JPH1147610A - Photocatalyst sheet and its preparation - Google Patents
Photocatalyst sheet and its preparationInfo
- Publication number
- JPH1147610A JPH1147610A JP9219969A JP21996997A JPH1147610A JP H1147610 A JPH1147610 A JP H1147610A JP 9219969 A JP9219969 A JP 9219969A JP 21996997 A JP21996997 A JP 21996997A JP H1147610 A JPH1147610 A JP H1147610A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- photocatalyst
- fine particles
- resin
- polytetrafluoroethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 106
- 239000010410 layer Substances 0.000 claims abstract description 90
- 239000010419 fine particle Substances 0.000 claims abstract description 57
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 39
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000012790 adhesive layer Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 13
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008119 colloidal silica Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 5
- 230000003746 surface roughness Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 5
- 239000001023 inorganic pigment Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 3
- 241000233866 Fungi Species 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000004299 exfoliation Methods 0.000 abstract 1
- 235000019645 odor Nutrition 0.000 abstract 1
- 238000010422 painting Methods 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000006864 oxidative decomposition reaction Methods 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は抗菌、除菌、防汚、
防臭、浄化等に使用する光触媒シ−ト及びその製造方法
に関するものである。TECHNICAL FIELD The present invention relates to antibacterial, antibacterial, antifouling,
The present invention relates to a photocatalyst sheet used for deodorization and purification, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化物半導体である酸化チタン等の光触
媒微粒子にバンドギャップ以上のエネルギ−を有する光
を照射すると、励起により電子及び正孔が発生され、表
面に近接した有機物や微生物が酸化により分解され、無
機酸化物においては、最終酸化物にまで酸化されるに至
る。そこで、この光触媒微粒子をバインダ−で担持させ
た光触媒シ−トを所定の場所に配設し、空気中に浮遊す
る細菌や臭気性ガスを分解して抗菌、除菌、防汚、防
臭、浄化等を行うことが提案されている。2. Description of the Related Art When photocatalytic fine particles such as titanium oxide, which is an oxide semiconductor, are irradiated with light having an energy higher than the band gap, electrons and holes are generated by excitation, and organic substances and microorganisms close to the surface are oxidized. It is decomposed and, in the case of inorganic oxides, is oxidized to the final oxide. Therefore, a photocatalyst sheet in which the photocatalyst fine particles are carried by a binder is disposed at a predetermined place, and the bacteria and odorous gas floating in the air are decomposed to disinfect, sterilize, stain, deodorize, and purify. It has been proposed to do so.
【０００３】従来、ビニルエ−テル−フルオロオレフィ
ンコポリマ−やビニルエステル−フルオロオレフィンコ
ポリマ−等のフッ素系ポリマ−とイソシアネ−ト系硬化
剤等の架橋剤と光触媒微粒子との溶剤溶液を支持体上に
塗布し、架橋反応で硬化させて光触媒層を形成すること
が公知である（特開平７−１７１４０８号）。この光触
媒層は、難分解性であるフッ素系ポリマ−をバインダ−
としているから、活性化光触媒微粒子でバインダ−が酸
化劣化されるのをよく防止でき、光触媒微粒子の安定な
結着が期待できる。Conventionally, a solvent solution of a fluorine-based polymer such as vinyl ether-fluoroolefin copolymer or vinyl ester-fluoroolefin copolymer, a crosslinking agent such as an isocyanate-based curing agent, and photocatalyst fine particles on a support. It is known that a photocatalyst layer is formed by coating and curing by a cross-linking reaction (JP-A-7-171408). This photocatalytic layer is made of a hardly decomposable fluorine-based polymer as a binder.
Therefore, the binder can be prevented from being oxidized and deteriorated by the activated photocatalyst fine particles, and stable binding of the photocatalyst fine particles can be expected.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、光触媒
微粒子の表面の大部分がバインダ−で覆われ、光触媒微
粒子と空気との直接的な接触がそれだけ少なくなるの
で、空気中の細菌等に対する光触媒微粒子の酸化分解効
率の低下が避けられない。However, since most of the surface of the photocatalyst fine particles is covered with the binder, and the direct contact between the photocatalyst fine particles and the air is reduced accordingly, the photocatalytic fine particles are less susceptible to bacteria and the like in the air. A reduction in oxidative decomposition efficiency is inevitable.
【０００５】ところで、フッ素系ポリマ−の製膜法とし
て、フッ素系ポリマ−のディスパ−ジョンを塗布し、加
熱により塗布膜中の溶媒を蒸発させ、更に加熱焼成によ
りフッ素系ポリマ−粒子間を焼結することが知られてい
る。この膜製法では、焼成に、前記した架橋硬化法に較
べ相当に高温（３７０〜３９０℃）の加熱が必要であ
る。しかしながら、本発明者の検討結果によれば、フッ
素系ポリマ−とし特にポリテトラフルオロエチレンを使
用し、このポリテトラフルオロエチレン粉末と光触媒微
粒子とのディスパ−ジョンを塗布し、焼成して得た光触
媒層は、上記架橋硬化法による光触媒層に較べて著しく
優れた分解性能を呈することが判明した。この高分解性
能の原因を解明するために、その光触媒層の組織を顕微
鏡で観察したところ、光触媒微粒子と樹脂との間に空気
層が存在し、この空気層が繋がって連続気泡状を成して
いることが判明した。As a method of forming a fluoropolymer film, a fluoropolymer dispersion is applied, the solvent in the applied film is evaporated by heating, and the fluoropolymer particles are fired by heating and firing. It is known to tie. In this film manufacturing method, heating at a considerably higher temperature (370 to 390 ° C.) is required for baking compared to the above-mentioned cross-linking and curing method. However, according to the study results of the present inventor, the photocatalyst obtained by applying a dispersion of this polytetrafluoroethylene powder and photocatalyst fine particles by using a fluorine-based polymer, particularly polytetrafluoroethylene, and firing the photocatalyst was obtained. It was found that the layer exhibited remarkably superior decomposition performance as compared with the photocatalytic layer obtained by the above-mentioned crosslinking curing method. To elucidate the cause of this high resolution performance, the structure of the photocatalyst layer was observed with a microscope, and an air layer was present between the photocatalyst fine particles and the resin, and this air layer was connected to form an open cell. Turned out to be.
【０００６】上記空気層の形成は、ポリテトラフルオロ
エチレンポリマ−がビニルエ−テル−フルオロオレフィ
ンコポリマ−やビニルエステル−フルオロオレフィンコ
ポリマ−等のフッ素系ポリマ−に較べて難溶着性であ
り、しかも、光触媒微粒子に較べてポリテトラフルオロ
エチレンポリマ−の熱収縮率が著しく大きいために、焼
成後の冷却時、光触媒微粒子と樹脂との界面が剥離さ
れ、樹脂の冷却収縮に伴いその剥離箇所の空間が拡大さ
れていく結果であると推察される。この推察の妥当性
は、焼成による光触媒層の形成において、ポリテトラフ
ルオロエチレンポリマ−に代えパ−フルオロアルキルビ
ニルエ−テル−テトラフルオロエチレンコポリマ−を用
いると、顕著な分解性能の低下が観られることからも、
裏付けられる。[0006] The formation of the air layer is such that the polytetrafluoroethylene polymer is harder to weld than a fluorine-based polymer such as a vinyl ether-fluoroolefin copolymer or a vinyl ester-fluoroolefin copolymer. Since the thermal contraction rate of the polytetrafluoroethylene polymer is significantly larger than that of the photocatalyst fine particles, the interface between the photocatalyst fine particles and the resin is separated during cooling after firing, and the space of the separated portion is reduced due to the cooling shrinkage of the resin. It is presumed to be the result of the expansion. The validity of this presumption is that when a perfluoroalkylvinyl ether-tetrafluoroethylene copolymer is used in place of the polytetrafluoroethylene polymer in the formation of the photocatalyst layer by firing, a remarkable decrease in decomposition performance is observed. From that,
Supported.
【０００７】本発明の目的は、上記知見に基づき、ポリ
テトラフルオロエチレン粉末と光触媒微粒子とを含有す
るディスパ−ジョンの塗布・焼成で光触媒層を形成する
ことにより、酸化分解効率に優れた光触媒シ−トを提供
することにある。An object of the present invention is to form a photocatalyst layer by applying and firing a dispersion containing polytetrafluoroethylene powder and photocatalyst fine particles based on the above findings, thereby providing a photocatalyst system having excellent oxidative decomposition efficiency. -To provide a service.
【０００８】[0008]
【課題を解決するための手段】本発明に係る光触媒シ−
トは、ポリテトラフルオロエチレン樹脂の焼成層内に光
触媒微粒子が分散され、樹脂と光触媒微粒子との間に微
小空気層が形成されて成る光触媒層を有することを特徴
とする構成であり、光触媒層の裏面には、補強層として
着色顔料または充填剤を含有するポリテトラフルオロエ
チレン樹脂の焼成層を設け、補強層の裏面には、易接着
性層としてコロイダルシリカを含有する熱溶融性パ−フ
ロロ樹脂の焼成層を設け、易接着性層の裏面には接着層
を設けることができる。本発明に係る光触媒シ−トの製
造方法は、ポリテトラフルオロエチレン粉末と光触媒微
粒子を含有するディスパ−ジョンの塗布層を加熱して溶
媒を蒸発除去し、更に加熱してポリテトラフルオロエチ
レン粉末を焼結・焼成し、而るのち、冷却して光触媒層
を形成することを特徴とする構成である。The photocatalytic sheath according to the present invention is provided.
The photocatalyst layer has a photocatalyst layer in which photocatalyst fine particles are dispersed in a fired layer of polytetrafluoroethylene resin, and a fine air layer is formed between the resin and the photocatalyst fine particles. A calcined layer of a polytetrafluoroethylene resin containing a coloring pigment or a filler is provided as a reinforcing layer on the back surface of the resin, and a hot-melt perfluoropolymer containing colloidal silica as an easily adhesive layer is provided on the back surface of the reinforcing layer. A fired layer of resin may be provided, and an adhesive layer may be provided on the back surface of the easily adhesive layer. In the method for producing a photocatalyst sheet according to the present invention, the coating layer of the dispersion containing the polytetrafluoroethylene powder and the photocatalyst fine particles is heated to evaporate and remove the solvent, and further heated to remove the polytetrafluoroethylene powder. It is a configuration characterized by sintering and firing, and then cooling to form a photocatalyst layer.
【０００９】[0009]
【発明の実施の形態】以下、図面を参照しつつ本発明の
実施の形態について説明する。図１は本発明に係る光触
媒シ−トの一例を示している。図１において、１はポリ
テトラフルオロエチレン樹脂の焼成層内に光触媒微粒子
が分散され、樹脂と光触媒微粒子との間に微小空気層が
形成されて成る光触媒層を示し、ポリテトラフルオロエ
チレン粉末と光触媒微粒子とを含有したディスパ−ジョ
ンをキャスティング用キャリヤに塗布し、加熱により塗
布層中の溶媒を蒸発除去し、更に加熱焼成によりポリテ
トラフルオロエチレン粒子間を焼結し、ついで冷却し、
キャスティング用キャリヤから剥離することによって形
成してあり、光触媒微粒子とポリテトラフルオロエチレ
ン樹脂との間の空気層の生成は、上記冷却時でのポリテ
トラフルオロエチレン樹脂の光触媒微粒子よりも大なる
熱収縮及びポリテトラフルオロエチレン樹脂の光触媒微
粒子に対する非融着性に依存している。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 shows an example of a photocatalyst sheet according to the present invention. In FIG. 1, reference numeral 1 denotes a photocatalyst layer in which fine particles of photocatalyst are dispersed in a fired layer of polytetrafluoroethylene resin and a fine air layer is formed between the resin and the fine particles of photocatalyst. The dispersion containing fine particles is applied to a casting carrier, the solvent in the coating layer is removed by evaporation by heating, and the polytetrafluoroethylene particles are sintered by heating and sintering, and then cooled,
The air layer formed between the photocatalyst fine particles and the polytetrafluoroethylene resin is formed by peeling off from the casting carrier. And the non-fusibility of the polytetrafluoroethylene resin to the photocatalyst fine particles.
【００１０】上記光触媒微粒子には、優れた光触媒活性
を呈するアナタ−ゼ型酸化チタン微粒子を使用すること
が好ましい。また、光触媒微粒子の活性を高めるため
に、アルカリ金属イオンを担持させることができる。上
記ポリテトラフルオロエチレン粉末の粒径は、０．２〜
０．３μｍ、光触媒微粒子の粒径は、０．００７〜０．
５μｍであり、焼成によりポリテトラフルオロエチレン
の粒子間が焼結され、その焼成の温度でのポリテトラフ
ルオロエチレン粒子の流動が実質状生じないためにポリ
テトラフルオロエチレン粒子の焼結箇所に間隙が形成さ
れ易く、この間隙が上記空気層に繋がって光触媒層組織
の連続気泡化が促される。而して、ポリテトラフルオロ
エチレン樹脂と光触媒微粒子との空気層の厚みは、数ナ
ノメ−タ〜数ミクロンの微細間隙であり、水等の液体の
通過は生じないが、連続気泡のために空気は充分に出入
りし得る。上記ディスパ−ジョン中の光触媒微粒子の配
合量が多すぎると、ポリテトラフルオロエチレンによる
光触媒微粒子間の結着強度が不充分となるので、ポリテ
トラフルオロエチレン粉末／光触媒微粒子の混合比は、
３／７〜８／２とすることが好ましい。It is preferable to use an anatase type titanium oxide fine particle exhibiting excellent photocatalytic activity as the photocatalytic fine particles. Further, in order to enhance the activity of the photocatalyst fine particles, an alkali metal ion can be supported. The particle size of the polytetrafluoroethylene powder is 0.2 to
0.3 μm, and the particle size of the photocatalyst fine particles is 0.007 to 0.1.
5 μm, and sintering sinters between the polytetrafluoroethylene particles. Since the flow of the polytetrafluoroethylene particles at the sintering temperature does not substantially occur, a gap is formed between the sintering points of the polytetrafluoroethylene particles. This gap is easily formed, and this gap is connected to the air layer, so that the photocatalyst layer structure is made to be open cells. Thus, the thickness of the air layer between the polytetrafluoroethylene resin and the photocatalyst fine particles is a fine gap of several nanometers to several microns, and the passage of liquid such as water does not occur. Can get in and out. If the content of the photocatalyst fine particles in the dispersion is too large, the bonding strength between the photocatalyst fine particles by polytetrafluoroethylene becomes insufficient, so that the mixing ratio of polytetrafluoroethylene powder / photocatalyst fine particles is:
It is preferably 3/7 to 8/2.
【００１１】上記光触媒層は、上記した通り、ディスパ
−ジョンのキャスティング用キャリヤへの塗布、乾燥、
焼成、冷却、キャスティング用キャリヤからの剥離によ
り製作され、光触媒層の表面平滑性はキャスティング用
キャリヤの平滑性で規制される。而るに、光触媒層の表
面粗さが大きすぎると、防汚に支障となり、また表面積
が大となりその表面に突出する光触媒微粒子が多くなっ
て光触媒微粒子の脱落防止上も好ましくないので、光触
媒層の表面粗さＲｚ（JIS B 0601)は２μｍ以下とし、
キャスティング用キャリヤの表面粗さＲｚは４μｍ以下
とすることが好ましい。このキャスティング用キャリヤ
には、上記表面粗さ以外に、上記焼成時の加熱によって
も変形等を生じない耐熱性及び剥離性が要求され、金属
箔や金属シ−トが適切である。[0011] As described above, the photocatalyst layer is coated on the carrier for casting of the dispersion, dried, and dried.
It is manufactured by firing, cooling, and peeling from the casting carrier, and the surface smoothness of the photocatalyst layer is regulated by the smoothness of the casting carrier. However, if the surface roughness of the photocatalyst layer is too large, it will hinder antifouling, and the surface area will be large, so that the number of photocatalyst fine particles protruding on the surface is also unfavorable in preventing the photocatalytic fine particles from falling off. Has a surface roughness Rz (JIS B 0601) of 2 μm or less,
The casting carrier preferably has a surface roughness Rz of 4 μm or less. In addition to the surface roughness, the casting carrier is required to have heat resistance and releasability that do not cause deformation or the like even by heating during the firing, and a metal foil or a metal sheet is appropriate.
【００１２】上記キャスティング用キャリヤへのディス
パ−ジョンの塗布には、キャリヤをディスパ−ジョン中
に浸漬して引き上げる方法、ディスパ−ジョンをスプレ
−する方法、ディスパ−ジョンを刷毛塗する方法、ディ
スパ−ジョンを流延する方法、ロ−ルコ−タにより塗布
する方法等を使用できる。上記ディスパ−ジョンの濃度
は、塗布方法に応じて設定されるが、通常４０％〜６０
％とされる。The method of applying the dispersion to the casting carrier includes a method of dipping the carrier into the dispersion and pulling it up, a method of spraying the dispersion, a method of brush-coating the dispersion, and a method of brush-coating the dispersion. A method of casting John, a method of coating with a roll coater, and the like can be used. The concentration of the dispersion is set according to the coating method, and is usually 40% to 60%.
%.
【００１３】図１において、２は補強層であり、上記キ
ャスティング用キャリヤからの剥離時の張力に耐え得る
強度を付与し、また、光触媒シ−トに所望の厚みを付与
するために使用され、例えば、耐摩耗性充填剤や無機顔
料を添加したポリテトラフルオロエチレン粉末のディス
パ−ジョンの塗布、乾燥、焼成、冷却により形成でき
る。その厚みは、例えば、１０〜４０μｍとされる。３
は易接着性層であり、例えば、加熱溶融性パ−フロロ樹
脂粉末（例えば、パ−フルオロアルキルビニルエ−テル
−テトラフルオロエチレンコポリマ−やヘキサフルオロ
プロピレン−テトラフルオロエチレンコポリマ−の粉
末。粒径０．２〜０．３μｍ）とコロイダルシリカ（粒
径０．０１〜０．０２μｍ）とを含有するディスパ−ジ
ョンの塗布、乾燥、焼成、冷却により形成できる。その
厚みは、例えば、１〜５μｍとされる。この易接着性層
においては、パ−フロロ樹脂とコロイダルシリカとの間
が密着され、その間での空隙の発生が実質上ないので、
緻密組織である。４は接着層であり、粘着剤層を使用す
ることが好ましく、シリコ−ン系、アクリル系等の通常
の粘着剤を使用できる。５は接着層４に接着した剥離紙
である。In FIG. 1, reference numeral 2 denotes a reinforcing layer, which is used for imparting strength capable of withstanding a tension at the time of peeling from the casting carrier and for giving a desired thickness to the photocatalytic sheet. For example, it can be formed by applying a dispersion of a polytetrafluoroethylene powder to which a wear-resistant filler or an inorganic pigment is added, drying, baking, and cooling. Its thickness is, for example, 10 to 40 μm. 3
Is an easily adhesive layer, for example, a heat-meltable perfluoro resin powder (for example, powder of perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer or hexafluoropropylene-tetrafluoroethylene copolymer. It can be formed by coating, drying, baking, and cooling a dispersion containing 0.2 to 0.3 μm) and colloidal silica (particle size: 0.01 to 0.02 μm). Its thickness is, for example, 1 to 5 μm. In this easily adhesive layer, the perfluoro resin and the colloidal silica are in close contact with each other, and there is substantially no void between them.
It is a dense organization. Reference numeral 4 denotes an adhesive layer, preferably an adhesive layer, which can be a conventional silicone or acrylic adhesive. Reference numeral 5 denotes a release paper adhered to the adhesive layer 4.
【００１４】図１に示す光触媒シ−トの製造には、ポリ
テトラフルオロエチレン粉末と光触媒微粒子とのディス
パ−ジョンをキャスティング用キャリヤに塗布し、この
塗布層を乾燥、焼成及び冷却して光触媒層１を形成し、
更に、充填剤または無機顔料とポリテトラフルオロエチ
レン粉末とのディスパ−ジョンを光触媒層層上に塗布、
乾燥、焼成及び冷却して補強層２を形成し、更にパ−フ
ロロ樹脂粉末とコロイダルシリカとのディスパ−ジョン
を塗布、乾燥、焼成及び冷却して易接着層３を形成し、
この易接着層３に粘着剤４を塗布し、更に剥離紙５を接
着してから、光触媒シ−トをキャスティング用キャリヤ
から剥離する方法、上記易接着層３の形成後に、三層
（光触媒層１と補強層２と易接着性層３）を一体的にキ
ャスティング用キャリヤから剥離し、更に粘着剤４の塗
布及び剥離紙５の接着を行う方法によることができる。For the production of the photocatalyst sheet shown in FIG. 1, a dispersion of polytetrafluoroethylene powder and photocatalyst fine particles is applied to a casting carrier, and the applied layer is dried, fired and cooled to form a photocatalyst layer. Form one,
Further, a dispersion of a filler or an inorganic pigment and polytetrafluoroethylene powder is applied on the photocatalyst layer,
The reinforcing layer 2 is formed by drying, firing and cooling, and a dispersion of a perfluoro resin powder and colloidal silica is applied, dried, fired and cooled to form an easily adhesive layer 3,
A method of applying a pressure-sensitive adhesive 4 to the easy-adhesion layer 3, further adhering a release paper 5, and then peeling off the photocatalyst sheet from the casting carrier. 1, the reinforcing layer 2, and the easily-adhesive layer 3) can be integrally peeled off from the casting carrier, and then the adhesive 4 can be applied and the release paper 5 can be adhered.
【００１５】本発明に係る光触媒シ−トにおいては、デ
ィスパ−ジョンの光触媒微粒子と樹脂バインダ−との間
に空気層が存在し、この空気層が光触媒層の連続気泡組
織のために外気と通じているから、空気が光触媒微粒子
の外表面にほぼ全面で接触して通過し、空気中の細菌や
有害ガスを活性化光触媒微粒子で効率よく酸化分解でき
る。また、光触媒微粒子を担持している樹脂が難分解性
のポリテトラフルオロエチレンであるから、樹脂バイン
ダ−を崩壊無く長期安定に保持でき、かつ、光触媒微粒
子を樹脂層の気泡内に抱き込ませてあるから、光触媒微
粒子を長期にわたり安定に担持できる。従って、空気中
の細菌や有害ガスを長期にわたり効率よく酸化分解でき
る。In the photocatalyst sheet according to the present invention, an air layer exists between the photocatalyst fine particles of the dispersion and the resin binder, and this air layer communicates with the outside air due to the open cell structure of the photocatalyst layer. Therefore, the air almost completely contacts and passes through the outer surface of the photocatalyst fine particles, and bacteria and harmful gas in the air can be efficiently oxidized and decomposed by the activated photocatalytic fine particles. In addition, since the resin carrying the photocatalyst fine particles is a hardly decomposable polytetrafluoroethylene, the resin binder can be stably maintained for a long time without collapse, and the photocatalyst fine particles are entrapped in the bubbles of the resin layer. Therefore, the photocatalyst fine particles can be stably supported over a long period of time. Therefore, bacteria and harmful gases in the air can be efficiently oxidatively decomposed over a long period of time.
【００１６】特に、上記実施例の光触媒シ−トにおいて
は、上記補強層が光触媒層と同様に連続気泡化されて
も、活性化光触媒微粒子による酸化分解で発生する水酸
ラジカルや活性酸素が、緻密組織の易接着層のために接
着剤層から確実に遮断されるから、光触媒微粒子の活性
化に基づく接着剤層の劣化を防止でき、長期の安定な接
着使用を保証できる。勿論、積層状態で保管しても、剥
離紙によって光触媒層と粘着剤層との直接接触を防止で
きるから、保管中での紫外線の入射で光触媒微粒子が活
性化しても、接着剤層を安定に保持できる。In particular, in the photocatalyst sheet of the above embodiment, even if the reinforcing layer is made into open cells as in the case of the photocatalyst layer, hydroxyl radicals and active oxygen generated by oxidative decomposition by activated photocatalyst fine particles, Since the dense tissue is easily adhered to the adhesive layer due to the adhesive layer, deterioration of the adhesive layer due to activation of the photocatalyst fine particles can be prevented, and long-term stable adhesive use can be guaranteed. Of course, even when stored in a laminated state, the release paper can prevent direct contact between the photocatalyst layer and the pressure-sensitive adhesive layer. Therefore, even if the photocatalyst fine particles are activated by the incidence of ultraviolet rays during storage, the adhesive layer is stably maintained. Can hold.
【００１７】本発明に係る光触媒シ−トの使用中での活
性化（励起）は、紫外線の照射の外、プラズマ照射によ
っても行うことができる。本発明に係る除菌、防汚、防
臭、浄化等に使用でき、具体的には、空気浄化装置や冷
蔵庫内に粘着固定し、建物の内装材から発生する溶剤ガ
スの分解除去や果物や農作物の熟成を速めるエチレンの
分解除去等に使用できる。なお、紫外線の照射条件が比
較的緩い場合、本発明に係る光触媒シ−トは、補強層の
裏面にスパッタリングやコロナ処理等の易接着化処理を
施し、この処理面に接着剤層を設ける形態で実施するこ
ともできる。The activation (excitation) during use of the photocatalyst sheet according to the present invention can be carried out not only by ultraviolet irradiation but also by plasma irradiation. It can be used for sanitization, antifouling, deodorization, purification, etc. according to the present invention. Specifically, it is adhesively fixed in an air purification device or a refrigerator to decompose and remove solvent gas generated from interior materials of buildings, fruits and crops. It can be used to decompose and remove ethylene, which accelerates ripening. When the irradiation condition of the ultraviolet rays is relatively mild, the photocatalyst sheet according to the present invention is configured such that the back surface of the reinforcing layer is subjected to an easy adhesion treatment such as sputtering or corona treatment, and an adhesive layer is provided on the treated surface. Can also be implemented.
【００１８】[0018]
〔実施例〕ポリテトラフルオロエチレン粉末（粒子径ほ
ぼ０．２５μｍ）とアナタ−ゼ型酸化チタン微粒子（粒
子径０．０２μｍ）を重量比６：４で含有する固形分濃
度４０％の水ディスパ−ジョンを調製した。このディス
パ−ジョンに厚さ５０μｍ、表面粗さＲｚ３．８μｍの
ステンレス箔を浸漬し引上げ、１００℃×６０秒の加熱
で水を蒸発・除去し、更に３９０℃×９０秒の加熱で焼
成し、厚み７μｍの光触媒層を形成した。次に、ポリテ
トラフルオロエチレン粉末の水ディスパ−ジョンに緑色
無機顔料を１０重量％添加し、このディスパ−ジョンへ
の上記光触媒層付きステンレス箔の浸漬・引上げ、１０
０℃×６０秒での水の蒸発除去、３９０℃×９０秒での
焼成の一連の処理を二回行って、厚み２１μｍの補強層
を形成した。次に、パ−フルオロアルキルビニルエ−テ
ル−テトラフルオロエチレン共重合体の水ディスパ−ジ
ョンにコロイダルシリカ（粒径０．０１〜０．０２μ
ｍ）を２０重量％添加し、このディスパ−ジョンへの浸
漬・引上げ、１００℃×６０秒での水の蒸発除去、３９
０℃×９０秒での焼成を行って厚さ２μｍの緻密な易接
着性層を形成した。これらの三層の積層厚みは３０μｍ
であり、この積層体をステンレス箔から剥離し、易接着
性層にアクリル系粘着剤を乾燥厚さ５０μｍで塗布して
光触媒シ−トを得た。この光触媒シ−トの光触媒層の表
面粗さＲｚは１．８μｍであった。EXAMPLE A water dispersion containing a polytetrafluoroethylene powder (particle size: approximately 0.25 μm) and anatase type titanium oxide fine particles (particle size: 0.02 μm) at a weight ratio of 6: 4 and a solid concentration of 40% was used. John was prepared. A stainless steel foil having a thickness of 50 μm and a surface roughness Rz of 3.8 μm is immersed and pulled up in this dispersion, water is evaporated and removed by heating at 100 ° C. × 60 seconds, and further baked by heating at 390 ° C. × 90 seconds. A photocatalyst layer having a thickness of 7 μm was formed. Next, 10% by weight of a green inorganic pigment is added to a water dispersion of polytetrafluoroethylene powder, and the stainless steel foil with the photocatalyst layer is immersed and pulled into the dispersion.
A series of treatments of removing water by evaporation at 0 ° C. × 60 seconds and firing at 390 ° C. × 90 seconds was performed twice to form a reinforcing layer having a thickness of 21 μm. Next, water dispersion of the perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer was added to colloidal silica (particle size: 0.01 to 0.02 μm).
m) was added to the dispersion, immersed in the dispersion and pulled up, and evaporated to remove water at 100 ° C. for 60 seconds.
Baking was performed at 0 ° C. for 90 seconds to form a dense, easily-adhesive layer having a thickness of 2 μm. The laminated thickness of these three layers is 30 μm
The laminate was peeled from the stainless steel foil, and an acrylic adhesive was applied to the easily adhesive layer at a dry thickness of 50 μm to obtain a photocatalyst sheet. The surface roughness Rz of the photocatalyst layer of this photocatalyst sheet was 1.8 μm.
【００１９】この光触媒シ−トの５ｃｍ×５ｃｍ片に対
し、大腸菌濃度１０5個／ミリリットルの菌液０．５ミ
リリットルを光触媒層上に滴下し、ブラックライト（紫
外線強度０．１ｍＷ／ｃｍ2）を照射し、寒天培養して
コロニ−数を測定する殺菌試験を行ったところ、１時間
照射で菌数１０個以下に減少した。光照射なしの場合、
３時間経過後でも、菌数は殆ど減少せず、ほぼ１０5個
のままであった。また、市販の１５Ｗのブラックライト
をセットした内容積４リットルの密閉容器中に、光触媒
シ−トの５ｃｍ×５ｃｍ片を光触媒層をブラックライト
に向けて配置し、悪臭物質としてアセトアルデヒド１０
０ｐｐｍを注入した後、ブラックライトを点灯して１ｍ
Ｗ／ｃｍ2の紫外線を照射し、所定時間の照射後、ガス
クロマトグラフを用いて容器内のアセトアルデヒド濃度
を測定するアセトアルデヒド分解試験を行ったところ、
６０分紫外線照射でアセトアルデヒド濃度が３０ｐｐｍ
に減少した。To a 5 cm × 5 cm piece of this photocatalyst sheet, 0.5 ml of a bacterial solution having a concentration of 10 5 cells / ml of Escherichia coli was dropped on the photocatalyst layer, and a black light (ultraviolet intensity: 0.1 mW / cm 2 ) was obtained. A sterilization test was performed by culturing the agar and agar culture, and the number of bacteria was reduced to 10 or less by irradiation for 1 hour. Without light irradiation,
Even after 3 hours, the number of bacteria hardly decreased and remained at about 10 5 . A 5 cm × 5 cm piece of a photocatalyst sheet was placed in a closed container having a capacity of 4 liters, on which a commercially available 15 W black light was set, with the photocatalyst layer facing the black light.
After injecting 0ppm, turn on the black light and 1m
After irradiating with UV light of W / cm 2 and irradiating for a predetermined time, an acetaldehyde decomposition test was performed to measure the acetaldehyde concentration in the container using a gas chromatograph.
Acetaldehyde concentration is 30ppm by UV irradiation for 60 minutes
Decreased to.
【００２０】〔比較例〕実施例に対し、光触媒層形成用
の水ディスパ−ジョン中のポリテトラフルオロエチレン
に代え、パ−フルオロアルキルビニルエ−テル−テトラ
フルオロエチレン共重合体を使用した以外、実施例と同
じとした。実施例と同様にして殺菌試験を行い、光照射
１時間後の菌数を測定したところ、約１０4個であっ
た。また、実施例と同様にしてアセトアルデヒド分解試
験を行い、６０分紫外線照射後でのアセトアルデヒド濃
度を測定したところほぼ９０ｐｐｍであった。[Comparative Example] In comparison with the example, a perfluoroalkylvinyl ether-tetrafluoroethylene copolymer was used instead of polytetrafluoroethylene in the water dispersion for forming the photocatalyst layer. It was the same as the example. A sterilization test was performed in the same manner as in the example, and the number of bacteria one hour after light irradiation was measured. As a result, it was about 10 4 . In addition, an acetaldehyde decomposition test was performed in the same manner as in the example, and the concentration of acetaldehyde after irradiation with ultraviolet rays for 60 minutes was approximately 90 ppm.
【００２１】このように、比較例が実施例に較べ、殺菌
性及びアセトアルデヒド分解性等に劣るのは、パ−フル
オロアルキルビニルエ−テル−テトラフルオロエチレン
共重合体が光触媒微粒子によく加熱融着し、光触媒微粒
子の表面の大部分がパ−フルオロアルキルビニルエ−テ
ル−テトラフルオロエチレン共重合体で覆われる結果で
あると推定される。As described above, the comparative example is inferior in sterilization and acetaldehyde decomposability as compared with the example because the perfluoroalkylvinylether-tetrafluoroethylene copolymer is well fused to the photocatalyst fine particles by heating. However, it is estimated that most of the surfaces of the photocatalyst fine particles are covered with the perfluoroalkylvinyl ether-tetrafluoroethylene copolymer.
【００２２】なお、実施例品においては、３ｍＷ／ｃｍ
2×２０００時間の過酷な紫外線照射のもとでも、接着
剤層に何等の異常も観られず、剥離は生じなかったが、
易接着性層を省略し、補強層の裏面をスパッタリング処
理し、この処理面に粘着剤層を設けたものでは、３ｍＷ
／ｃｍ2×１００時間の紫外線照射で粘着剤層に剥離が
生じた。Incidentally, in the example product, 3 mW / cm
Even under severe UV irradiation for 2 x 2000 hours, no abnormality was observed in the adhesive layer, and no peeling occurred.
In the case where the easily adhesive layer was omitted, the back surface of the reinforcing layer was subjected to a sputtering treatment, and the pressure-sensitive adhesive layer was provided on the treated surface, 3 mW
/ Cm 2 × 100 hours of ultraviolet irradiation peeled off the pressure-sensitive adhesive layer.
【００２３】[0023]
【発明の効果】本発明に係る光触媒シ−トにおいては、
光触媒微粒子とバインダ−樹脂との間に微細空気層が存
在し、その空気層と樹脂層の連続気泡との繋りにより外
部の空気が光触媒微粒子のほぼ全面に接触して流通する
から、その空気中細菌等に対する活性光触媒微粒子の酸
化分解効率を向上できる。また、光触媒微粒子が樹脂バ
ンンダ−内に抱えられ、かつ樹脂自体が難分解性である
から、光触媒微粒子を安定に担持できる。従って、本発
明に係る光触媒シ−トによれば、長期間優れた効率で除
菌、防汚、防臭、浄化を行い得る。According to the photocatalyst sheet of the present invention,
A fine air layer exists between the photocatalyst fine particles and the binder-resin, and the outside air comes into contact with almost the entire surface of the photocatalyst fine particles due to the connection between the air layer and the continuous bubbles of the resin layer. It is possible to improve the efficiency of oxidative decomposition of active photocatalytic fine particles against bacteria and the like. Further, since the photocatalyst fine particles are held in the resin binder and the resin itself is hardly decomposable, the photocatalyst fine particles can be stably supported. Therefore, according to the photocatalyst sheet of the present invention, sterilization, antifouling, deodorization, and purification can be performed with excellent efficiency for a long time.
【図１】本発明に係る光触媒シ−トを示す図面である。FIG. 1 is a drawing showing a photocatalyst sheet according to the present invention.
１ 光触媒層 ２ 補強層 ３ 易接着性層 ４ 粘着剤層 ５ 剥離紙 DESCRIPTION OF SYMBOLS 1 Photocatalyst layer 2 Reinforcement layer 3 Adhesive layer 4 Adhesive layer 5 Release paper
Claims (6)
内に光触媒微粒子が分散され、樹脂と光触媒微粒子との
間に微小空気層が形成されて成る光触媒層を有すること
を特徴とする光触媒シ−ト。1. A photocatalyst sheet having a photocatalyst layer in which fine particles of photocatalyst are dispersed in a fired layer of polytetrafluoroethylene resin and a fine air layer is formed between the resin and the fine particles of photocatalyst. .
内に光触媒微粒子が分散され、樹脂と光触媒微粒子との
間に微小空気層が形成されて成る光触媒層の裏面に補強
層が設けられ、該補強層の裏面に易接着性層が設けら
れ、該易接着性層の裏面に接着層が設けられていること
を特徴とする光触媒シ−ト。2. A reinforcing layer is provided on a back surface of a photocatalyst layer in which photocatalyst fine particles are dispersed in a fired layer of polytetrafluoroethylene resin and a fine air layer is formed between the resin and the photocatalyst fine particles. A photocatalyst sheet comprising: an easy-adhesion layer provided on the back surface of the layer; and an adhesion layer provided on the back surface of the easy-adhesion layer.
る請求項１または２記載の光触媒シ−ト。3. The photocatalyst sheet according to claim 1, wherein the surface roughness Rz of the photocatalyst layer is 4 μm or less.
ポリテトラフルオロエチレン樹脂の焼成層であり、易接
着性層がコロイダルシリカを含有する熱溶融性パ−フロ
ロ樹脂の焼成層である請求項２または３記載の光触媒シ
−ト。4. The fired layer of a polytetrafluoroethylene resin containing a color pigment or a filler, and the easily adhesive layer is a fired layer of a heat-fusible perfluoro resin containing colloidal silica. Item 4. The photocatalyst sheet according to item 2 or 3.
内の焼結された樹脂粒子間に間隙が残存している請求項
１乃至４何れか記載の光触媒シ−ト。5. The photocatalyst sheet according to claim 1, wherein gaps remain between the sintered resin particles in the fired layer of the polytetrafluoroethylene resin.
微粒子を含有するディスパ−ジョンの塗布層を加熱して
溶媒を蒸発除去し、更に加熱してポリテトラフルオロエ
チレン粉末を焼結・焼成し、而るのち、冷却して光触媒
層を形成する請求項２記載の光触媒シ−トの製造方法。6. A coating layer of a dispersion containing polytetrafluoroethylene powder and photocatalyst fine particles is heated to evaporate and remove the solvent, and further heated to sinter and fire the polytetrafluoroethylene powder. 3. The method for producing a photocatalyst sheet according to claim 2, wherein the photocatalyst layer is formed by cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21996997A JP3831080B2 (en) | 1997-07-31 | 1997-07-31 | Photocatalytic sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21996997A JP3831080B2 (en) | 1997-07-31 | 1997-07-31 | Photocatalytic sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1147610A true JPH1147610A (en) | 1999-02-23 |
| JP3831080B2 JP3831080B2 (en) | 2006-10-11 |
Family
ID=16743873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21996997A Expired - Fee Related JP3831080B2 (en) | 1997-07-31 | 1997-07-31 | Photocatalytic sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3831080B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6890645B2 (en) | 2000-06-21 | 2005-05-10 | Fuji Photo Film B.V. | Photocatalytic sheet or film and its manufacturing process |
| WO2006137446A1 (en) * | 2005-06-22 | 2006-12-28 | Ube-Nitto Kasei Co., Ltd. | Antifouling printing sheet |
| US7998562B2 (en) | 2003-07-22 | 2011-08-16 | Taiyo Kogyo Corporation | Photocatalyst sheet and method of producing same |
| JP2019104191A (en) * | 2017-12-14 | 2019-06-27 | カンボウプラス株式会社 | Antifouling sheet |
-
1997
- 1997-07-31 JP JP21996997A patent/JP3831080B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6890645B2 (en) | 2000-06-21 | 2005-05-10 | Fuji Photo Film B.V. | Photocatalytic sheet or film and its manufacturing process |
| US7998562B2 (en) | 2003-07-22 | 2011-08-16 | Taiyo Kogyo Corporation | Photocatalyst sheet and method of producing same |
| WO2006137446A1 (en) * | 2005-06-22 | 2006-12-28 | Ube-Nitto Kasei Co., Ltd. | Antifouling printing sheet |
| JPWO2006137446A1 (en) * | 2005-06-22 | 2009-01-22 | 宇部日東化成株式会社 | Antifouling printing sheet |
| JP2019104191A (en) * | 2017-12-14 | 2019-06-27 | カンボウプラス株式会社 | Antifouling sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3831080B2 (en) | 2006-10-11 |
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