JPH07241475A - Photocatalyst body, its production and method for removing harmful substance using the same - Google Patents
Photocatalyst body, its production and method for removing harmful substance using the sameInfo
- Publication number
- JPH07241475A JPH07241475A JP6058227A JP5822794A JPH07241475A JP H07241475 A JPH07241475 A JP H07241475A JP 6058227 A JP6058227 A JP 6058227A JP 5822794 A JP5822794 A JP 5822794A JP H07241475 A JPH07241475 A JP H07241475A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- particles
- polymer
- polymer particles
- bodies
- 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.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 104
- 239000000126 substance Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002245 particle Substances 0.000 claims abstract description 97
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010303 mechanochemical reaction Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 231100000167 toxic agent Toxicity 0.000 claims 2
- 239000003440 toxic substance Substances 0.000 claims 2
- 239000012530 fluid Substances 0.000 abstract description 6
- 230000005484 gravity Effects 0.000 abstract description 5
- 150000002896 organic halogen compounds Chemical class 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- -1 polyethylene Polymers 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 241000186361 Actinobacteria <class> Species 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229950011008 tetrachloroethylene Drugs 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 208000035985 Body Odor Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 206010040904 Skin odour abnormal Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005645 nematicide Substances 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
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 102220115768 rs886039839 Human genes 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection 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
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Physical Water Treatments (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Fire-Extinguishing Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は優れた光触媒機能を有す
る光触媒体およびその製造方法に関する。さらに、その
光触媒体を用いて有害物質を除去する方法に関する。TECHNICAL FIELD The present invention relates to a photocatalyst having an excellent photocatalytic function and a method for producing the same. Furthermore, it relates to a method for removing harmful substances using the photocatalyst.
【０００２】[0002]
【従来の技術】光触媒粒子にそのバンドギャップ以上の
エネルギーを持つ波長の光を照射すると光励起により伝
導帯に電子を、価電子帯に正孔を生じる。この光励起に
より生じた電子の持つ強い還元力や正孔の持つ強い酸化
力は、有害物質の分解・浄化、アンモニア、アルデヒド
類、アミン類などの悪臭ガスの脱臭のほか、水の分解、
殺菌、放線菌、菌類、藻類などの殺菌・殺藻などの光触
媒反応に利用されている。たとえば、特公平２−９８５
０号公報には、酸化チタンなどの光触媒粒子を用いて廃
棄物中の有害物質を除去し、浄化することが記載されて
いる。また、特公平４−７８３２６号公報には、酸化チ
タンなどの光触媒粒子を用いてトイレのし尿臭、ペット
の臭い、たばこの臭い、調理臭、体臭などを脱臭するこ
とが記載されている。さらに、特公平４−２９３９３号
公報には、光照射により酸化チタンなどの光触媒粒子に
生起した所定電圧を細胞に接触印可して細胞を殺すこと
が記載されている。2. Description of the Related Art When photocatalyst particles are irradiated with light having a wavelength greater than the band gap, photoexcitation produces electrons in the conduction band and holes in the valence band. The strong reducing power of electrons and the strong oxidizing power of holes generated by this photoexcitation are due to decomposition and purification of harmful substances, deodorization of malodorous gases such as ammonia, aldehydes and amines, and decomposition of water.
It is used for photocatalytic reactions such as sterilization, actinomycetes, fungi, and algae. For example, Japanese Patent Publication 2-985
Japanese Unexamined Patent Application Publication No. 0-202 describes that photocatalyst particles such as titanium oxide are used to remove and purify harmful substances in waste. Further, Japanese Patent Publication No. 4-78326 describes that photocatalyst particles such as titanium oxide are used to deodorize toilet urine odor, pet odor, cigarette odor, cooking odor, body odor, and the like. Further, Japanese Patent Publication No. 4-29393 describes that a predetermined voltage generated on photocatalyst particles such as titanium oxide by light irradiation is applied to cells to kill them.
【０００３】[0003]
【発明が解決しようとする課題】光触媒粒子を光触媒反
応に用いる場合、光触媒反応時の反応装置からの光触媒
粒子の飛散や流出を防止したり、光触媒反応終了後の反
応装置から光触媒粒子を分離・回収しやすくする必要が
ある。このため、光触媒粒子を、高表面積の担体粒子や
ハニカム構造あるいは三次元網目構造を有する構造体な
どのセラミックス製または金属製の支持体に担持あるい
は被覆した状態で用いるのが一般的である。光触媒粒子
を支持体に担持したこのような光触媒体では、飛散や流
出を少なくすることができ、また、分離・回収を容易に
することができる。しかしながら、前記の光触媒体で
は、光触媒粒子に光が照射されにくいため、光触媒粒子
の光触媒機能が発現しにくく、充分満足できる光触媒機
能が得られない。しかも、光触媒反応時に、光触媒粒子
が支持体から剥離するなどの問題もある。When photocatalyst particles are used in a photocatalytic reaction, the photocatalyst particles are prevented from scattering and flowing out from the reaction device during the photocatalytic reaction, and the photocatalyst particles are separated from the reaction device after the photocatalytic reaction is completed. Need to be easily collected. Therefore, the photocatalyst particles are generally used in a state of being carried or coated on a ceramic or metal support such as carrier particles having a high surface area or a structure having a honeycomb structure or a three-dimensional network structure. With such a photocatalyst body in which photocatalyst particles are carried on a support, scattering and outflow can be reduced, and separation / recovery can be facilitated. However, in the above-mentioned photocatalyst, the photocatalyst particles are difficult to be irradiated with light, so that the photocatalyst function of the photocatalyst particles is hard to be expressed, and a satisfactory photocatalyst function cannot be obtained. Moreover, there is a problem that the photocatalyst particles are separated from the support during the photocatalytic reaction.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記の問
題を解決すべく研究した結果、（１）ポリマー粒子の表
面および／またはその表面近傍に光触媒粒子を含有して
なる光触媒体は、光触媒反応時の反応装置からの光触媒
粒子の飛散や流出を少なくすることができ、また、光触
媒反応終了後の反応装置からの光触媒粒子の分離・回収
を容易にすることができるとともに、光の利用効率を高
めることができるため優れた触媒機能を有すること、し
かも、ポリマー粒子に強固に接着できるため、ポリマー
粒子からの光触媒粒子の剥離が少ないこと、（２）本発
明の光触媒体を得るには、光触媒粒子の存在下モノマー
を重合する方法またはポリマー粒子と光触媒粒子とをメ
カノケミカル反応させる方法が簡便であり、かつ、効率
がよいこと、（３）本発明の光触媒体は、種々の光触媒
反応に用いることができるが、特に、有害物質の除去反
応に好適であることなどを見出し、本発明を完成した。
すなわち、本発明は優れた光触媒機能を有する光触媒体
を提供することにある。さらに、本発明の光触媒体を用
いて、有害物質を迅速、かつ、効率よく除去する方法を
提供することにある。The inventors of the present invention have conducted research to solve the above-mentioned problems, and as a result, (1) a photocatalyst body containing photocatalyst particles on the surface of polymer particles and / or in the vicinity thereof In addition, it is possible to reduce the scattering and outflow of photocatalyst particles from the reaction device during the photocatalytic reaction, and also to facilitate the separation and recovery of the photocatalyst particles from the reaction device after the photocatalytic reaction is completed, and Since the utilization efficiency can be increased, the catalyst has an excellent catalytic function, and since the polymer particles can be firmly adhered, the photocatalyst particles are less likely to be peeled from the polymer particles. (2) To obtain the photocatalyst body of the present invention The method of polymerizing a monomer in the presence of photocatalyst particles or the method of causing a mechanochemical reaction between polymer particles and photocatalyst particles is simple and efficient, (3) Photocatalyst of the present invention can be used for various photocatalytic reactions, in particular, it found such to be suitable for removal reaction of harmful substances, the present invention has been completed.
That is, the present invention provides a photocatalyst having an excellent photocatalytic function. Another object of the present invention is to provide a method for rapidly and efficiently removing harmful substances by using the photocatalyst of the present invention.
【０００５】本発明は、ポリマー粒子の表面および／ま
たはその表面近傍に光触媒粒子を含有してなる光触媒体
である。本発明の光触媒体は、光触媒粒子とポリマー粒
子との単なる混合物とは異なり、ポリマー粒子の表面に
光触媒粒子が担持あるいは被覆されている状態および／
またはポリマー粒子の表面近傍に光触媒粒子が取り込ま
れ、光触媒粒子の一部が露出している状態を保持した粒
子である。本発明の光触媒体の平均粒径は適宜設定でき
るが、０．１μｍ〜３０ｍｍ、好ましくは０．５μｍ〜
５ｍｍ、より好ましくは１μｍ〜１ｍｍ、もっとも好ま
しくは３μｍ〜０．５ｍｍである。また、本発明の光触
媒体は球状、円柱状、立方体状、直方体状、中空状など
の一定の形状のものが好ましく、特に、球状のものが好
ましい。本発明の光触媒体の比重は、好ましくは３．０
以下、より好ましくは２．５以下、もっとも好ましくは
２．０以下である。The present invention is a photocatalyst body comprising photocatalyst particles on the surface of polymer particles and / or in the vicinity thereof. The photocatalyst body of the present invention is different from a mere mixture of photocatalyst particles and polymer particles in that the photocatalyst particles are supported or coated on the surface of the polymer particles and / or
Alternatively, the photocatalyst particles are incorporated in the vicinity of the surface of the polymer particles, and the photocatalyst particles are partially exposed. The average particle diameter of the photocatalyst of the present invention can be appropriately set, but is 0.1 μm to 30 mm, preferably 0.5 μm to
It is 5 mm, more preferably 1 μm to 1 mm, and most preferably 3 μm to 0.5 mm. Further, the photocatalyst of the present invention preferably has a certain shape such as a spherical shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, or a hollow shape, and a spherical shape is particularly preferable. The specific gravity of the photocatalyst of the present invention is preferably 3.0.
Or less, more preferably 2.5 or less, and most preferably 2.0 or less.
【０００６】本発明において、ポリマー粒子とは重合体
で作られた粒子のことである。ポリマー粒子の材質は、
フェノール系ポリマー、メラミン系ポリマー、ユリア系
ポリマー、ウレタン系ポリマー、ポリエステル系ポリマ
ー、スチレン系ポリマー、アクリル系ポリマー、ビニル
系ポリマー、シリコン系ポリマー、ポリエチレン系ポリ
マー、ポリアミド系ポリマー、フッ素系ポリマーやそれ
らのコポリマーなどの少なくとも一種を用いることがで
きる。特に、耐熱性、耐科学薬品性に優れたフッ素系ポ
リマー、シリコン系ポリマーまたはそれらのコポリマー
が好ましい。フッ素系ポリマーとしては、たとえば、ポ
リフッ化ビニル、ポリフッ化ビニリデン、ポリ塩化三フ
ッ化エチレン、ポリ四フッ化エチレン、ポリ四フッ化エ
チレン−六フッ化プロピレンコポリマー、エチレン−ポ
リ四フッ化エチレンコポリマー、エチレン−塩化三フッ
化エチレンコポリマー、四フッ化エチレン−パーフルオ
ロアルキルビニルエーテルコポリマーなどの結晶性ポリ
マー、パーフルオロシクロポリマー、ビニルエーテル−
フルオロオレフィンコポリマー、ビニルエステル−フル
オロオレフィンコポリマーなどの非晶質ポリマー、各種
のフッ素系ゴムなどを用いることができる。また、シリ
コン系ポリマーとしては、たとえば、直鎖シリコン系ポ
リマー、アクリル変性シリコン系ポリマー、各種のシリ
コン系ゴムなどを用いることができる。In the present invention, polymer particles are particles made of a polymer. The material of the polymer particles is
Phenol type polymer, melamine type polymer, urea type polymer, urethane type polymer, polyester type polymer, styrene type polymer, acrylic type polymer, vinyl type polymer, silicone type polymer, polyethylene type polymer, polyamide type polymer, fluorine type polymer and those At least one such as a copolymer can be used. Particularly, a fluorine-based polymer, a silicon-based polymer or a copolymer thereof having excellent heat resistance and chemical resistance is preferable. Examples of the fluorine-based polymer include polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, ethylene-polytetrafluoroethylene copolymer, Crystalline polymers such as ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, perfluorocyclopolymer, vinyl ether-
Amorphous polymers such as fluoroolefin copolymers and vinyl ester-fluoroolefin copolymers, various fluorine-based rubbers, and the like can be used. Further, as the silicon-based polymer, for example, a linear silicon-based polymer, an acrylic modified silicon-based polymer, various silicon-based rubbers, etc. can be used.
【０００７】本発明において、光触媒粒子は、たとえ
ば、酸化チタン、チタン酸ストロンチウム、酸化タング
ステン、酸化亜鉛、酸化スズ、硫化カドミウムなどの公
知の光触媒粒子を少なくとも一種選択して用いることが
できる。特に、優れた光触媒機能を有し、白色であり、
しかも、安全性が高い酸化チタンが好ましい。本発明に
おいて、酸化チタンとはアナタース型酸化チタン、ルチ
ル型酸化チタン、無定形酸化チタン、メタチタン酸、オ
ルソチタン酸などの各種の酸化チタンあるいは水酸化チ
タン、含水酸化チタンを意味する。また、前記の光触媒
粒子の表面に白金、ロジウムなどの金属や鉄の酸化物ま
たは水酸化物などの金属酸化物を担持して用いてもよ
い。ポリマー粒子に含有する光触媒粒子の含有量は、ポ
リマー粒子の重量基準に対して、好ましくは０．１〜８
０重量％、より好ましくは０．５〜７５重量％、さらに
好ましくは１〜７０重量％、もっとも好ましくは３〜６
０重量％である。光触媒粒子の含有量が前記範囲より少
ないと充分な光触媒機能が得られ難いので好ましくな
く、また、光触媒粒子の含有量が前記範囲より多いと、
光触媒粒子がポリマー粒子から剥離しやすくなるため好
ましくない。In the present invention, as the photocatalyst particles, for example, at least one known photocatalyst particle such as titanium oxide, strontium titanate, tungsten oxide, zinc oxide, tin oxide, and cadmium sulfide can be selected and used. In particular, it has an excellent photocatalytic function and is white,
Moreover, titanium oxide, which has high safety, is preferable. In the present invention, titanium oxide means various kinds of titanium oxide such as anatase type titanium oxide, rutile type titanium oxide, amorphous titanium oxide, metatitanic acid, orthotitanic acid, titanium hydroxide, and hydrous titanium oxide. In addition, a metal such as platinum or rhodium or a metal oxide such as an oxide or hydroxide of iron may be supported on the surface of the photocatalyst particles. The content of the photocatalyst particles contained in the polymer particles is preferably 0.1 to 8 based on the weight of the polymer particles.
0% by weight, more preferably 0.5-75% by weight, still more preferably 1-70% by weight, most preferably 3-6.
It is 0% by weight. If the content of the photocatalyst particles is less than the above range, it is difficult to obtain a sufficient photocatalytic function, which is not preferable, and if the content of the photocatalyst particles is more than the above range,
It is not preferable because the photocatalyst particles are easily separated from the polymer particles.
【０００８】本発明の光触媒体は種々の方法で得ること
ができるが、たとえば、光触媒粒子の存在下、モノマ
ーを重合する方法、ポリマーを溶解した溶液に光触媒
粒子を入れ、次いで、該溶液をスプレーし、乾燥する方
法、ポリマー粒子の表面を溶解または湿潤した後、該
ポリマー粒子と光触媒粒子とを混合する方法、メカノ
ケミカル反応により光触媒粒子をポリマー粒子の表面に
衝突させる方法、ポリマー粒子と光触媒粒子とを混練
し、成形または粉砕する方法などを用いることができ
る。本発明では、前記またはの方法が、簡便であ
り、かつ、効率がよいため好ましい。なお、前記〜
の方法で得られた光触媒体の表面をジェット気流攪拌機
などで研磨してもよい。The photocatalyst of the present invention can be obtained by various methods, for example, a method of polymerizing a monomer in the presence of photocatalyst particles, a method in which photocatalyst particles are dissolved in a polymer, and then the solution is sprayed. And drying, a method of dissolving or wetting the surface of the polymer particles and then mixing the polymer particles with the photocatalyst particles, a method of causing the photocatalyst particles to collide with the surface of the polymer particles by a mechanochemical reaction, the polymer particles and the photocatalyst particles The method of kneading and and molding or crushing can be used. In the present invention, the above method or method is preferable because it is simple and efficient. In addition, the above
The surface of the photocatalyst obtained by the above method may be polished by a jet airflow stirrer or the like.
【０００９】本発明の光触媒体を種々の光触媒反応に用
いるには、処理対象物質の存在下、該光触媒体にそのバ
ンドギャップ以上のエネルギーを持つ波長の光を照射す
る。光の利用効率を高めるため、本発明の光触媒体を、
処理対象物質を含む流体に流動させて用いるのが好まし
い。光触媒体を流動させるには、たとえば、光触媒粒子
を入れた反応装置の下部から流体を導入したり、あるい
は、光触媒体を入れた流体を攪拌機で攪拌したりするな
ど種々の方法を用いることができる。本発明の光触媒体
は有害物質の除去反応に好適であり、特に、被処理水に
含有した有害物質の除去反応に好適である。光触媒反応
により分解あるいは酸化して除去する有害物質として
は、人体や生活環境に悪影響を及ぼす物質やその可能性
がある物質であり、たとえば、除草剤、殺菌剤、殺虫
剤、殺線虫剤などの種々の農薬、種々の界面活性剤、蛋
白質やアミノ酸などの種々の生物学的酸素要求物質、炭
化水素、有機ハロゲン化合物、有機リン化合物などの有
機物質、窒素化合物、硫黄化合物、シアン化合物、クロ
ム化合物などの無機化合物、細菌、放線菌、菌類、藻
類、カビ類などの微生物などが挙げられる。炭化水素と
しては、具体的には、アルデヒド類、アミン類、メルカ
プタン類、油類、アルコール類が例示できる。有機ハロ
ゲン化合物としては、具体的には、ポリ塩化ビフェニ
ル、フロン、トリハロメタン、トリクロロエチレン、テ
トラクロロエチレンが例示できる。また、窒素化合物と
しては、具体的には、アンモニア、窒素酸化物が例示で
きる。本発明の光触媒体は、特に、ポリ塩化ビフェニ
ル、トリハロメタン、トリクロロエチレン、テトラクロ
ロエチレンなどの有機ハロゲン化合物を効率よく分解し
除去することができる。バンドギャップ以上のエネルギ
ーを持つ波長の光としては、紫外線を含有した光が好ま
しく、たとえば、太陽光や蛍光灯、ブラックライト、ハ
ロゲンランプ、キセノンフラッシュランプ、水銀灯など
の光を用いることができる。特に３００〜４００ｎｍの
近紫外線を含有した光が好ましい。光の照射量や照射時
間などは処理対象物質の量などによって適宜設定でき
る。In order to use the photocatalyst of the present invention for various photocatalytic reactions, the photocatalyst is irradiated with light having a wavelength having an energy equal to or higher than its band gap in the presence of a substance to be treated. In order to increase the light utilization efficiency, the photocatalyst of the present invention is
It is preferably used by flowing it into a fluid containing the substance to be treated. In order to make the photocatalyst flow, various methods can be used, such as introducing a fluid from the lower part of the reactor containing the photocatalyst particles, or stirring the fluid containing the photocatalyst with a stirrer. . INDUSTRIAL APPLICABILITY The photocatalyst of the present invention is suitable for a reaction to remove harmful substances, and particularly suitable for a reaction to remove harmful substances contained in water to be treated. Hazardous substances that are decomposed or oxidized by photocatalytic reactions and removed are substances that have a potential adverse effect on the human body and living environment, such as herbicides, fungicides, insecticides, nematicides, etc. Various agricultural chemicals, various surfactants, various biological oxygen demand substances such as proteins and amino acids, hydrocarbons, organic halogen compounds, organic substances such as organic phosphorus compounds, nitrogen compounds, sulfur compounds, cyan compounds, chromium Examples thereof include inorganic compounds such as compounds, microorganisms such as bacteria, actinomycetes, fungi, algae, and molds. Specific examples of the hydrocarbon include aldehydes, amines, mercaptans, oils and alcohols. Specific examples of the organic halogen compound include polychlorinated biphenyl, freon, trihalomethane, trichloroethylene, and tetrachloroethylene. Specific examples of the nitrogen compound include ammonia and nitrogen oxides. The photocatalyst of the present invention can efficiently decompose and remove organic halogen compounds such as polychlorinated biphenyls, trihalomethanes, trichloroethylene, and tetrachloroethylene. As the light having a wavelength having an energy equal to or more than the band gap, light containing ultraviolet rays is preferable, and for example, light of sunlight, fluorescent lamp, black light, halogen lamp, xenon flash lamp, mercury lamp or the like can be used. Particularly, light containing near-ultraviolet rays of 300 to 400 nm is preferable. The irradiation amount and irradiation time of light can be appropriately set depending on the amount of the substance to be treated.
【００１０】[0010]
【実施例】 実施例１ 硫酸チタニルを加熱加水分解して得られた酸性酸化チタ
ンゾル（石原産業社製、ＣＳ−Ｎ）に水酸化ナトリウム
をｐＨが７になるように添加した後、濾過し、洗浄し、
１１０℃の温度で乾燥し、次いで、得られた乾燥物を雷
潰機で粉砕して、酸化チタン粉末を得た。次に、前記の
酸化チタン粉末とポリメチルメタクリレート製のビーズ
（綜研化学社製、ＭＲ−７ＧＳ、平均粒径７．２μｍ）
とを重量比で２：１の割合で混合し、次いで、ハイブリ
ダイザーシステム（奈良機械社製、ＮＨＳ−Ｏ型）に入
れ、メカノケミカル反応を行って、ポリマー粒子の表面
およびその表面近傍に酸化チタン光触媒粒子を担持し
た、球状の光触媒体（試料Ａ）を得た。この試料Ａの酸
化チタンの含有量は５６重量％であり、また、この試料
Ａの比重は２．０であった。この試料Ａの平均粒径は
７．７μｍであった。Example 1 Sodium hydroxide was added to an acidic titanium oxide sol (CS-N manufactured by Ishihara Sangyo Co., Ltd.) obtained by heating and hydrolyzing titanyl sulfate so that the pH was 7, and then filtered. Washed,
It was dried at a temperature of 110 ° C., and then the obtained dried product was crushed by a thunder crusher to obtain a titanium oxide powder. Next, the titanium oxide powder and beads made of polymethylmethacrylate (manufactured by Soken Chemical Industry Co., Ltd., MR-7GS, average particle size 7.2 μm)
Are mixed at a weight ratio of 2: 1 and then put into a hybridizer system (NHS-O type manufactured by Nara Machinery Co., Ltd.) to carry out a mechanochemical reaction to oxidize the surface of the polymer particles and the vicinity thereof. A spherical photocatalyst (sample A) carrying titanium photocatalyst particles was obtained. The titanium oxide content of this sample A was 56% by weight, and the specific gravity of this sample A was 2.0. The average particle size of this sample A was 7.7 μm.
【００１１】実施例２ アクリル酸ブチルモノマー７０重量％、１、３−ブチレ
ングリコールジメタクリレートモノマー２０重量％およ
び実施例１の酸化チタン粉末１０重量％とを６０℃の温
度で１時間懸濁重合して、アクリル系コポリマー粒子の
表面およびその表面近傍に酸化チタン光触媒粒子を担持
した、球状の光触媒体（試料Ｂ）を得た。この試料Ｂの
酸化チタンの含有量は９重量％であり、また、この試料
Ｂの比重は１．３であった。この試料Ｂの平均粒径は１
０．３μｍであった。Example 2 70% by weight of butyl acrylate monomer, 20% by weight of 1,3-butylene glycol dimethacrylate monomer and 10% by weight of titanium oxide powder of Example 1 were subjected to suspension polymerization at a temperature of 60 ° C. for 1 hour. Thus, a spherical photocatalyst body (Sample B) was obtained in which titanium oxide photocatalyst particles were carried on the surface of the acrylic copolymer particles and in the vicinity thereof. The titanium oxide content of this sample B was 9% by weight, and the specific gravity of this sample B was 1.3. The average particle size of this sample B is 1
It was 0.3 μm.
【００１２】実施例で得られた試料（Ａ、Ｂ）の光触媒
機能を以下のようにして調べた。試料Ａ０．２ｇ、試料
Ｂ１．２ｇをそれぞれ純水２５ｍｌに分散させた。次
に、これらの懸濁液２５ｍｌに２−プロパノール２５μ
ｌを添加した後、攪拌流動下、１５０Ｗのキセノンラン
プを２時間照射して、２−プロパノールの光触媒反応を
行った。反応前の２−プロパノールの濃度と反応後の２
−プロパノールの濃度から各々の試料による分解速度を
算出した。その結果を表１に示す。この表から明らかな
ように、本発明の光触媒体は光触媒機能に優れていた。
本発明の光触媒体は比重が小さいため、処理対象物質を
含んだ流体に均一に流動した状態で用いることができの
で、該処理対象物質との接触がよくなること、光の利用
効率が高まることなどにより、優れた光触媒機能を有す
ると考えられる。しかも、本発明の光触媒体は、光触媒
反応時の反応装置からの光触媒粒子の飛散や流出を少な
くすることができ、また、光触媒反応終了後の反応装置
からの光触媒粒子の分離・回収を容易にすることができ
た。また、ポリマー粒子からの光触媒粒子の剥離が少な
いことも確認できた。The photocatalytic function of the samples (A, B) obtained in the examples was investigated as follows. 0.2 g of sample A and 1.2 g of sample B were dispersed in 25 ml of pure water. Next, 25 ml of 2-propanol was added to 25 ml of these suspensions.
After the addition of 1 liter, a 150 W xenon lamp was irradiated for 2 hours under stirring and flow to perform a photocatalytic reaction of 2-propanol. The concentration of 2-propanol before the reaction and 2 after the reaction
-The decomposition rate of each sample was calculated from the concentration of propanol. The results are shown in Table 1. As is clear from this table, the photocatalyst of the present invention was excellent in the photocatalytic function.
Since the photocatalyst of the present invention has a small specific gravity, it can be used in a state in which it uniformly flows in a fluid containing a substance to be treated, so that the substance to be treated is well contacted and the light utilization efficiency is improved. Therefore, it is considered to have an excellent photocatalytic function. Moreover, the photocatalyst of the present invention can reduce the scattering and outflow of the photocatalyst particles from the reaction device during the photocatalytic reaction, and also facilitates the separation and recovery of the photocatalyst particles from the reaction device after the photocatalytic reaction is completed. We were able to. It was also confirmed that the photocatalyst particles were not peeled off from the polymer particles.
【００１３】[0013]
【表１】 [Table 1]
【００１４】[0014]
【発明の効果】本発明は、ポリマー粒子の表面および／
またはその表面近傍に光触媒粒子を含有してなる光触媒
体であって、光触媒反応時の反応装置からの光触媒粒子
の飛散や流出を少なくすることができ、また、光触媒反
応終了後の反応装置からの光触媒粒子の分離・回収を容
易にすることができる。しかも、優れた光触媒機能を有
するため、有機ハロゲン化合物、悪臭ガス、油、細菌、
菌類、藻類などの人体や生活環境に悪影響を及ぼす物質
やその可能性がある物質を迅速、かつ、効率よく除去す
ることができるので、工業用途ばかりでなく一般家庭用
の除去剤、脱臭体、殺菌体などとして極めて有用なもの
である。本発明方法は、光触媒粒子の存在下モノマーを
重合する方法またはポリマー粒子と光触媒粒子とをメカ
ノケミカル反応させる方法であって、本発明の光触媒体
を簡便、かつ、効率よく得ることができるなど有用な方
法である。さらに、本発明の有害物質の除去方法は、本
発明の光触媒体にそのバンドギャップ以上のエネルギー
を持つ波長の光を照射する方法であって、有害物質を迅
速、かつ、効率よく除去することができるなど、有用な
方法である。The present invention relates to the surface of polymer particles and / or
Or a photocatalyst body containing photocatalyst particles in the vicinity of its surface, which can reduce the scattering and outflow of photocatalyst particles from the reaction device during the photocatalytic reaction, and from the reaction device after the end of the photocatalytic reaction. The separation / collection of photocatalyst particles can be facilitated. Moreover, since it has an excellent photocatalytic function, organic halogen compounds, malodorous gas, oil, bacteria,
Since it is possible to quickly and efficiently remove substances that may adversely affect the human body or living environment, such as fungi and algae, and substances that have the potential to do so, not only for industrial use but also for general household use, deodorant, It is extremely useful as a sterilizer. The method of the present invention is a method of polymerizing a monomer in the presence of photocatalyst particles or a method of performing a mechanochemical reaction between polymer particles and photocatalyst particles, and is useful in that the photocatalyst of the present invention can be obtained simply and efficiently. That's the method. Furthermore, the method for removing harmful substances of the present invention is a method of irradiating the photocatalyst of the present invention with light having a wavelength having an energy equal to or higher than the band gap, and it is possible to remove harmful substances quickly and efficiently. This is a useful method.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ａ６２Ｄ 3/00 ＺＡＢ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area // A62D 3/00 ZAB
Claims (8)
面近傍に光触媒粒子を含有してなることを特徴とする光
触媒体。1. A photocatalyst body comprising photocatalyst particles on the surface of polymer particles and / or near the surface thereof.
とする請求項１に記載の触媒体。2. The catalyst body according to claim 1, wherein the photocatalyst particles are titanium oxide.
粒子を０．１〜８０重量％含有してなることを特徴とす
る請求項１に記載の光触媒体。3. The photocatalyst body according to claim 1, wherein the photocatalyst particles are contained in an amount of 0.1 to 80% by weight based on the weight of the polymer particles.
よび／またはシリコン系ポリマー粒子であることを特徴
とする請求項１に記載の光触媒体。4. The photocatalyst body according to claim 1, wherein the polymer particles are fluorine-based polymer particles and / or silicon-based polymer particles.
て、ポリマー粒子の表面および／またはその表面近傍に
光触媒粒子を含有させることを特徴とする光触媒体の製
造方法。5. A method for producing a photocatalyst body, which comprises polymerizing a monomer in the presence of photocatalyst particles to contain the photocatalyst particles on the surface of the polymer particles and / or in the vicinity of the surface.
カル反応させ、ポリマー粒子の表面および／またはその
表面近傍に光触媒粒子を含有させることを特徴とする光
触媒体の製造方法。6. A method for producing a photocatalyst, characterized in that the polymer particles and the photocatalyst particles are subjected to a mechanochemical reaction to contain the photocatalyst particles on the surface of the polymer particles and / or in the vicinity of the surface.
媒体にそのバンドギャップ以上のエネルギーを持つ波長
の光を照射することを特徴とする有害物質の除去方法。7. A method for removing a harmful substance, which comprises irradiating the photocatalyst according to claim 1 with light having a wavelength having an energy larger than the band gap in the presence of the harmful substance.
含む被処理水に流動させ、次いで、そのバンドギャップ
以上のエネルギーを持つ波長の光を照射することを特徴
とする有害物質の除去方法。8. A toxic substance characterized in that the photocatalyst according to claim 1 is made to flow into the water to be treated containing the toxic substance, and then the photocatalyst is irradiated with light having a wavelength having an energy not less than the band gap. Removal method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6058227A JPH07241475A (en) | 1994-03-02 | 1994-03-02 | Photocatalyst body, its production and method for removing harmful substance using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6058227A JPH07241475A (en) | 1994-03-02 | 1994-03-02 | Photocatalyst body, its production and method for removing harmful substance using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07241475A true JPH07241475A (en) | 1995-09-19 |
Family
ID=13078203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6058227A Pending JPH07241475A (en) | 1994-03-02 | 1994-03-02 | Photocatalyst body, its production and method for removing harmful substance using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07241475A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997041069A1 (en) * | 1996-04-30 | 1997-11-06 | Tao Inc. | Sink-and-float body for purification and purificator |
| JPH10363A (en) * | 1996-06-13 | 1998-01-06 | Dainippon Toryo Co Ltd | Formation of coating film having photochemical activity |
| JPH11228875A (en) * | 1998-02-19 | 1999-08-24 | Dainippon Toryo Co Ltd | Coating material composition for outdoor use |
| US6090736A (en) * | 1997-12-25 | 2000-07-18 | Agency Of Industrial Science And Technology | Photocatalytic powder for environmental clarification and process for producing same, said powder-containing polymer composition, and shaped article of said composition and process for producing same |
| JP2008036465A (en) * | 2006-08-01 | 2008-02-21 | Fujitsu Ltd | Photocatalytic composite material and its manufacturing method |
-
1994
- 1994-03-02 JP JP6058227A patent/JPH07241475A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997041069A1 (en) * | 1996-04-30 | 1997-11-06 | Tao Inc. | Sink-and-float body for purification and purificator |
| JPH10363A (en) * | 1996-06-13 | 1998-01-06 | Dainippon Toryo Co Ltd | Formation of coating film having photochemical activity |
| US6090736A (en) * | 1997-12-25 | 2000-07-18 | Agency Of Industrial Science And Technology | Photocatalytic powder for environmental clarification and process for producing same, said powder-containing polymer composition, and shaped article of said composition and process for producing same |
| US6291067B1 (en) | 1997-12-25 | 2001-09-18 | Japan As Represented By Director General Of The Agency Of Industrial Science And Technology | Photocatalytic powder for environmental clarification and powder-containing polymer composition thereof |
| JPH11228875A (en) * | 1998-02-19 | 1999-08-24 | Dainippon Toryo Co Ltd | Coating material composition for outdoor use |
| JP2008036465A (en) * | 2006-08-01 | 2008-02-21 | Fujitsu Ltd | Photocatalytic composite material and its manufacturing method |
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