JP2000350936A - Carrier for photocatalyst - Google Patents
Carrier for photocatalystInfo
- Publication number
- JP2000350936A JP2000350936A JP11164089A JP16408999A JP2000350936A JP 2000350936 A JP2000350936 A JP 2000350936A JP 11164089 A JP11164089 A JP 11164089A JP 16408999 A JP16408999 A JP 16408999A JP 2000350936 A JP2000350936 A JP 2000350936A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- carrier
- present
- fluorine
- repeating unit
- 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.)
- Withdrawn
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 229920005604 random copolymer Polymers 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims description 14
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- -1 hydrocarbon halide Chemical class 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 125000005739 1,1,2,2-tetrafluoroethanediyl group Chemical group FC(F)([*:1])C(F)(F)[*:2] 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000010419 fine particle Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101100321670 Fagopyrum esculentum FA18 gene Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒反応を利用
し、臭気物質や汚れ物質などの有害物質を分解し得る光
触媒を担持する担体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carrier for supporting a photocatalyst capable of decomposing harmful substances such as odorous substances and dirt substances by utilizing a photocatalytic reaction.
【０００２】[0002]
【従来の技術】光触媒は、紫外光を照射すると光励起に
より、伝導帯に電子を価電子帯に正孔をそれぞれ生じ、
この電子の持つ還元力や正孔の持つ酸化力によって、殺
菌、脱臭および有機物分解作用を生じる。このような原
理を応用して、日用品や建築材料等の物品に光触媒を応
用する試みが成されている。2. Description of the Related Art When photocatalysts are irradiated with ultraviolet light, they generate electrons in a conduction band and holes in a valence band by photoexcitation, respectively.
The reducing power of the electrons and the oxidizing power of the holes cause sterilization, deodorization and decomposition of organic substances. Attempts have been made to apply photocatalysts to articles such as daily necessities and building materials by applying such a principle.
【０００３】光触媒は、一般に、粉末状もしくは溶液に
懸濁させた形で使用した方が一般的に触媒活性が高いと
言われているものの、実用的には、該光触媒を目的とす
る箇所に安定に固定して使用するためには、何らかの担
体上に担持する必要がある。[0003] Photocatalysts are generally said to have higher catalytic activity when used in the form of powder or suspended in a solution, but practically, photocatalysts are used in places where the photocatalyst is intended. In order to use it stably fixed, it is necessary to carry it on some kind of carrier.
【０００４】この場合、光触媒は上記物品を構成する素
材自体を担体とし、これに直接担持させたり、フィルム
を担体とし、これに光触媒を担持せしめた後、上記物品
に該フィルムを貼付したりするのが一般的である。[0004] In this case, the photocatalyst is formed by directly supporting the material constituting the article as a carrier, or by using a film as a carrier and supporting the photocatalyst thereon, and then attaching the film to the article. It is common.
【０００５】ところが、上記担体として有機物を主体と
する材質を使用した場合、光触媒を担持するとその触媒
作用により担体自体が分解されたり劣化し、耐久性に問
題がある。[0005] However, when a material mainly composed of an organic substance is used as the carrier, when the photocatalyst is carried, the carrier itself is decomposed or deteriorated by the catalytic action, and there is a problem in durability.
【０００６】そのため、上記担体として、耐候性、耐薬
品性の優れたフッ素樹脂を使用することが提案されてい
る。例えば、特開平４−２８４８５１号公報には、光触
媒粒子とフッ素樹脂との混合物を積層し圧着する方法が
開示されている。特開平４−３３４５５２号公報には、
光触媒粒子をフッ素樹脂に熱融着する方法が開示されて
いる。Therefore, it has been proposed to use a fluororesin having excellent weather resistance and chemical resistance as the carrier. For example, Japanese Patent Application Laid-Open No. 4-284851 discloses a method in which a mixture of photocatalyst particles and a fluororesin is laminated and pressed. JP-A-4-334552 discloses that
A method for thermally fusing photocatalyst particles to a fluororesin is disclosed.
【０００７】上記フッ素樹脂としては、ポリテトラフル
オロエチレン、テトラフルオロエチレン−ヘキサフルオ
ロプロピレンコポリマー、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コポリマー、テトラ
フルオロエチレン−ヘキサフルオロプロピレンコポリマ
ー、テトラフルオロエチレン−エチレンコポリマー等が
例示されている。Examples of the fluororesin include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer and the like. Is illustrated.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、提案さ
れている上記フッ素樹脂を担体として、光触媒を担持せ
しめた光触媒担持体は、光の照射面において該光触媒の
機能を発揮するものの、例えば、板状或いはシート状に
成形された薄物成形体において、光の照射面に対して反
対面に存在する光触媒はその機能が殆ど発揮されないと
いう現象を生ずる。However, the proposed photocatalyst carrier having the above-mentioned fluororesin as a carrier and carrying a photocatalyst exhibits the function of the photocatalyst on the surface irradiated with light. Alternatively, in a thin molded article formed in a sheet shape, a phenomenon occurs in which the photocatalyst existing on the surface opposite to the light irradiation surface hardly exhibits its function.
【０００９】そのため、フッ素樹脂によってケースを成
形すると共に、その内面に光触媒を存在（担持）せし
め、その外部より光を照射してケース内のガスを処理す
る場合や、フッ素樹脂によって光源、例えば、蛍光灯、
電球等のカバーを成形すると共に、その外面に光触媒を
存在せしめ、上記光源からの光によって該カバーに接触
するガスを処理しようとした場合、光触媒が殆ど機能せ
ず、その目的を達成することが困難であるという問題を
有する。For this reason, the case is formed of a fluororesin, and a photocatalyst is present (supported) on the inner surface of the case, and light is irradiated from the outside to treat the gas in the case. Fluorescent light,
When a cover such as a light bulb is formed, a photocatalyst is present on the outer surface of the cover, and when the gas coming into contact with the cover is treated by light from the light source, the photocatalyst hardly functions, thereby achieving the object. It has the problem of being difficult.
【００１０】従って、本発明の目的は、担体に担持され
た光触媒に直接照射される光は素より、担体自体を透過
した光によっても光触媒が十分に機能することが可能
な、広い適用範囲を持った、光触媒用担体を提供するこ
とにある。[0010] Therefore, an object of the present invention is to provide a wide application range in which the photocatalyst supported on the carrier is not directly irradiated but the photocatalyst can function sufficiently even by the light transmitted through the carrier itself. Another object of the present invention is to provide a photocatalyst carrier.
【００１１】[0011]
【課題を解決するための手段】本発明者らは上記課題を
解決すべく鋭意研究を重ねた結果、特定の構造及び組成
を有する含フッ素ランダム共重合体が、透明性に優れ且
つ光触媒の作用に有効な波長の光が極めて効率よく透過
し得ることを見い出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a fluorine-containing random copolymer having a specific structure and composition has excellent transparency and an action of a photocatalyst. The present inventors have found that light having a wavelength effective for transmission can be transmitted extremely efficiently, and have completed the present invention.
【００１２】即ち、本発明は下記一般式（Ｉ） −ＣＦ2ＣＦ2− （Ｉ） で表される繰り返し単位と下記一般式（II） −ＣＦ（ＯＲf）ＣＦ2− （II） （但し、Ｒfはハロゲン化炭化水素である）で表される
繰り返し単位を有し、且つ上記一般式（Ｉ）で示される
繰り返し単位が６０〜９２モル％であり、上記一般式
（II）で示される繰り返し単位が８〜４０モル％である
含フッ素ランダム共重合体からなることを特徴とする光
触媒用担体である。That is, the present invention relates to a repeating unit represented by the following general formula (I) -CF 2 CF 2- (I) and the following general formula (II) -CF (OR f ) CF 2- (II) , R f is a halogenated hydrocarbon), and the repeating unit represented by the general formula (I) is 60 to 92 mol%, and represented by the general formula (II). A photocatalyst carrier comprising a fluorine-containing random copolymer having a repeating unit of 8 to 40 mol%.
【００１３】[0013]
【発明の実施の形態】本発明の含フッ素ランダム共重合
体を構成する前記一般式（II）で示される繰り返し単位
中、Ｒfはハロゲン化炭化水素であれば特に制限はない
が、アルキル基等の炭化水素の一部ないし全部がフッ
素、塩素、臭素等のハロゲン原子で置換された基が好適
である。前記一般式（II）中において、特に本発明にお
いて好適なＲf基は、下記一般式（III） −ＣaＦbＸcＨ(2a+1-b-c) （III） （但し、Ｘは塩素原子または臭素原子であり、ａは１以
上の整数であり、ｂは０〜2ａ＋１の整数であり、ｃは
０または１であり、且つ１≦ｂ＋ｃ≦２ａ＋１の関係を
有する）で示される基である。前記一般式（III）にお
いて、炭素数は特に制限はないが、原料モノマーの入手
の容易さからａは１〜８が好ましい。前記一般式（II）
においてＲfで表される基を具体的に示せば、−ＣＦ3、
−Ｃ2Ｆ5、−Ｃ3Ｆ7、−Ｃ 4Ｆ9、−Ｃ5Ｆ11、−Ｃ
6Ｆ13、−Ｃ7Ｆ15、−Ｃ8Ｆ17、−ＣＨ2ＣＦ3、−ＣＨ2
Ｃ2Ｆ5、−ＣＨ2Ｃ3Ｆ7、−ＣＨ2Ｃ4Ｆ9、−ＣＨ2Ｃ5Ｆ
11、−ＣＨ2Ｃ6Ｆ13、−ＣＨ2Ｃ7Ｆ15、−ＣＨ2Ｃ
8Ｆ17、−ＣＨ2ＣＦ2Ｈ、−ＣＨ2ＣＦ2Ｃｌ、−ＣＨ2Ｃ
Ｆ2Ｂｒ、−ＣＨ2Ｃ2Ｆ4Ｈ、−ＣＨ2Ｃ2Ｆ4Ｃｌ、−Ｃ
Ｈ2Ｃ2Ｆ4Ｂｒ、−ＣＨ 2Ｃ3Ｆ6Ｈ、−ＣＨ2Ｃ3Ｆ6Ｃ
ｌ、−ＣＨ2Ｃ3Ｆ6Ｂｒ、−ＣＨ2Ｃ4Ｆ8Ｈ、−ＣＨ 2Ｃ4
Ｆ8Ｃｌ、−ＣＨ2Ｃ4Ｆ8Ｂｒ、−ＣＨ2Ｃ5Ｆ10Ｈ、−Ｃ
Ｈ2Ｃ5Ｆ10Ｃｌ、−ＣＨ2Ｃ5Ｆ10Ｂｒ、−ＣＨ2Ｃ6Ｆ12
Ｈ、−ＣＨ2Ｃ6Ｆ12Ｃｌ、−ＣＨ2Ｃ6Ｆ12Ｂｒ、−ＣＨ
2Ｃ7Ｆ14Ｈ、−ＣＨ2Ｃ7Ｆ14Ｃｌ、−ＣＨ2Ｃ7Ｆ14Ｂ
ｒ、−ＣＨ2Ｃ8Ｆ16Ｈ、−ＣＨ2Ｃ8Ｆ16Ｃｌ、−ＣＨ2
Ｃ8Ｆ16Ｂｒ等が挙げられる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Fluorine-containing random copolymer of the present invention
A repeating unit represented by the general formula (II) constituting a body
Medium, RfIs not particularly limited as long as it is a halogenated hydrocarbon
However, some or all of hydrocarbons such as alkyl groups
Preferred are groups substituted with halogen atoms such as nitrogen, chlorine and bromine
It is. In the general formula (II), the present invention
Suitable RfThe group is represented by the following general formula (III) -CaFbXcH(2a + 1-bc) (III) (where X is a chlorine atom or a bromine atom, and a is 1 or more)
Is an integer above, b is an integer from 0 to 2a + 1, and c is
0 or 1 and 1 ≦ b + c ≦ 2a + 1
Has). In the general formula (III)
And the number of carbon atoms is not particularly limited.
A is preferably 1 to 8 from the viewpoint of ease. The general formula (II)
At RfSpecifically, the group represented byThree,
-CTwoFFive, -CThreeF7, -C FourF9, -CFiveF11, -C
6F13, -C7F15, -C8F17, -CHTwoCFThree, -CHTwo
CTwoFFive, -CHTwoCThreeF7, -CHTwoCFourF9, -CHTwoCFiveF
11, -CHTwoC6F13, -CHTwoC7F15, -CHTwoC
8F17, -CHTwoCFTwoH, -CHTwoCFTwoCl, -CHTwoC
FTwoBr, -CHTwoCTwoFFourH, -CHTwoCTwoFFourCl, -C
HTwoCTwoFFourBr, -CH TwoCThreeF6H, -CHTwoCThreeF6C
1, -CHTwoCThreeF6Br, -CHTwoCFourF8H, -CH TwoCFour
F8Cl, -CHTwoCFourF8Br, -CHTwoCFiveFTenH, -C
HTwoCFiveFTenCl, -CHTwoCFiveFTenBr, -CHTwoC6F12
H, -CHTwoC6F12Cl, -CHTwoC6F12Br, -CH
TwoC7F14H, -CHTwoC7F14Cl, -CHTwoC7F14B
r, -CHTwoC8F16H, -CHTwoC8F16Cl, -CHTwo
C8F16Br and the like.
【００１４】本発明において、光触媒用担体である含フ
ッ素ランダム共重合体は、前記一般式（Ｉ）及び前記一
般式（II）で示される各繰り返し単位がランダムに配列
したものである。In the present invention, the fluorine-containing random copolymer which is a carrier for a photocatalyst has a structure in which the repeating units represented by the general formulas (I) and (II) are randomly arranged.
【００１５】従来、光触媒の担体として提案されている
フッ素樹脂の中には、透明性が高いものも存在する。例
えば、ＰＦＡ樹脂（テトラフルオロエチレン−パーフル
オロプロピルビニルエーテルコポリマー）は高い透明性
を示す。しかし、上記フッ素樹脂は、後記の比較例に示
されるように、光の照射面に対して反対面に存在する光
触媒に、照射した光が十分作用せず、該光触媒の機能が
発揮されない。Conventionally, some fluororesins that have been proposed as photocatalyst carriers have high transparency. For example, PFA resin (tetrafluoroethylene-perfluoropropyl vinyl ether copolymer) shows high transparency. However, as shown in a comparative example described later, the above-mentioned fluororesin does not sufficiently act on the photocatalyst existing on the surface opposite to the light irradiation surface, and the function of the photocatalyst is not exhibited.
【００１６】これに対して、本発明における特定の含フ
ッ素ランダム共重合体よりなる光触媒用担体は、光の照
射面の反対面に存在する光触媒が透過した光によって十
分機能するという驚くべき性質を有する。On the other hand, the carrier for a photocatalyst comprising the specific fluorine-containing random copolymer in the present invention has a surprising property that the photocatalyst present on the surface opposite to the surface irradiated with light functions sufficiently by the light transmitted therethrough. Have.
【００１７】本発明において、含フッ素ランダム共重合
体は、前記一般式（Ｉ）と前記一般式（II）で示される
各繰り返し単位の組成は、上記した本発明の効果を十分
発揮するためには、前記一般式（Ｉ）で示される繰り返
し単位が６０〜９２モル％であり、前記一般式（II）で
示される繰り返し単位が８〜４０モル％であることが重
要であり、前記一般式（Ｉ）で示される繰り返し単位が
８０〜９０モル％であり、前記一般式（II）で示される
繰り返し単位が１０〜２０モル％であることが特に好ま
しい。In the present invention, the composition of each repeating unit represented by the above general formula (I) and the above general formula (II) is required for the fluorine-containing random copolymer to sufficiently exhibit the above-mentioned effects of the present invention. It is important that the repeating unit represented by the general formula (I) is 60 to 92 mol% and the repeating unit represented by the general formula (II) is 8 to 40 mol%. It is particularly preferred that the repeating unit represented by (I) is from 80 to 90 mol% and the repeating unit represented by the general formula (II) is from 10 to 20 mol%.
【００１８】また、上記含フッ素ランダム共重合体の分
子量は、光触媒用担体として用いることができる程度の
強度を示す分子量を有していれば特に制限されない。The molecular weight of the above-mentioned fluorine-containing random copolymer is not particularly limited as long as it has a molecular weight which shows such strength that it can be used as a photocatalyst carrier.
【００１９】一般に、含フッ素ランダム共重合体の分子
量は、各種溶媒に不溶であるため通常の手段では分子量
を求めることができない。しかしながら、樹脂の溶融流
動性を示す尺度であるメルトフローレート（以下、ＭＦ
Ｒと略称する）は分子量を反映することが知られてお
り、ＭＦＲによって分子量を推定することが可能であ
る。Generally, the molecular weight of a fluorine-containing random copolymer cannot be determined by ordinary means because it is insoluble in various solvents. However, the melt flow rate (hereinafter referred to as MF) which is a measure of the melt flowability of the resin
R) is known to reflect the molecular weight, and the molecular weight can be estimated by MFR.
【００２０】本発明における含フッ素ランダム共重合体
の分子量は、ＭＦＲで０．５〜５００ｇ／１０分である
ことが好ましく、１〜１００ｇ／１０分であることが更
に好ましい。The molecular weight of the fluorine-containing random copolymer in the present invention is preferably 0.5 to 500 g / 10 min, more preferably 1 to 100 g / 10 min in MFR.
【００２１】尚、ＭＦＲの測定方法は、日本工業規格
（ＪＩＳ）Ｋ−７２１０に規定されており、本発明の含
フッ素ランダム共重合体のＭＦＲは２６０℃、５ｋｇの
荷重で測定した値である。The method for measuring the MFR is specified in Japanese Industrial Standards (JIS) K-7210, and the MFR of the fluorine-containing random copolymer of the present invention is a value measured at 260 ° C. under a load of 5 kg. .
【００２２】本発明の光触媒用担体として用いられる含
フッ素ランダム共重合体は、どのような方法で製造され
ても良いが、次に述べる方法により好適に製造される。The fluorine-containing random copolymer used as the photocatalyst carrier of the present invention may be produced by any method, but is preferably produced by the following method.
【００２３】即ち、テトラフルオロエチレンと下記一般
式（IV） ＣＦ2＝ＣＦＯＲf （IV） （但し、Ｒfはハロゲン化炭化水素である）で表わされ
る含フッ素ビニルエーテルとの共重合体によって作るこ
とができる。That is, it is prepared by a copolymer of tetrafluoroethylene and a fluorine-containing vinyl ether represented by the following general formula (IV) CF 2 ＣＦCFOR f (IV) (where R f is a halogenated hydrocarbon). Can be.
【００２４】ここで、Ｒfは前記一般式（III）で説明し
たものと同じである。Here, R f is the same as that described in the general formula (III).
【００２５】また、該共重合体が水素原子を含む場合
は、フッ素ガス等のフッ素化剤を用いてフッ素化して作
られる共重合体も本発明の光触媒用担体として好適に用
いることができる。When the copolymer contains a hydrogen atom, a copolymer prepared by fluorination using a fluorinating agent such as fluorine gas can be suitably used as the photocatalyst carrier of the present invention.
【００２６】さらに、本発明の光触媒用担体となる含フ
ッ素ランダム共重合体は、柔軟性、帯電防止性等の性質
を改良するために、他の繰り返し単位、例えば−ＣＦ3
（ＣＦ3）ＣＦ2−、−ＣＦ2ＣＨ2−、−ＣＦ2ＣＦＣｌ
−等、或いは側鎖にイオン交換基を有する繰り返し単位
を含んでもよい。但し、これら成分の含有率は繰り返し
単位の１０モル％以下である事が好ましい。Further, in order to improve properties such as flexibility and antistatic properties, the fluorine-containing random copolymer serving as the photocatalyst carrier of the present invention may contain other repeating units such as -CF 3.
(CF 3) CF 2 -, - CF 2 CH 2 -, - CF 2 CFCl
Or a repeating unit having an ion exchange group in the side chain. However, the content of these components is preferably 10 mol% or less of the repeating unit.
【００２７】本発明において、光触媒は、公知のものが
特に制限なく使用される。例えば、０．５〜５eＶ、好
ましくは１〜４eＶの禁止帯幅を有し、光触媒反応をも
たらす光反応性半導体である。具体的には、酸化亜鉛、
酸化タングステン、酸化チタン、及び酸化セリウム等の
金属酸化物粒子が挙げられる。そのうち、特に酸化チタ
ンはその構造安定性、光反応性有害物除去能、更には、
取り扱い上の安全性等から生活空間において使用するに
は最も適しており、本発明に使用する光触媒として好ま
しい。In the present invention, known photocatalysts are used without any particular limitation. For example, it is a photoreactive semiconductor having a bandgap of 0.5 to 5 eV, preferably 1 to 4 eV and causing a photocatalytic reaction. Specifically, zinc oxide,
Examples include metal oxide particles such as tungsten oxide, titanium oxide, and cerium oxide. Among them, especially titanium oxide has its structural stability, ability to remove photoreactive harmful substances,
It is most suitable for use in a living space due to safety in handling and the like, and is preferable as a photocatalyst used in the present invention.
【００２８】また、上記酸化チタン微粒子としてはアナ
ターゼ型、ルチル型、含水型等の各種酸化チタン微粒子
があるが、最も優れた光触媒作用を示すアナターゼ型の
酸化チタン微粒子を使用するのが好ましい。As the titanium oxide fine particles, there are various types of titanium oxide fine particles such as anatase type, rutile type and water-containing type, and it is preferable to use anatase type titanium oxide fine particles exhibiting the most excellent photocatalytic action.
【００２９】本発明において、光触媒の形状、大きさに
は特に制限はなく、公知の大きさのものを用いることが
できる。一般的に、平均粒子径が１ｎｍ〜５μｍの光触
媒は活性が高いため好適であり、１ｎｍ〜１μｍのもの
がより好ましい。In the present invention, the shape and size of the photocatalyst are not particularly limited, and those having a known size can be used. Generally, a photocatalyst having an average particle diameter of 1 nm to 5 μm is suitable because of high activity, and a photocatalyst having an average particle diameter of 1 nm to 1 μm is more preferable.
【００３０】また、光触媒を上記微粒子とすることによ
り、後記する光触媒の担持方法として含フッ素ランダム
共重合体に混練して使用する態様を採る場合、担体の光
の透過率を低減することなく、該光触媒を存在せしめる
ことができるというメリットをも有する。Further, when the photocatalyst is formed into the above-mentioned fine particles, and a method for supporting the photocatalyst described below is employed in which the photocatalyst is kneaded with a fluorine-containing random copolymer and used, the light transmittance of the carrier is not reduced. There is also an advantage that the photocatalyst can be present.
【００３１】本発明の光触媒用担体の形状は特に制限は
なく、用途に応じて必要な形状に成形して用いればよ
い。本発明の光触媒用担体として特に好適に用いられる
形状を例示するならばフィルム、シート、チューブ、パ
イプ、カバー、ケース等の薄物成形体が挙げられる。か
かる成形体は、担体を光が透過することが可能であり、
本発明の効果を極めて顕著に発揮することができる。The shape of the photocatalyst carrier of the present invention is not particularly limited, and may be used after being formed into a necessary shape according to the application. Examples of shapes particularly preferably used as the photocatalyst carrier of the present invention include thin molded articles such as films, sheets, tubes, pipes, covers, and cases. Such a molded body is capable of transmitting light through the carrier,
The effects of the present invention can be extremely remarkably exhibited.
【００３２】上記光触媒用担体に光触媒を担持させ、光
触媒担持体とする態様は特に制限されない。代表的な態
様としては、例えば、光触媒の粒子を光触媒用担体上に
圧着する方法、光触媒の粒子を光触媒用担体上に熱融着
する方法、光触媒の粒子を光触媒用担体上に熔射する方
法、結着剤を介して光触媒の粒子を光触媒用担体上に接
着する方法、光触媒を含む水性塗液を光触媒用担体表面
に塗付、乾燥させる方法、光触媒の粒子を光触媒用担体
を構成する含フッ素ランダム共重合体と溶融混練する方
法、光触媒前駆体と上記含フッ素ランダム共重合体を溶
融混練し、該光触媒前駆体を後処理によって光触媒に変
換する方法、光触媒先駆体を担体中に拡散吸着させた
後、後処理によって光触媒に変換する方法、本発明の含
フッ素共重合体がイオン交換基を有する場合にはイオン
交換によって金属イオンを該含フッ素共重合体に導入し
た後に酸化により光触媒能を有する金属酸化物とする方
法、等が挙げられる。The photocatalyst supported on the photocatalyst carrier to form a photocatalyst carrier is not particularly limited. Typical embodiments include, for example, a method of pressing photocatalyst particles on a photocatalyst carrier, a method of heat-fusing photocatalyst particles on a photocatalyst carrier, and a method of spraying photocatalyst particles on a photocatalyst carrier. A method of adhering photocatalyst particles onto a photocatalyst carrier via a binder, a method of applying an aqueous coating solution containing the photocatalyst to the surface of the photocatalyst carrier, and drying the photocatalyst particles. A method of melt-kneading with a fluorine random copolymer, a method of melt-kneading a photocatalyst precursor and the above-mentioned fluorine-containing random copolymer, converting the photocatalyst precursor into a photocatalyst by post-treatment, and diffusing and adsorbing a photocatalyst precursor into a carrier. After the reaction, a method of converting to a photocatalyst by a post-treatment, and when the fluorinated copolymer of the present invention has an ion exchange group, the metal ion is introduced into the fluorinated copolymer by ion exchange, followed by acidification. How a metal oxide having a photocatalytic activity, and the like are exemplified by.
【００３３】これらの態様のうち、混練によって光触媒
用担体中に光触媒の粒子を存在させ、その表面に光触媒
が露出するように構成した態様が最も好ましい。かかる
態様において、前記薄物成形体とする場合には、これを
延伸することにより光触媒の添加効果をより一層高める
ことができる。Of these embodiments, the most preferred embodiment is one in which the photocatalyst particles are present in the photocatalyst carrier by kneading and the photocatalyst is exposed on the surface thereof. In such an embodiment, when the thin molded article is formed, the effect of adding the photocatalyst can be further enhanced by stretching the thin molded article.
【００３４】また、薄物成形体にあっては、使用時にお
ける光照射面に対して少なくとも反対面に光触媒が存在
するように担持させる態様が、本発明の効果を有効に利
用することができるため好ましい。Further, in the thin molded article, the effect of the present invention can be effectively used in a mode in which the photocatalyst is supported at least on the surface opposite to the light irradiation surface in use. preferable.
【００３５】本発明の光触媒用担体に担持させる光触媒
の量は特に制限はないが、通常、機能面における光触媒
の濃度が０．５〜５０重量％、好ましくは１〜３０重量
％となるように担持させれば良い。The amount of the photocatalyst supported on the photocatalyst carrier of the present invention is not particularly limited, but is usually adjusted so that the concentration of the photocatalyst on the functional surface is 0.5 to 50% by weight, preferably 1 to 30% by weight. What is necessary is just to carry.
【００３６】本発明において、光触媒用担体として使用
する含フッ素ランダム共重合体には、種々の添加剤を使
用することができる。上記の添加剤としては、シランカ
ップリング剤、好ましくはヘキサメチルジシラザンある
いはシリコーンオイル、好ましくはフッ素変性シリコー
ンオイルなどが挙げられる。In the present invention, various additives can be used for the fluorine-containing random copolymer used as the carrier for the photocatalyst. Examples of the additive include a silane coupling agent, preferably hexamethyldisilazane or a silicone oil, preferably a fluorine-modified silicone oil.
【００３７】[0037]
【発明の効果】以上の説明より理解されるように、本発
明にかかる、含フッ素ランダム共重合体よりなる光触媒
用担体を用いることにより、通常の使用において光触媒
能を充分に発揮するのみならず、該担体自身を透過する
光を利用した使用態様においても、殺菌、脱臭および有
機物分解作用に優れた効果を発揮することができる。As will be understood from the above description, the use of the photocatalyst carrier comprising a fluorine-containing random copolymer according to the present invention not only exerts sufficient photocatalytic activity in ordinary use but also Even in a mode of use utilizing light transmitted through the carrier itself, excellent effects of sterilization, deodorization, and decomposition of organic substances can be exhibited.
【００３８】また、本発明の光触媒用担体を使用して得
られる光触媒担持体の特性を利用した有効な用途として
は、電灯等のカバー材、ケース材、窓用コーティングフ
ィルム、テント材のような膜構造建築物の膜材、温室用
フィルムなど、光触媒用担体が薄物成形体であって、使
用時における光照射面に対して反対面の表面に光触媒が
存在する用途が挙げられる。The photocatalyst carrier obtained by using the photocatalyst carrier of the present invention can be effectively used as a cover material for electric lamps, case materials, coating films for windows, tent materials, and the like. Examples include applications in which the photocatalyst carrier is a thin molded article, such as a membrane material for a membrane structure building or a greenhouse film, and the photocatalyst is present on the surface opposite to the light irradiation surface during use.
【００３９】勿論、道路脇のビル壁面、高速道路の遮音
板、家具、壁に貼り付ける内装材、等、光の照射面にお
いて光触媒を機能させる用途においても有効に使用する
ことができる。Of course, the present invention can also be effectively used in applications in which a photocatalyst functions on a light irradiation surface, such as a wall surface of a building beside a road, a sound insulating plate on a highway, furniture, an interior material attached to a wall, and the like.
【００４０】[0040]
【実施例】以下に本発明の実施例をあげて本発明をさら
に詳しく説明するが、本発明はこれら実施例のみに限定
されるものではない。EXAMPLES The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.
【００４１】実施例１ −ＣＦ2ＣＦ2−で表わされる繰り返し単位８５モル％と
−ＣＦ（ＯＣＨ2ＣＦ2ＣＦ3）ＣＦ2−で表わされる繰り
返し単位１５モル％ととなるように共重合して得られた
含フッ素ランダム共重合体粉末９０重量％、及び平均粒
子径２０ｎｍのＴｉＯ2粉末（石原産業（株）製、ＳＴ
−２１：商品名）１０重量％をラボプラストミル
（（株）東洋精機製）で溶融混練し、含フッ素ランダム
共重合体中に酸化チタン微粒子を均一に分散し、担持さ
せた。Example 1 A copolymer was copolymerized so that 85 mol% of the repeating unit represented by -CF 2 CF 2- and 15 mol% of the repeating unit represented by -CF (OCH 2 CF 2 CF 3 ) CF 2-. 90% by weight of the obtained fluorine-containing random copolymer powder and a TiO 2 powder having an average particle diameter of 20 nm (manufactured by Ishihara Sangyo Co., Ltd., ST
21: 10% by weight) was melt-kneaded with Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), and titanium oxide fine particles were uniformly dispersed and supported in a fluorine-containing random copolymer.
【００４２】得られたＴｉＯ2を担持した含フッ素ラン
ダム共重合体を金型に充填し、加熱溶融し、フィルム
（６０×６０×０．２５ｍｍ）を圧縮成形した。The obtained fluorinated random copolymer supporting TiO 2 was filled in a mold, heated and melted, and a film (60 × 60 × 0.25 mm) was compression-molded.
【００４３】作成したＴｉＯ2担持フィルムを容積１Ｌ
のパイレックス製ガラス容器の内面全体に貼り付けた。
この容器中に空気とアセトアルデヒドの混合ガスを、ア
セトアルデヒド濃度が２５ｐｐｍになるように導入し
た。The prepared TiO 2 supporting film is stored in a volume of 1 L.
Was attached to the entire inner surface of a Pyrex glass container.
A mixed gas of air and acetaldehyde was introduced into this container so that the acetaldehyde concentration became 25 ppm.
【００４４】次いで、反応容器の外側からブラックライ
ト（４Ｗ）の光を照射し、容器内部のアセトアルデヒド
ガス濃度をガスクロマトグラフにより測定し、その減少
速度より光触媒活性を評価し、表１に示した。Next, the reactor was irradiated with black light (4 W) from the outside of the reaction vessel, the acetaldehyde gas concentration inside the vessel was measured by gas chromatography, and the photocatalytic activity was evaluated based on the decrease rate, and the results are shown in Table 1.
【００４５】アセトアルデヒドガス分解速度は一定で約
０．１ｐｐｍ／分であり、光触媒担持樹脂を介した透過
光を利用したＴｉＯ2による汚染物質分解能が確認され
た。The acetaldehyde gas decomposition rate was constant at about 0.1 ppm / min, and the resolution of contaminants by TiO 2 using light transmitted through the photocatalyst-supporting resin was confirmed.
【００４６】また、上記を担持したフィルムよりなる光
触媒担持体は、２ヶ月という長期の光照射によっても劣
化せず、安定して使用することができた。Further, the photocatalyst carrier comprising a film supporting the above was not degraded by long-term light irradiation of two months, and could be used stably.
【００４７】実施例２ 実施例１で用いた含フッ素ランダム共重合体をフッ素ガ
スによってフッ素化し、−ＣＦ2ＣＦ2−で表わされる繰
り返し単位と−ＣＦ（ＯＣＦ2ＣＦ2ＣＦ3）ＣＦ2−で表
わされる繰り返しから成る含フッ素ランダム共重合体を
得た。Example 2 The fluorine-containing random copolymer used in Example 1 was fluorinated with fluorine gas, and a repeating unit represented by -CF 2 CF 2- and -CF (OCF 2 CF 2 CF 3 ) CF 2- A fluorinated random copolymer consisting of repeating units represented by the following formula was obtained.
【００４８】その後、実施例１と同様にしてＴｉＯ2を
担持したフィルムを作成した。ついで該フィルムを二軸
延伸機で２．５倍に延伸し、同様の評価方法により光触
媒能を評価し、表１に示した。Thereafter, a film supporting TiO 2 was prepared in the same manner as in Example 1. Then, the film was stretched 2.5 times with a biaxial stretching machine, and the photocatalytic activity was evaluated by the same evaluation method.
【００４９】また、上記を担持したフィルムよりなる光
触媒担持体は、２ヶ月という長期の光照射によっても劣
化せず、安定して使用することができた。Further, the photocatalyst carrier made of a film supporting the above was not degraded by long-term light irradiation of two months, and could be used stably.
【００５０】比較例１ −ＣＦ2ＣＦ2−で表わされる繰り返し単位９８．５モル
％、−ＣＦ3（ＯＣ3Ｆ 7）ＣＦ2−で表わされる繰り返し
単位１．５モル％の含フッ素ランダム共重合体を用いた
他は実施例１と同様にしてＴｉＯ2担持フィルムを作
り、アセトアルデヒドの分解能を測定し、表１に示し
た。Comparative Example 1 -CFTwoCFTwo98.5 mol of repeating units represented by-
%, -CFThree(OCThreeF 7) CFTwoRepetition represented by-
1.5 mol% of a fluorine-containing random copolymer was used.
Other than the above, the TiOTwoMake carrier film
And the resolution of acetaldehyde was measured.
Was.
【００５１】この場合、アセトアルデヒドはほとんど分
解されていなかった。In this case, acetaldehyde was hardly decomposed.
【００５２】[0052]
【表１】 実施例３ −ＣＦ（ＯＲf）ＣＦ2−で表わされる繰り返し単位中Ｒ
fで示される基の種類と該繰り返し単位の含有量を種々
変えた含フッ素ランダム共重合体を用いた他は実施例１
と同様にしてＴｉＯ2を担持したフィルムを作成し、光
触媒能を評価した。Ｒfの種類、含フッ素ランダム共重
合体中の−ＣＦ（ＯＲf）ＣＦ2−で表わされる繰り返し
単位の含有率、及び１２０分後のアセトアルデヒドの濃
度を表２に示した。[Table 1] Example 3 R in the repeating unit represented by —CF (OR f ) CF 2 —
Example 1 except that a fluorine-containing random copolymer in which the type of the group represented by f and the content of the repeating unit were variously changed was used.
A film carrying TiO 2 was prepared in the same manner as described above, and the photocatalytic ability was evaluated. Table 2 shows the type of R f , the content of the repeating unit represented by —CF (OR f ) CF 2 — in the fluorine-containing random copolymer, and the concentration of acetaldehyde after 120 minutes.
【００５３】[0053]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 214/20 Ｂ０１Ｄ 53/36 Ｊ //(Ｃ０８Ｆ 214/20 Ｃ 216:14） Ｆターム(参考） 4D048 AA22 AA24 AB01 AB03 AB05 BA07X BA13X BA41X BA43X BA45X BB03 CA01 CA06 EA01 4G069 AA01 AA04 AA08 AA09 AA11 BA04B BA04C BA48A BA48C BB04B BB04C BE34A BE34B BE34C CA01 CA03 CA10 CA17 DA06 EA08 EB18X EB18Y FA02 FA06 FB66 FB70 4J100 AC26P AE39Q CA04 DA62 JA15 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08F 214/20 B01D 53/36 J // (C08F 214/20 C 216: 14) F-term (Reference) 4D048 AA22 AA24 AB01 AB03 AB05 BA07X BA13X BA41X BA43X BA45X BB03 CA01 CA06 EA01 4G069 AA01 AA04 AA08 AA09 AA11 BA04B BA04C BA48A BA48C BB04B BB04C BE34A BE34B BE34C CA01 CA03 CA10 CA17 FA18 EB18 EB18 EB04 EB08
Claims (4)
繰り返し単位を有し、且つ上記一般式（Ｉ）で示される
繰り返し単位が６０〜９２モル％であり、上記一般式
（II）で示される繰り返し単位が８〜４０モル％である
含フッ素ランダム共重合体からなることを特徴とする光
触媒用担体。1. A following general formula (I) -CF 2 CF 2 - repeating units and the following general formula represented by (I) (II) -CF ( OR f) CF 2 - (II) ( where, R f Is a halogenated hydrocarbon), and the repeating unit represented by the above general formula (I) is 60 to 92 mol%, and the repeating unit represented by the above general formula (II) Is a fluorine-containing random copolymer having a content of from 8 to 40 mol%.
担持してなる光触媒担持体。2. A photocatalyst carrier comprising the photocatalyst carrier according to claim 1 carrying a photocatalyst.
用時における光照射面に対して反対面の表面に光触媒が
存在する請求項２記載の光触媒担持体。3. The photocatalyst carrier according to claim 2, wherein the photocatalyst carrier is a thin molded article, and the photocatalyst is present on a surface opposite to a light irradiation surface during use.
子が実質的に存在しない請求項３記載の光触媒担持体。4. The photocatalyst carrier according to claim 3, wherein substantially no particles having a particle diameter of 1 μm or more are present in the photocatalyst carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11164089A JP2000350936A (en) | 1999-06-10 | 1999-06-10 | Carrier for photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11164089A JP2000350936A (en) | 1999-06-10 | 1999-06-10 | Carrier for photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000350936A true JP2000350936A (en) | 2000-12-19 |
Family
ID=15786573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11164089A Withdrawn JP2000350936A (en) | 1999-06-10 | 1999-06-10 | Carrier for photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000350936A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005288323A (en) * | 2004-03-31 | 2005-10-20 | Keio Gijuku | Photocatalyst material and its manufacturing method |
| JP2016050291A (en) * | 2014-09-02 | 2016-04-11 | 株式会社トクヤマ | Composition for photocatalyst coating |
-
1999
- 1999-06-10 JP JP11164089A patent/JP2000350936A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005288323A (en) * | 2004-03-31 | 2005-10-20 | Keio Gijuku | Photocatalyst material and its manufacturing method |
| JP2016050291A (en) * | 2014-09-02 | 2016-04-11 | 株式会社トクヤマ | Composition for photocatalyst coating |
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| Date | Code | Title | Description |
|---|---|---|---|
| A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20040303 |