触媒の性能を効果的に発揮させることは重要な因子であり、光触媒の性能を効果的に発揮させるためには、基本的に光触媒塗膜のできるだけ多くの光触媒の粒子を露出させた状態で基材に担持させる必要がある。 Photocatalysts have deodorant, antibacterial, and antiviral properties, and will continue to attract attention. Effective performance of the photocatalyst is an important factor, and in order to effectively exert the performance of the photocatalyst, it is basically necessary to expose as many photocatalyst particles of the photocatalyst coating film as possible. It is necessary to carry on the material.
光触媒の各種基材への担持方法は従来よりいくつか知られており、例えば、セラミックなどの金属基材にはスパッタリングあるいは焼結にて担持する方法や、アンカー効果などを利用した不織布への担持などが挙げられる。
特に、不織布への担持は、繊維のアンカー効果などを利用しているため、光触媒の露出状態が良好のまま担持させることができる。
また、近年、プラスチックフィルムに光触媒を担持したフィルムも研究開発が進んでいる。
There are several known methods for supporting a photocatalyst on various substrates. For example, a method of supporting a metal substrate such as a ceramic by sputtering or sintering, or a method of supporting a nonwoven fabric using an anchor effect or the like. And the like.
In particular, since the photocatalyst is supported on the nonwoven fabric using the anchor effect of the fibers, the photocatalyst can be supported while the exposed state is good.
In recent years, research and development of a film in which a photocatalyst is supported on a plastic film has been advanced.
しかし、基材がプラスチックフィルムで光触媒を担持させる場合、バインダーを光触媒と混合する必要があるが、光触媒の一部がバインダーに埋もれてしまう場合がある。そこでバインダーとして用いる樹脂に光触媒を混合する際には光触媒の充填量を多くして、できるだけ多くの光触媒を塗膜表面から露出させることが行われているが、塗膜性能やコストの面などから光触媒の充填量には限界がある。 However, when a photocatalyst is supported by a plastic film as a base material, it is necessary to mix the binder with the photocatalyst, but a part of the photocatalyst may be buried in the binder. Therefore, when mixing the photocatalyst with the resin used as the binder, the amount of the photocatalyst is increased to expose the photocatalyst as much as possible from the coating film surface, but from the viewpoint of the coating film performance and cost, etc. There is a limit to the amount of the photocatalyst charged.
そこで最近では、光触媒を多孔質材料と組み合わせて用いることによって、光触媒の露出面積を大きくする試みが種々なされており、例えば特許文献１では、多孔質となるセメント質基材に光触媒を含有させ、光触媒と気相との接触面積を増加させることで触媒活性を高めるようにしている。 In recent years, various attempts have been made to increase the exposed area of the photocatalyst by using a photocatalyst in combination with a porous material. For example, in Patent Document 1, a porous cementitious base material contains a photocatalyst, The catalytic activity is increased by increasing the contact area between the photocatalyst and the gas phase.
しかし、従来のプラスチックフィルムでは、特許文献１のセメント質基材のような多孔質構造とすることは困難であった。 However, it has been difficult for a conventional plastic film to have a porous structure like the cementitious substrate of Patent Document 1.
本発明は上記従来の課題を解決するものであり、空隙を有する層に露出する光触媒の量を増加させて触媒活性を高めることができ、しかも光触媒の担持が良好な積層体を提供することを見出し、本発明を完成させた。 The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a laminate that can increase the amount of a photocatalyst exposed to a layer having a void, thereby increasing the catalytic activity, and moreover, favorably carry a photocatalyst. Heading, the present invention has been completed.
すなわち本発明は、基材および該基材上に空隙を有する層で構成され、その空隙部に光触媒粒子が担持された積層体である。 That is, the present invention is a laminate comprising a base material and a layer having voids on the base material, and the photocatalyst particles are supported in the void portions.
さらに本発明は、基材が好ましくは熱可塑性樹脂であり、より好ましくは前記熱可塑性樹脂がエチレンービニルアルコール共重合体である、上記の積層体である。 Further, the present invention is the above-mentioned laminate, wherein the base material is preferably a thermoplastic resin, and more preferably the thermoplastic resin is an ethylene-vinyl alcohol copolymer.
そして本発明は空隙を有する層は好ましくは熱可塑性樹脂であり、より好ましくは前記熱可塑性樹脂がエチレンービニルアルコール共重合体であり、さらに好ましくはメジアン径（Ｄ５０）が０．１〜４μｍのエチレンービニルアルコール共重合体粒子である、上記の積層体である。 In the present invention, the layer having voids is preferably a thermoplastic resin, more preferably the thermoplastic resin is an ethylene-vinyl alcohol copolymer, and still more preferably the median diameter (D 50 ) is 0.1 to 4 μm. And the ethylene-vinyl alcohol copolymer particles of the above.
本発明の積層体は、空隙を有する層に露出する光触媒の量を増加させて触媒活性を高めることができ、しかも光触媒の担持が良好なものとなる。 The laminate of the present invention can enhance the catalytic activity by increasing the amount of the photocatalyst exposed to the layer having the voids, and also has a good photocatalyst support.
本発明の積層体の基材に用いられる素材は、特に限定されるものではないが、熱可塑性樹脂であることが好ましい。前記熱可塑性樹脂としては、ポリエチレンテレフタレートなどのポリエステル、塩化ビニル系樹脂、アクリル系樹脂、エチレンービニルアルコール共重合体からなる樹脂などが挙げられ、これら樹脂の中から状況に応じて適宜選択して用いられるが、後述する空隙層との密着を考慮するとエチレンービニルアルコール共重合体からなる樹脂が最も好ましい。 The material used for the substrate of the laminate of the present invention is not particularly limited, but is preferably a thermoplastic resin. Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate, vinyl chloride resins, acrylic resins, resins made of ethylene-vinyl alcohol copolymer, and the like. Although it is used, a resin composed of an ethylene-vinyl alcohol copolymer is most preferable in consideration of the adhesion to the void layer described later.
基材の形態としては、プラスチックフィルム、不織布、成型体などが挙げられるが、透明性や耐久性の点からプラスチックフィルムであることが好ましい。基材の厚さは特に制限はなく、５〜１００μｍ、好ましくは１０〜５０μｍ、より好ましくは１０〜２０μｍの範囲の中から、使用目的に応じて適宜選定することができる。 Examples of the form of the substrate include a plastic film, a nonwoven fabric, and a molded body, and a plastic film is preferable in terms of transparency and durability. The thickness of the substrate is not particularly limited, and can be appropriately selected from the range of 5 to 100 μm, preferably 10 to 50 μm, more preferably 10 to 20 μm according to the purpose of use.
本発明において用いられる基材は透明であることが好ましいが、着色又は蒸着されていてもよく、さらに紫外線吸収剤、抗菌剤などの添加剤が含有されていてもよい。また、その表面に設けられる層との密着性を向上させる目的で、所望により片面または両面に酸化法や凹凸化法などにより表面処理を施すことができる。前記酸化法としては例えばコロナ放電処理、クロム酸処理（湿式）、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられ、また前記凹凸化法としては例えばサンドプラスト法、溶剤処理法などが挙げられる。これらの表面処理法は基材の種類に応じて適宜選定される。基材がプラスチックフィルムの場合、一般にはコロナ放電処理法が効果および操作性などの面から好ましく用いられる。 The substrate used in the present invention is preferably transparent, but may be colored or vapor-deposited, and may further contain additives such as an ultraviolet absorber and an antibacterial agent. Further, for the purpose of improving the adhesion to a layer provided on the surface, one or both surfaces can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, and ozone / ultraviolet irradiation treatment. Examples of the unevenness method include a sandplast method and a solvent treatment method. No. These surface treatment methods are appropriately selected according to the type of the base material. When the base material is a plastic film, generally, a corona discharge treatment method is preferably used from the viewpoint of effects and operability.
さらに本発明において、前記基材に設けられる光触媒を担持する空隙層は熱可塑性樹脂であることが好ましい。前記熱可塑性樹脂としては、基材との密着性を考慮するとエチレンービニルアルコール共重合体であることが好ましく、さらにエチレンービニルアルコール共重合体が粒子状であることが好ましい。粒子状である場合、エチレンービニルアルコール共重合体の粒子径は光触媒の露出しやすさの点から、メジアン径（Ｄ５０）が０．１〜４．０μｍの範囲であることが好ましく、０．３〜２．０μｍの範囲であることがより好ましい。 Further, in the present invention, the void layer provided on the base material and supporting the photocatalyst is preferably a thermoplastic resin. The thermoplastic resin is preferably an ethylene-vinyl alcohol copolymer in consideration of adhesion to a substrate, and more preferably the ethylene-vinyl alcohol copolymer is in a particulate form. In the case of particulates, the ethylene-vinyl alcohol copolymer preferably has a median diameter (D 50 ) in the range of 0.1 to 4.0 μm from the viewpoint of easy exposure of the photocatalyst. More preferably, it is in the range of 0.3 to 2.0 μm.
本発明の積層体の空隙層に好適に用いられるエチレンービニルアルコール共重合体は、溶液時の保管安定性の点から、エチレン含有量が２０〜５５モル％、特に２５〜５０モル％、酢酸ビニル成分のケン化度９０モル％以上、特に９５モル％以上であることが好ましい。エチレンービニルアルコール共重合体は、エチレンー酢酸ビニル共重合体のケン化によって得られるが、該樹脂は公知の任意の重合法、例えば溶液重合、懸濁重合、エマルジョン重合などにより製造でき、エチレンー酢酸ビニル共重合体のケン化も公知の方法で行うことができる。 The ethylene-vinyl alcohol copolymer preferably used for the void layer of the laminate of the present invention has an ethylene content of 20 to 55 mol%, particularly 25 to 50 mol%, and acetic acid, from the viewpoint of storage stability in solution. The saponification degree of the vinyl component is preferably at least 90 mol%, particularly preferably at least 95 mol%. The ethylene-vinyl alcohol copolymer is obtained by saponification of an ethylene-vinyl acetate copolymer, and the resin can be produced by any known polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization, and the like. Saponification of the vinyl copolymer can also be performed by a known method.
前述したように本発明で用いられるエチレンービニルアルコール共重合体は粒子状であることが好ましいが、エチレンービニルアルコール共重合体粒子は以下の製造方法により製造される。エチレン含有率が同一あるいは異なるエチレンービニルアルコールを水／アルコール比で５／９５〜８０／２０の範囲にある溶媒中にて７０〜８５℃で溶解し、均一透明なエチレンービニルアルコール共重合体の完全溶解溶液を作製する。続いて得られた均一透明なエチレンービニルアルコール共重合体溶液を高速攪拌させながら溶液温度を２０℃以下となるようにエチレンービニルアルコール溶液を冷却することで、メジアン径（Ｄ５０）が好ましくは０．１〜４．０μｍ、より好ましくは０．３〜２．０μｍの範囲であるエチレンービニルアルコール微粒子を含む不均一白濁溶液を調製し、後述する方法で該溶液を基材に塗布し乾燥することで、エチレンービニルアルコール共重合体粒子を含む層が形成される。 As described above, the ethylene-vinyl alcohol copolymer used in the present invention is preferably in the form of particles, but the ethylene-vinyl alcohol copolymer particles are produced by the following production method. Ethylene-vinyl alcohol having the same or different ethylene content is dissolved in a solvent having a water / alcohol ratio in the range of 5/95 to 80/20 at 70 to 85 ° C. to obtain a homogeneous and transparent ethylene-vinyl alcohol copolymer. Make a complete dissolution solution of Subsequently, the median diameter (D 50 ) is preferably obtained by cooling the ethylene-vinyl alcohol solution so that the solution temperature becomes 20 ° C. or less while rapidly stirring the obtained homogeneous and transparent ethylene-vinyl alcohol copolymer solution. Prepares a heterogeneous cloudy solution containing ethylene-vinyl alcohol fine particles in the range of 0.1 to 4.0 μm, more preferably 0.3 to 2.0 μm, and coats the solution on a substrate by a method described later. By drying, a layer containing ethylene-vinyl alcohol copolymer particles is formed.
このようにして得られる本発明のエチレンービニルアルコール共重合体粒子の粒子形状としては、特に制限はなく、楕円球状、球状などが挙げられるが、熱安定性の観点から球状であることが好ましい。 The particle shape of the ethylene-vinyl alcohol copolymer particles of the present invention obtained in this way is not particularly limited, and includes an elliptical sphere, a sphere and the like, and is preferably spherical from the viewpoint of thermal stability. .
空隙層の厚さは、均質な塗布性、密着性、および光触媒のコストなどの点から０．０５〜１ｇ／ｍ２・ｄｒｙの範囲であることが好ましく、特に０．１〜０．３ｇ／ｍ２・ｄｒｙの範囲が好適である。また空隙層における空隙は隣り合うエチレンービニルアルコール共重合体粒子間において形成される。空隙層における空隙の大きさは、光触媒が担持できるサイズであればよく、具体的には０．０１〜５μｍであることが好ましく、より好ましくは０．１〜２μｍである。 The thickness of the void layer is preferably in the range of 0.05 to 1 g / m 2 · dry from the viewpoint of uniform coatability, adhesion, photocatalyst cost, and the like, and particularly preferably 0.1 to 0.3 g / d The range of m 2 · dry is preferable. The voids in the void layer are formed between adjacent ethylene-vinyl alcohol copolymer particles. The size of the voids in the void layer may be any size as long as the photocatalyst can be supported, and specifically, is preferably 0.01 to 5 μm, and more preferably 0.1 to 2 μm.
光触媒を有する空隙層の形成方法としては、従来公知の方法、例えばバーコート法、ナイフコート法、ブレードコート法、ダイコート法、グラビアコート法、カーテンコート法などを用いて基材上に塗工し、乾燥処理を施すことにより行うことができる。乾燥処理は使用する基材により条件は異なるが、基材の融点以下の温度で乾燥することが好ましい。 As a method for forming a void layer having a photocatalyst, a conventionally known method, such as a bar coating method, a knife coating method, a blade coating method, a die coating method, a gravure coating method, and a coating method using a curtain coating method, are used. And drying treatment. The conditions for the drying treatment vary depending on the substrate used, but it is preferable to dry at a temperature lower than the melting point of the substrate.
本発明において、光触媒の種類は特に限定されるものではなく、一般的な光触媒が使用可能であり、アナターゼ型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタン、酸化亜鉛、酸化錫、酸化第二鉄、三酸化二ビスマス、三酸化タングステン、チタン酸ストロンチウム等が挙げられるが、これらの中でも三酸化タングステンが可視光領域の光で最も有効に使用することができる。 In the present invention, the type of photocatalyst is not particularly limited, and a general photocatalyst can be used, and an anatase type titanium oxide, a rutile type titanium oxide, a brookite type titanium oxide, a zinc oxide, a tin oxide, and a second oxide Examples include iron, bismuth trioxide, tungsten trioxide, and strontium titanate. Of these, tungsten trioxide can be used most effectively with light in the visible light region.
光触媒の担持方法は特に限定はなく、光触媒スラリー分散液にエチレンービニルアルコール共重合体粒子が含有した溶液を添加した混合溶液を基材に塗布するか、もしくはエチレンービニルアルコール共重合体粒子が含有した溶液を基材に塗布後、光触媒スラリー溶液をオーバーコートする方法などが挙げられる。 The method for supporting the photocatalyst is not particularly limited, and a mixed solution obtained by adding a solution containing the ethylene-vinyl alcohol copolymer particles to the photocatalyst slurry dispersion liquid is applied to the substrate, or the ethylene-vinyl alcohol copolymer particles are applied. After applying the contained solution to the substrate, a method of overcoating the photocatalyst slurry solution and the like can be mentioned.
以下、本発明については、実施例を挙げてさらに具体的に説明する。なお本発明は実施例の記載により限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the description of the embodiments.
＜光触媒性能評価＞
（１）事前準備として、得られたサンプル（後述する実施例１、比較例１参照）を４〜６日間、東芝ライテック社製ケミカルランプ（商品名；ＦＬ２０Ｓ−ＢＬ）で照射し、空隙層表面に付着していた異物を除去しておいた。
（２）次にコーイチ社製サンプリングバック（商品名；５Ｌ Ｆ２（ＰＶＤＦ）バック）に、上記（１）にて事前準備したサンプル（１０ｃｍ×１０ｃｍ）を入れた。
（３）続いて、上記バックに、アセトアルデヒド濃度が８０〜１００ｐｐｍ、全体容量が２Ｌとなるように調整した。
（４）その後、オーム電機社製蛍光灯（商品名；ＴＢＬ−２１／５Ｎ）で、６０００Ｌｕｘの照度を当て、２４時間後、４８時間後のＦ２（ＰＶＤＦ）バック内のアセトアルデヒド残存率をガステック社製検知管（商品名；９２Ｍ）で評価した。
<Evaluation of photocatalytic performance>
(1) As a preliminary preparation, the obtained sample (see Example 1 and Comparative Example 1 described later) was irradiated for 4 to 6 days with a chemical lamp (trade name: FL20S-BL) manufactured by Toshiba Lighting & Technology Corporation, and the surface of the void layer was The foreign matter adhering to was removed.
(2) Next, the sample (10 cm × 10 cm) prepared in advance in the above (1) was placed in a sampling bag (trade name: 5L F2 (PVDF) bag) manufactured by Koichi.
(3) Subsequently, the bag was adjusted so that the acetaldehyde concentration was 80 to 100 ppm and the total volume was 2 L.
(4) After that, illuminance of 6000 Lux was applied with a fluorescent lamp (trade name: TBL-21 / 5N) manufactured by Ohm Electric Co., Ltd. The evaluation was performed using a detector tube (trade name; 92M) manufactured by the company.
＜実施例１＞
１）クラレ製エチレンービニルアルコール樹脂（商品名；ＥＰ−Ｅ１０５、エチレン含有量４４％、ケン化度９９％）を用い、該エチレンービニルアルコール樹脂を含水ノルマルプロパノール溶液中に、組成比（質量比）がエチレンービニルアルコール樹脂１０％／含水ノルマルプロパノール溶液９０％となるように添加した後、７０℃に加熱・攪拌し溶解することでエチレンービニルアルコール溶液を調製した。
２）次に、上記１）で加熱した溶液を氷冷水下、強攪拌後、ＨＯＲＩＢＡ社製粒子径分布測定装置（製品名；ＬＡ−３００）を用いてメジアン径（Ｄ５０）を算出したところ、メジアン径（Ｄ５０）が１．０μｍのエチレンービニルアルコール粒子を含有する溶液（溶液Ａ）を得た。
３）一方、上記２）で調製したエチレンービニルアルコール溶液に、東芝社製光触媒粒子（商品名；ルネキャットＲ３Ｓ−１０００Ｂ−００）を組成比（質量比）で光触媒粒子／エチレンービニルアルコール溶液＝７０／３０となるように混合・攪拌し、光触媒分散液（溶液Ｂ）を得た。
４）クラレ製エチレンービニルアルコール樹脂フィルム（商品名；ＥＦ−Ｍ））を基材とし、該基材の上に溶液Ｂをセレクトローラーで塗布後、７０℃で２分間乾燥を実施し、メジアン径（Ｄ５０）が１．０μｍのエチレンービニルアルコール粒子で構成された空隙を有する層（塗工量０．２ｇ／ｍ２、ｄｒｙ）の空隙部に光触媒粒子が絡み合うことで担持された積層体を得た。得られた積層体の光触媒性能評価を表１に示す。
<Example 1>
1) Kuraray's ethylene-vinyl alcohol resin (trade name: EP-E105, ethylene content 44%, degree of saponification 99%), and the composition ratio (mass) of the ethylene-vinyl alcohol resin in a water-containing normal propanol solution (Ratio) was 10% of ethylene-vinyl alcohol resin / 90% of water-containing normal propanol solution, and then heated and stirred at 70 ° C. and dissolved to prepare an ethylene-vinyl alcohol solution.
2) Next, the solution heated in the above 1) was vigorously stirred under ice-cold water, and then the median diameter (D 50 ) was calculated using a particle size distribution analyzer (product name: LA-300) manufactured by HORIBA. A solution (solution A) containing ethylene-vinyl alcohol particles having a median diameter (D 50 ) of 1.0 μm was obtained.
3) On the other hand, the photocatalyst particles (trade name: Renecat R3S-1000B-00) manufactured by Toshiba Corporation were added to the ethylene-vinyl alcohol solution prepared in 2) in a composition ratio (mass ratio) of photocatalyst particles / ethylene-vinyl alcohol solution. = 70/30 to obtain a photocatalyst dispersion liquid (solution B).
4) Kuraray's ethylene-vinyl alcohol resin film (trade name: EF-M)) was used as a base material, and solution B was applied on the base material with a select roller, followed by drying at 70 ° C for 2 minutes, followed by median drying. Laminated body in which photocatalyst particles are entangled with the voids of a layer having voids (coating amount: 0.2 g / m 2 , dry) composed of ethylene-vinyl alcohol particles having a diameter (D50) of 1.0 μm Got. Table 1 shows the evaluation of photocatalytic performance of the obtained laminate.
＜比較例１＞
１）クラレ製エチレンービニルアルコール樹脂（商品名；ＥＰ−Ｅ１０５、エチレン含有量４４％、ケン化度９９％）を用い、実施例１と同じ条件で加熱・攪拌し溶解することでエチレンービニルアルコール溶液を調製した。
２）上記１）で調製した溶液は冷却および攪拌を行わないことで粒子を含有しないエチレンービニルアルコール溶液（溶液Ｃ）を調製した。
３）一方、上記実施例１の３）と同様の方法にて、光触媒分散液(溶液Ｄ)を調製した。
４）基材は実施例１と同じクラレ製エチレンービニルアルコール樹脂フィルム（商品名；ＥＦ−Ｍ））を用い、実施例の４）と同じ条件にて積層体を得た。得られた積層体は空隙を有さない層に光触媒粒子が担持されていた。得られた積層体の光触媒性能評価を表１に示す。
<Comparative Example 1>
1) Using Kuraray's ethylene-vinyl alcohol resin (trade name; EP-E105, ethylene content 44%, saponification degree 99%), heating and stirring under the same conditions as in Example 1 to dissolve the ethylene-vinyl alcohol An alcohol solution was prepared.
2) The solution prepared in 1) above was not cooled and stirred to prepare an ethylene-vinyl alcohol solution (solution C) containing no particles.
3) Meanwhile, a photocatalyst dispersion liquid (solution D) was prepared in the same manner as in 3) of Example 1 above.
4) A laminate was obtained under the same conditions as in Example 4), using the same Kuraray ethylene-vinyl alcohol resin film (trade name; EF-M) as in Example 1. In the obtained laminate, the photocatalyst particles were supported in a layer having no void. Table 1 shows the evaluation of the photocatalytic performance of the obtained laminate.
本発明の積層体は、家具、壁紙、衣装ケース、内・外装建材などの機能性フィルムなどに適用できる。
The laminate of the present invention can be applied to functional films such as furniture, wallpaper, costume cases, and interior / exterior building materials.
Claims (6)
Laminate according to claim 1, the layer having voids is formed of a median diameter (D 50) 0.1~4μm of ethylene-vinyl alcohol copolymer particles.
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