JP2000070673A - Antibacterial deodorizing photocatalyst type filter and its production - Google Patents
Antibacterial deodorizing photocatalyst type filter and its productionInfo
- Publication number
- JP2000070673A JP2000070673A JP10249585A JP24958598A JP2000070673A JP 2000070673 A JP2000070673 A JP 2000070673A JP 10249585 A JP10249585 A JP 10249585A JP 24958598 A JP24958598 A JP 24958598A JP 2000070673 A JP2000070673 A JP 2000070673A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- deodorizing
- titanium oxide
- dispersed
- particles
- 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
- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 134
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 123
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000002245 particle Substances 0.000 claims abstract description 192
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 116
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000463 material Substances 0.000 claims abstract description 70
- 229910052709 silver Inorganic materials 0.000 claims abstract description 48
- 239000004332 silver Substances 0.000 claims abstract description 48
- 239000010949 copper Substances 0.000 claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 50
- 230000001699 photocatalysis Effects 0.000 claims description 36
- 239000011230 binding agent Substances 0.000 claims description 35
- 239000002923 metal particle Substances 0.000 claims description 26
- 230000002209 hydrophobic effect Effects 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 8
- -1 titanium alkoxide Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 4
- 239000002519 antifouling agent Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 241000894006 Bacteria Species 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 235000019645 odor Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002341 toxic gas Substances 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
- 229920001817 Agar Polymers 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 102100022626 Glutamate receptor ionotropic, NMDA 2D Human genes 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- 101000972840 Homo sapiens Glutamate receptor ionotropic, NMDA 2D Proteins 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002729 alkyl fluoride group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- XNRABACJWNCNEQ-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.[Ag+].[O-][N+]([O-])=O XNRABACJWNCNEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Filtering Materials (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗菌脱臭性光触媒
型フィルタに関し、更に詳しくは、一般家庭や業務用等
に用いられる空気清浄剤のエアフィルタ等に好適な抗菌
脱臭性光触媒型フィルタ及びその製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial deodorizing photocatalytic filter, and more particularly, to an antibacterial deodorizing photocatalytic filter suitable for an air filter of an air cleaner used for general households and business use, and the like. It relates to a manufacturing method.
【０００２】[0002]
【従来の技術】従来、この種の抗菌脱臭性光触媒型フィ
ルタは、すでに家庭用或いは公共施設や老人ホーム等の
業務用の空気清浄機のエアフィルタ等として用いられて
いる。2. Description of the Related Art Conventionally, this kind of antibacterial deodorizing photocatalytic filter has already been used as an air filter for air purifiers for home use or business use such as in public facilities and nursing homes.
【０００３】この従来の光触媒型フィルタは、光触媒型
酸化チタンをフィルタ基材の表面にコーティングしたも
のであるが、このフィルタに空気を吸収し、フィルタ表
面の酸化チタンに紫外線を当てると、スーパーオキシド
（Ｏ２ ー）と水酸基ラジカル（・ＯＨ）が発生し、この
２つの物質は強力な酸化力をもっているため空気中の細
菌や悪臭、有毒ガスが分解されるというものである。[0003] This conventional photocatalytic filter is formed by coating the surface of a filter substrate with photocatalytic titanium oxide. When the filter absorbs air and irradiates the titanium oxide on the filter surface with ultraviolet light, it becomes superoxide. (O 2 over) and hydroxyl radical (· OH) is generated, bacteria and odors for air to have the two materials are strong oxidizing power, is that toxic gases are decomposed.
【０００４】例えば、ハウスダストに付着する細菌やウ
ィルス、タバコ臭、目や喉を刺激する新建材臭（ホルム
アルデヒド等の有毒ガス）、ペット臭、し尿臭等がこの
光触媒型フィルタによって除去・脱臭され、清浄な空気
・清潔な環境が維持されることになる。For example, bacteria and viruses adhering to house dust, tobacco odor, new building material odor (toxic gas such as formaldehyde) irritating eyes and throat, pet odor, human urine odor and the like are removed and deodorized by the photocatalytic filter. Therefore, clean air and a clean environment are maintained.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、この従
来一般に知られる光触媒型フィルタによれば、一応の細
菌除去・悪臭除去の効果は認められるものの、いろいろ
と比較実験を行ってみると悪臭除去効果が未だ十分では
なく、またこの種のフィルタは空気中の粉塵等による目
詰まりが生じるとこれを除去し繰り返し使用されるが、
その繰り返し再使用の間に脱臭性能が徐々に低下してい
き、その性能の低下の度合いが大きいために使用寿命が
短いという問題があった。However, according to the conventional photocatalyst type filter, although the effects of removing bacteria and removing odors are recognized, the effects of removing odors are found in various comparative experiments. It is still not enough, and this type of filter is used repeatedly to remove clogging caused by dust in the air, etc.
During the repeated reuse, the deodorizing performance gradually decreases, and there is a problem that the service life is short because the performance is greatly reduced.
【０００６】本発明の解決しようとする課題は、抗菌脱
臭効果が大きく、繰り返しの使用にもその性能が低下せ
ず、恒久的安定使用が期待される抗菌脱臭性光触媒型フ
ィルタを提供することにある。An object of the present invention is to provide an antibacterial deodorizing photocatalytic filter which has a large antibacterial deodorizing effect, does not deteriorate its performance even after repeated use, and is expected to be used permanently and stably. is there.
【０００７】[0007]
【課題を解決するための手段】この課題を解決するため
に本発明の抗菌脱臭性光触媒型フィルタは、請求項１に
記載のように、酸化チタン粒子に金属銀若しくは金属銅
の金属粒子を分散付着させた抗菌脱臭性粒子材料をフィ
ルタ基材の表面に分散担持させてなることを要旨とする
ものである。According to the present invention, there is provided an antibacterial deodorizing photocatalytic filter according to the present invention, wherein metallic particles of metallic silver or metallic copper are dispersed in titanium oxide particles. The gist is to disperse and carry the attached antibacterial deodorizing particle material on the surface of the filter substrate.
【０００８】フィルタ基材表面の抗菌脱臭性粒子材料に
ブラックライト等により紫外線を照射することにより、
その抗菌脱臭性粒子材料中の酸化チタン粒子が活性化
し、このフィルタ基材に吸引される空気中の細菌を死滅
させ、また空気中の悪臭成分が分解される。そして、こ
の抗菌脱臭性粒子材料の酸化チタン粒子に分散担持され
ている金属銀若しくは金属銅粒子が活性助剤として機能
し、空気中の細菌や悪臭の除去性能が高められ、また繰
り返しの利用にも高性能が持続されることになる。[0008] By irradiating the antibacterial deodorizing particle material on the surface of the filter substrate with ultraviolet light using a black light or the like,
The titanium oxide particles in the antibacterial deodorizing particle material are activated, kill bacteria in the air sucked into the filter substrate, and decompose the malodorous components in the air. And the silver or copper metal particles dispersed and supported on the titanium oxide particles of this antibacterial deodorizing particle material function as an active aid, and the performance of removing bacteria and bad odors in the air is enhanced. High performance will be maintained.
【０００９】この場合に、前記酸化チタン粒子は、請求
項２に記載のように、アナターゼ結晶構造のものである
ことが望ましい。酸化チタン粒子の結晶構造にはルチル
型やアナターゼ型のものがあるが、特にアナターゼ結晶
構造のものが紫外線を照射したときに光触媒性能が強く
働き、細菌や脱臭効果が大きい。In this case, it is desirable that the titanium oxide particles have an anatase crystal structure. Titanium oxide particles have a rutile type or anatase type crystal structure. Particularly, those having an anatase crystal structure have a strong photocatalytic performance when irradiated with ultraviolet light, and have a large bacterial and deodorizing effect.
【００１０】そして、請求項３に記載のように、前記酸
化チタン粒子の平均粒径は０．０４μｍ未満であり、前
記金属粒子の粒径は４ｎｍ未満であることが望ましい。
酸化チタン粒子の粒径が大きすぎれば、抗菌脱臭性粒子
材料としての比表面積が小さくなって殺菌や脱臭に時間
がかかり、脱臭性能等が十分に発揮されないばかりか、
フィルタの性能維持のためのクリーニングやフィルタ交
換等の頻度が増えることになる。酸化チタン粒子の平均
粒径は、更に好ましくは０．０２μｍ以下である。Preferably, the average particle size of the titanium oxide particles is less than 0.04 μm, and the particle size of the metal particles is less than 4 nm.
If the particle size of the titanium oxide particles is too large, the specific surface area as the antibacterial deodorizing particle material becomes small, and it takes time to sterilize and deodorize, and not only does the deodorizing performance and the like not sufficiently exert,
The frequency of cleaning and filter replacement for maintaining the performance of the filter increases. The average particle size of the titanium oxide particles is more preferably 0.02 μm or less.
【００１１】また、金属銀や金属銅粒子の粒径も大きす
ぎれば光触媒の活性助剤としての機能が十分に発揮され
ず、殺菌脱臭性能の更なる向上が期待されないばかり
か、フィルタの活性化触媒としての耐久性（繰り返し再
利用）も十分に発揮されないことになる。この金属粒子
の粒径は、更に好ましくは、２ｎｍ以下である。On the other hand, if the particle size of the metallic silver or metallic copper particles is too large, the function of the photocatalyst as an active aid will not be sufficiently exhibited, and further improvement in sterilization and deodorization performance will not be expected, and activation of the filter will not be expected. The durability as a catalyst (repeated reuse) will not be sufficiently exhibited. The particle size of the metal particles is more preferably 2 nm or less.
【００１２】そして、前記酸化チタン粒子に分散付着さ
れる金属粒子の付着量は、請求項４に記載のように、前
記酸化チタン粒子の単位重量当り０．１重量％以上５０
重量％以下、好ましくは０．５重量％以上５重量％以下
であることが望ましい。酸化チタン粒子に分散付着され
る金属銀や金属銅粒子の付着量を適正な範囲とすること
で抗菌性能や脱臭性能が発揮維持されるものである。The amount of the metal particles dispersed and attached to the titanium oxide particles may be 0.1% by weight or more per unit weight of the titanium oxide particles.
% By weight, preferably 0.5% by weight or more and 5% by weight or less. Antibacterial performance and deodorizing performance are exhibited and maintained by adjusting the amount of the metallic silver or metallic copper particles dispersed and attached to the titanium oxide particles to an appropriate range.
【００１３】この場合に請求項５に記載のように、前記
フィルタ基材の表面に分散担持される抗菌脱臭性粒子材
料の担持量は、１ｇ／ｍ２以上であることが望ましい。
フィルタ基材の表面に分散担持される抗菌脱臭性粒子材
料の担持量が多いほど抗菌脱臭効果が大きく、しかもそ
の抗菌脱臭性能が持続的に発揮される。In this case, as described in claim 5, the amount of the antibacterial deodorizing particulate material dispersedly supported on the surface of the filter substrate is preferably 1 g / m 2 or more.
The larger the amount of the antibacterial deodorizing particle material dispersedly supported on the surface of the filter substrate, the greater the antibacterial deodorizing effect and the sustained antibacterial deodorizing performance.
【００１４】更に、前記抗菌脱臭性粒子材料は、無機酸
化物系結着剤によりフィルタ基材表面に結合付着されて
いることが望ましい。この種の結合材としては、有機系
バインダと無機系バインダとが一般に知られているが、
有機系バインダは光触媒反応の影響を受けやすく、フィ
ルタ基材表面から脱落しやすくなるために好ましくな
い。また無機系バインダでも、例えば水ガラスはＮａを
含み負触媒となるため、好ましくない。Further, it is desirable that the antibacterial deodorizing particle material is bonded and attached to the surface of the filter substrate by an inorganic oxide binder. Organic binders and inorganic binders are generally known as this type of binder,
Organic binders are not preferred because they are easily affected by the photocatalytic reaction and easily fall off from the surface of the filter substrate. In addition, even an inorganic binder is not preferable because, for example, water glass contains Na and becomes a negative catalyst.
【００１５】酸化チタン光触媒層の担持バインダの要求
特性は、主に以下の通りである。 （１）アナターゼ型酸化チタン粒子の表面が脱臭・大気
浄化機能を十分に発揮するためには、多孔質で表面積が
広く取られるべきであり、またバインダによってこれら
が封じ込められないことである。この条件を満たすた
め、バインダ溶液は極めて低粘度（２５℃：２０ｃＰ以
下）であり、フィルタ基材表面のバインダ厚は０．５μ
ｍ以下が望ましい。 （２）アナターゼ型酸化チタン粒子の表面が光を十分に
取り入れて触媒活性が大きくなるようにするためには、
バインダ塗膜は光透過性を有するように透明度が高く、
かつフィルタ基材との接着力が優れている必要がある。 （３）バインダ塗膜の経時変化は小さく、耐水・耐候性
に優れていることが必要である。この条件を満たすた
め、疎水性かつ無機系の安定した被膜が望ましい。 （４）耐摩耗性に優れ、かつ若干の柔軟性を維持し、ひ
び割れ等のクラックが起きにくいことも必要とされる。The required characteristics of the binder for the titanium oxide photocatalyst layer are mainly as follows. (1) In order for the surface of the anatase type titanium oxide particles to sufficiently exhibit the deodorizing and air purifying functions, the surface must be made porous and have a large surface area, and they must not be sealed by a binder. To satisfy this condition, the binder solution has an extremely low viscosity (25 ° C .: 20 cP or less), and the binder thickness on the surface of the filter substrate is 0.5 μm.
m or less is desirable. (2) In order for the surface of the anatase type titanium oxide particles to sufficiently absorb light and increase the catalytic activity,
The binder coating has high transparency so as to have light transmittance,
In addition, the adhesive strength to the filter substrate needs to be excellent. (3) It is necessary that the binder coating has little change with time and has excellent water resistance and weather resistance. To satisfy this condition, a hydrophobic and inorganic stable film is desirable. (4) It is also required that the material has excellent abrasion resistance, maintains some flexibility, and hardly causes cracks such as cracks.
【００１６】このような条件を満たすものとして、アナ
ターゼ型酸化チタン粒子に金属銀若しくは金属銅粒子を
分散付着させた抗菌脱臭性粒子材料を無機系アルコキシ
ドの溶媒に分散懸濁し、これをフィルタ基材の表面に塗
着し、無機系アルコキシド溶媒の常温での脱アルコール
及び脱水重合により前記抗菌脱臭性粒子材料をフィルタ
基材の表面に分散担持させたものが最も好適である。As a material satisfying such conditions, an antibacterial deodorizing particle material in which metallic silver or metallic copper particles are dispersed and adhered to anatase type titanium oxide particles is dispersed and suspended in a solvent of an inorganic alkoxide, and this is used as a filter substrate. It is most preferable that the antibacterial deodorizing particle material is dispersed and carried on the surface of the filter substrate by applying alcohol to the inorganic alkoxide solvent at room temperature and dehydration polymerization at room temperature.
【００１７】この場合に無機系アルコキシド溶媒に疎水
性セグメントと親水性セグメントからなる親疎水性ブロ
ック共重合体を配合し、この親疎水性ブロック共重合体
がフィルタ基材表面に介在されることにより抗菌脱臭性
粒子材料のフィルタ基材への接着性と、フィルタ基材表
面の親水性が高められる。In this case, an inorganic alkoxide solvent is blended with a hydrophilic / hydrophobic block copolymer composed of a hydrophobic segment and a hydrophilic segment, and the hydrophilic / hydrophobic block copolymer is interposed on the surface of the filter base material to cause antibacterial deodorization. The adhesiveness of the conductive particle material to the filter substrate and the hydrophilicity of the filter substrate surface are enhanced.
【００１８】次に、前記酸化チタン粒子に金属銀若しく
は金属銅粒子を分散付着させた抗菌脱臭性粒子材料に
は、更に酸化チタン粒子の触媒性能を高める白金触媒若
しくはパラジウム触媒が含まれていると更によい。これ
により酸化チタン粒子の光触媒性能は更に高められるこ
とになる。Next, the antibacterial deodorizing particle material in which metallic silver or metallic copper particles are dispersed and attached to the titanium oxide particles contains a platinum catalyst or a palladium catalyst which further enhances the catalytic performance of the titanium oxide particles. Even better. This further enhances the photocatalytic performance of the titanium oxide particles.
【００１９】更に請求項８に記載のように、前記酸化チ
タン粒子に金属銀若しくは金属銅粒子を分散付着させた
抗菌脱臭性粒子材料には、酸化チタン粒子に金属銀及び
金属銅が付着されていない単独酸化チタン粒子が混合さ
れているものでもよい。従来の酸化チタン粒子単独品の
ものより光触媒活性がよく、クリーニングによる繰り返
し利用にも光触媒性能の持続性が確保される。Further, in the antibacterial deodorizing particle material in which metallic silver or metallic copper particles are dispersed and adhered to the titanium oxide particles, metallic silver and metallic copper are adhered to the titanium oxide particles. Or a mixture of single titanium oxide particles. The photocatalytic activity is better than that of the conventional titanium oxide particles alone, and the durability of the photocatalytic performance is ensured even when repeatedly used by cleaning.
【００２０】尚、前記フィルタ基材は、繊維、発泡樹
脂、セラミックス多孔質体又はハニカム形状のもの、金
属メッシュが好適なものとして用いられる。また、前記
フィルタ基材の表面に活性炭或いはゼオライト等の吸着
活性剤を担持させ、該吸着活性剤に前記抗菌脱臭性粒子
材料が分散担持されているものもよい。このような活性
炭やゼオライトは吸着性能が高いため、細菌や悪臭成分
の補足効果を更に高めることが期待される。The filter substrate is preferably made of fiber, foamed resin, porous ceramic or honeycomb, or metal mesh. Further, an adsorbent such as activated carbon or zeolite may be supported on the surface of the filter substrate, and the antibacterial deodorant particle material may be dispersed and supported on the adsorbent. Since such activated carbon and zeolite have high adsorption performance, they are expected to further enhance the effect of capturing bacteria and malodorous components.
【００２１】一方、本発明に係る抗菌脱臭性光触媒型フ
ィルタの製造方法は、請求項１１に記載のように、アナ
ターゼ型酸化チタン粒子に金属銀若しくは金属銅の金属
粒子を分散付着させた抗菌脱臭性粒子材料を無機系アル
コキシドの溶媒に分散懸濁し、これをフィルタ基材の表
面に塗着し、前記溶媒の常温での脱アルコール及び脱水
重合反応により前記抗菌脱臭性粒子材料をフィルタ基材
の表面に分散担持させるようにしたことを要旨とするも
のである。On the other hand, a method of manufacturing an antibacterial deodorizing photocatalytic filter according to the present invention is directed to an antibacterial deodorizing method in which metallic silver or metallic copper particles are dispersed and adhered to anatase type titanium oxide particles. The anti-bacterial deodorizing particle material is dispersed and suspended in a solvent of an inorganic alkoxide, applied to the surface of a filter substrate, and subjected to a dealcoholization and dehydration polymerization reaction of the solvent at room temperature to convert the antibacterial deodorizing particle material into a filter substrate. The gist is to disperse and carry on the surface.
【００２２】これにより、抗菌脱臭性粒子材料はフィル
タ基材の表面に無機酸化物系結合により堅固に結合付着
された状態が得られ、有機系バインダのような光触媒反
応の影響は回避される。また常温乾燥での処理であるた
め製造しやすいという便利さもある。As a result, the antibacterial and deodorizing particle material is firmly bonded and attached to the surface of the filter substrate by inorganic oxide bonding, and the influence of a photocatalytic reaction such as an organic binder is avoided. In addition, since the treatment is performed at room temperature drying, there is also the convenience of easy production.
【００２３】そして、前記アルコキシドは、請求項１２
に記載のように、チタニウムアルコキシド及びシラン系
アルコキシドの混合溶媒であることが望ましい。これに
より抗菌脱臭性粒子材料とフィルタ基材とが、化１に示
す結合により結着されているものであるから、無機系バ
インダでも水ガラス（Ｎａ成分を含む。）のような負触
媒の作用はなく、また、チタニウムアルコキシドとシラ
ン系アルコキシドとを混合することにより可撓性が生
じ、フィルタとしての柔軟性が維持され、ひび割れ等の
クラックも起きにくい。The alkoxide is preferably selected from the group consisting of
As described in above, a mixed solvent of a titanium alkoxide and a silane-based alkoxide is desirable. As a result, the antibacterial deodorizing particle material and the filter base material are bound by the bond shown in Chemical formula 1, and the action of a negative catalyst such as water glass (including a Na component) even with an inorganic binder. Further, by mixing the titanium alkoxide and the silane-based alkoxide, flexibility is generated, the flexibility as a filter is maintained, and cracks such as cracks are less likely to occur.
【００２４】[0024]
【化１】 Embedded image
【００２５】また、その場合に、請求項１３に記載のよ
うに、前記無機系アルコキシドの溶媒には、疎水性セグ
メントと親水性セグメントからなる親疎水性ブロック共
重合体を配合していることが望ましい。これにより親疎
水性ブロック共重合体のうち疎水性セグメントにより抗
菌脱臭性粒子材料のフィルタ基材への接着性が向上し、
親水性セグメントによりフィルタ基材の表面親水性が向
上する。In this case, it is desirable that the solvent of the inorganic alkoxide contains a hydrophilic / hydrophobic block copolymer composed of a hydrophobic segment and a hydrophilic segment. . Thereby, the adhesiveness of the antibacterial deodorizing particle material to the filter substrate is improved by the hydrophobic segment of the hydrophilic / hydrophobic block copolymer,
The hydrophilic segment improves the surface hydrophilicity of the filter substrate.
【００２６】更に、請求項１４に記載のように、前記無
機系アルコキシドの溶媒には、前記フィルタ基材の表面
に空気中の汚染物質が付着するのを防止するための防汚
剤を配合すれば、フィルタが空気中の汚染物質の付着に
より恒久的使用が損なわれるようなことが回避される。
その防汚剤としては、フッ化アルキル基若しくはシリコ
ン基を含む疎水性ポリマー等が有効である。Further, as described in claim 14, an antifouling agent for preventing the contaminants in the air from adhering to the surface of the filter substrate is added to the inorganic alkoxide solvent. This prevents the filter from being damaged for permanent use by the deposition of contaminants in the air.
As the antifouling agent, a hydrophobic polymer containing an alkyl fluoride group or a silicon group is effective.
【００２７】[0027]
【発明の実施の形態】以下に本発明の実施例について詳
細に説明する。初めに酸化チタン粒子に金属銀（Ａｇ）
若しくは金属銅（Ｃｕ）粒子を分散付着させた抗菌脱臭
性粒子材料の製造方法について説明する。次の実施例１
〜実施例５はアナターゼ型酸化チタン粒子に金属銀（Ａ
ｇ）粒子を分散付着させた抗菌脱臭性粒子材料の製造例
を示している。Embodiments of the present invention will be described below in detail. First, metallic silver (Ag) is added to the titanium oxide particles.
Alternatively, a method for producing an antibacterial deodorizable particle material in which metallic copper (Cu) particles are dispersed and attached will be described. Next Example 1
-Example 5 shows that the anatase type titanium oxide particles are coated with metallic silver (A
g) shows an example of the production of an antibacterial deodorizing particle material in which particles are dispersed and attached.
【００２８】（実施例１）硝酸銀１．２ｇ（Ａｇとして
０．７６ｇ含有）を１０ｍｌの純水に溶解し、この液に
アンモニア水４ｍｌを加えることによって、硝酸銀のア
ンモニア錯体を得た。これに平均粒径が０．００７μｍ
のアナターゼ型酸化チタン（ＴｉＯ２）粒子を用意し、
この酸化チタン粒子７５ｇを上記硝酸銀のアンモニア錯
体の溶液に加えた後、攪拌・分散させた。Example 1 1.2 g of silver nitrate (containing 0.76 g as Ag) was dissolved in 10 ml of pure water, and 4 ml of aqueous ammonia was added to the solution to obtain an ammonia complex of silver nitrate. The average particle size is 0.007 μm
Anatase type titanium oxide (TiO 2 ) particles of
After 75 g of the titanium oxide particles were added to the above solution of the silver nitrate ammonia complex, the mixture was stirred and dispersed.
【００２９】次に、この分散液に還元剤としてぶどう糖
８ｇを含むぶどう糖溶液１００ｍｌを添加した後、３０
〜５０℃に加熱して１時間攪拌することによって、酸化
チタン粒子の表面に金属銀を析出させ、次いでデカンテ
ーションで分離し、水洗浄及び乾燥することによって、
平均粒径０．０１μｍのアナターゼ酸化チタン粒子の表
面に０．７６ｇ（１重量％）の金属銀からなる金属粒子
が分散付着した抗菌脱臭性粒子材料を約７６ｇ得た。Next, 100 ml of a glucose solution containing 8 g of glucose as a reducing agent was added to this dispersion,
By heating to ５０50 ° C. and stirring for 1 hour, metal silver is deposited on the surface of the titanium oxide particles, then separated by decantation, washed with water and dried,
About 76 g of an antibacterial deodorizing particle material in which 0.76 g (1% by weight) of metal particles composed of metallic silver were dispersed and adhered to the surface of anatase titanium oxide particles having an average particle diameter of 0.01 μm.
【００３０】（実施例２）硝酸銀３．８ｇ（Ａｇとして
２．３７ｇ含有）を４０ｍｌの純水に溶解し、この液に
アンモニア水１０ｍｌを加えることによって、硝酸銀の
アンモニア錯体を得た後、平均粒径０．００７μｍの同
じくアナターゼ型酸化チタン粒子の表面に２．３７ｇ
（５重量％）の金属銀からなる金属粒子が分散付着した
抗菌脱臭性粒子を得た。Example 2 3.8 g of silver nitrate (containing 2.37 g as Ag) was dissolved in 40 ml of pure water, and 10 ml of aqueous ammonia was added to this solution to obtain an ammonium complex of silver nitrate. 2.37 g on the surface of the same anatase-type titanium oxide particles having a particle size of 0.007 μm
(5% by weight) of antibacterial deodorizing particles to which metal particles composed of metallic silver were dispersed and adhered.
【００３１】（実施例３）酸化チタンの平均粒径が０．
０２μｍであり、金属銀からなる金属粒子の付着量が
０．５重量％であるようにしたほかは、実施例１及び２
と同様にして、抗菌脱臭性粒子を得た。Example 3 The average particle size of titanium oxide was 0.1.
Examples 1 and 2 except that the thickness was 0.2 μm and the amount of metal particles made of metallic silver was 0.5% by weight.
In the same manner as in the above, antibacterial deodorizing particles were obtained.
【００３２】（実施例４）酸化チタンの平均粒径が０．
０２μｍであるものとしたほか、実施例１と同様にし
て、抗菌脱臭性粒子を得た。Example 4 The average particle size of titanium oxide was 0.1.
The antibacterial deodorizing particles were obtained in the same manner as in Example 1 except that the particle size was 02 μm.
【００３３】（実施例５）酸化チタンの平均粒径が０．
０２μｍであり、金属銀からなる金属粒子の付着量５重
量％であるようにしたほかは、実施例１と同様にして、
抗菌脱臭性粒子を得た。(Example 5) The average particle diameter of titanium oxide was 0.1%.
In the same manner as in Example 1, except that the thickness was 0.2 μm and the amount of metal particles composed of metallic silver was 5% by weight.
Antibacterial deodorizing particles were obtained.
【００３４】次に実施例６及び実施例７はアナターゼ型
酸化チタン粒子に金属銅（Ｃｕ）粒子を分散付着させた
抗菌脱臭性粒子材料の製造例を示している。Next, Examples 6 and 7 show production examples of an antibacterial deodorizing particle material in which metallic copper (Cu) particles are dispersed and attached to anatase type titanium oxide particles.
【００３５】（実施例６）硝酸銅３水和物１１．４ｇ
（Ｃｕとして３．０ｇ含有）を２０ｍｌの純水に溶解
し、この液にアンモニア水１ｍｌを加えることによっ
て、硝酸銅のアンモニア錯体を得た。これに平均粒径
０．００７μｍのアナターゼ型酸化チタン（ＴｉＯ ２）
粒子を用意し、この酸化チタン粒子９７ｇを上記硝酸銅
のアンモニア錯体の溶液に加えた後、攪拌・分散させ
た。Example 6 Copper nitrate trihydrate 11.4 g
(Containing 3.0 g as Cu) dissolved in 20 ml of pure water
Then, 1 ml of aqueous ammonia is added to this solution.
Thus, an ammonia complex of copper nitrate was obtained. Average particle size
0.007 μm anatase-type titanium oxide (TiO 2) 2)
Particles were prepared, and 97 g of the titanium oxide particles were added to the above-mentioned copper nitrate.
After adding to the ammonia complex solution, stir and disperse
Was.
【００３６】次に、この分散液に還元剤としてヒドラジ
ン水溶液２０ｍｌを添加した後、３０〜５０℃に加熱し
て１時間後攪拌することによって、酸化チタン粒子の表
面に金属銅を析出させ、次いでデカンテーションで分離
し、水洗浄及び乾燥することによって、平均粒径０．０
０７μｍのアナターゼ酸化チタン粒子の表面に３ｇ（３
重量％）の金属銅からなる金属粒子が分散付着した抗菌
脱臭性粒子を得た。Next, after adding 20 ml of a hydrazine aqueous solution as a reducing agent to this dispersion, the mixture was heated to 30 to 50 ° C. and stirred for 1 hour to precipitate metallic copper on the surface of the titanium oxide particles. Separated by decantation, washed with water and dried to obtain an average particle size of 0.0
3 g (3
% By weight) of metal particles made of metallic copper dispersed and adhered.
【００３７】（実施例７）金属銅からなる金属粒子の付
着量が１重量％であるようにしたほかは、実施例６と同
様にして、抗菌脱臭性粒子を得た。Example 7 Antibacterial deodorizing particles were obtained in the same manner as in Example 6, except that the amount of metal particles made of metallic copper was 1% by weight.
【００３８】次に、実施例８はアナターゼ型酸化チタン
粒子に金属銀（Ａｇ）粒子共に分散付着させた抗菌だ修
正粒子材料の製造例を示している。Next, Example 8 shows an example of producing an antibacterial modified particle material in which metal silver (Ag) particles are dispersed and attached to anatase type titanium oxide particles.
【００３９】（実施例８）硝酸銀１．７ｇ（Ａｇとして
１．１ｇ含有）と硝酸銅３水和物３．８ｇ（Ｃｕとして
１ｇ含有）を２０ｍｌの純水に溶解し、これにアンモニ
ア水２５ｍｌを加えて、硝酸銀と硝酸銅のアンモニア錯
体を得た。これに平均粒径が０．００７μｍのアナター
ゼ型酸化チタン粒子を用意し、この酸化チタン粒子を上
記硝酸銀と硝酸銅のアンモニア錯体の溶液に加えた後、
攪拌・分散させた。Example 8 1.7 g of silver nitrate (containing 1.1 g as Ag) and 3.8 g of copper nitrate trihydrate (containing 1 g as Cu) were dissolved in 20 ml of pure water, and 25 ml of aqueous ammonia was added thereto. Was added to obtain an ammonium complex of silver nitrate and copper nitrate. Anatase-type titanium oxide particles having an average particle size of 0.007 μm were prepared, and the titanium oxide particles were added to the solution of the above-mentioned ammonia complex of silver nitrate and copper nitrate.
It was stirred and dispersed.
【００４０】次に、この分散液に還元剤としてヒドラジ
ン水溶液２０ｍｌを添加した後３０〜５０℃に加熱して
１時間後攪拌し、酸化チタン粒子の表面に金属銀と金属
銅をそれぞれ析出させ、次いでデカンテーションで分離
し、水洗浄及び乾燥することによって、酸化チタン粒子
の表面に１．１ｇ（１重量％）の金属銀と１．０ｇ（１
重量％）の金属銅からなる金属粒子が付着した抗菌脱臭
性粒子材料を得た。Next, 20 ml of an aqueous hydrazine solution as a reducing agent was added to the dispersion, and the mixture was heated to 30 to 50 ° C. and stirred for 1 hour, to deposit metallic silver and metallic copper on the surface of the titanium oxide particles. Then, the particles were separated by decantation, washed with water and dried, so that 1.1 g (1% by weight) of metallic silver and 1.0 g (1 wt.
(% By weight) of a metal particle made of metallic copper was obtained.
【００４１】次の参考例１〜参考例３はアナターゼ型酸
化チタン粒子の粒径や酸化チタン粒子に付着される金属
銀（Ａｇ）粒子の付着量を変えたものである。また比較
例１は酸化チタン単独品の例を示したものである。In the following Reference Examples 1 to 3, the particle size of anatase type titanium oxide particles and the amount of metallic silver (Ag) particles attached to the titanium oxide particles were changed. Comparative Example 1 shows an example of a titanium oxide alone product.
【００４２】（参考例１）酸化チタンの平均粒径が０．
２μｍであり、金属銀の付着量が１．５２ｇ（２重量
％）であるようにしたほかは、実施例１と同様にして、
抗菌脱臭性粒子材料を得た。(Reference Example 1) The average particle diameter of titanium oxide is 0.1.
2 μm, and the amount of deposited metallic silver was 1.52 g (2% by weight).
An antibacterial deodorizing particle material was obtained.
【００４３】（参考例２）酸化チタンの平均粒径が０．
０２μｍであり、金属銀の付着量が０．０７６ｇ（０．
１重量％）であることのほかは、実施例１と同様にし
て、抗菌脱臭性粒子材料を得た。(Reference Example 2) The average particle size of titanium oxide is 0.1.
02 μm, and the adhesion amount of metallic silver was 0.076 g (0.
1% by weight), and an antibacterial deodorizing particle material was obtained in the same manner as in Example 1.
【００４４】（参考例３）金属銀の付着量が５．３２ｇ
（７重量％）であるようにしたほかは、実施例１と同様
にして、抗菌脱臭性粒子材料を得た。Reference Example 3 The amount of deposited metallic silver was 5.32 g.
(7% by weight), except that an antibacterial deodorizing particle material was obtained in the same manner as in Example 1.
【００４５】（比較例１）酸化チタンの平均粒径を０．
０２μｍとし、金属粒子を付着しない抗菌脱臭性粒子材
料を得た。(Comparative Example 1) The average particle size of titanium oxide was set at 0.
The particle size was set to 02 μm to obtain an antibacterial deodorizing particle material to which no metal particles adhere.
【００４６】（最小発育阻止濃度（ＭＩＣ）の測定） １．接種菌液の調整 必要な器具・試験片の滅菌を行った後、菌株ディスクを
ＭＨＢ培地に入れ、３７℃で１６〜２０時間増菌し、増
菌した培地ごと３０００ｒｐｍで１０分間遠心し、沈さ
にＭＨＢ培地１０ｍｌを加えて原液とした。次いで原液
をＭＨＢ培地で希釈し、１．０〜５．０×１０４個／ｍ
ｌの接種菌液を調整し、初期菌数算定のため、接種菌液
を３０〜３００個／ｍｌとなるように希釈し、標準寒天
培地にて混釈培養を行い、３７℃で２４時間培養後コロ
ニー数を算定した。(Measurement of Minimum Growth Inhibitory Concentration (MIC)) Preparation of Inoculated Bacterial Solution After sterilization of necessary instruments and test pieces, the strain disk was placed in MHB medium, and the cells were enriched at 37 ° C. for 16 to 20 hours. Then, 10 ml of MHB medium was added to obtain a stock solution. Next, the stock solution was diluted with MHB medium, and 1.0 to 5.0 × 10 4 cells / m 2
of the inoculum was diluted to 30 to 300 cells / ml for initial cell count calculation, pour-cultured on a standard agar medium, and cultured at 37 ° C for 24 hours. Thereafter, the number of colonies was calculated.
【００４７】２．試験用培地の作製 Ｌ字型試験管にＭＨＢ培地を１０ｍｌ分注し、１２１℃
で１５分間オートクレーブにかけ、この培地に試料を１
００μｍ／ｍｌを基準として、２倍量ずつ添加して系列
を調整し、この２倍系列培地に接種用菌液を０．１ｍｌ
添加した。2. Preparation of test medium 10 ml of MHB medium was dispensed into an L-shaped test tube,
Autoclave for 15 minutes at
Based on 00 μm / ml, the series was adjusted by adding twice the amount, and 0.1 ml of the inoculum was added to the double series medium.
Was added.
【００４８】３．試験用培地の培養 試料が均一に混合されるような条件で振とうしながら、
３５〜３７℃で２４時間培養した。3. Culture the test medium While shaking the sample so that the sample is evenly mixed,
The cells were cultured at 35 to 37 ° C for 24 hours.
【００４９】４．判定 所定時間培養後、肉眼観察により、発育が阻止された最
低濃度をもって、試験菌に対する試料の最小発育阻止濃
度（ＭＩＣ）とした。ここで、一般に、ＭＩＣ値が６０
０μｇ／ｌ以下であれば抗菌性があるとされている。こ
の結果を表１に示す。4. Judgment After culturing for a predetermined time, the minimum concentration at which growth was inhibited by visual observation was defined as the minimum inhibitory concentration (MIC) of the sample against the test bacteria. Here, generally, the MIC value is 60
If it is 0 μg / l or less, it is considered to have antibacterial properties. Table 1 shows the results.
【００５０】[0050]
【表１】 [Table 1]
【００５１】（脱臭性の評価）蓋のできるガラス製容器
内のシャーレ中に試料を１ｇ入れ、その試料に２０ｃｍ
の距離から１０Ｗの蛍光灯を照らした。このとき、ガラ
ス製容器内には、濃度が１００ｐｐｍとなるようにアセ
トアルデヒドを入れ、そのアセトアルデヒドの濃度の変
化を時間と共に測定し、残存率が５０％となる時間で脱
臭性能を評価した。この結果を同じく表１に示す。(Evaluation of Deodorizing Property) 1 g of a sample was placed in a petri dish in a glass container having a lid, and the sample was placed in a dish of 20 cm.
Illuminated a 10 W fluorescent lamp from a distance of At this time, acetaldehyde was put into the glass container so that the concentration became 100 ppm, and the change in the concentration of the acetaldehyde was measured with time, and the deodorizing performance was evaluated when the residual ratio became 50%. The results are also shown in Table 1.
【００５２】表１に示すように、実施例１〜８の場合に
は、ＭＩＣ値がすべて６００μｇ／ｌ以下であって、有
効なる抗菌性能を有していることが認められた。また、
脱臭時間はすべて３時間以内であり、有効な脱臭性能を
有していることが認められた。As shown in Table 1, in the case of Examples 1 to 8, the MIC values were all 600 μg / l or less, and it was confirmed that they had effective antibacterial performance. Also,
The deodorizing time was all within 3 hours, and it was confirmed that the deodorizing agent had effective deodorizing performance.
【００５３】これに対して、酸化チタン粒子の平均粒径
が０．２μｍと大きい参考例１のものでは、抗菌性能は
有効に発揮されるが、脱臭に時間がかかり、脱臭性能が
若干悪くなった。On the other hand, in the case of Reference Example 1 in which the average particle size of the titanium oxide particles is as large as 0.2 μm, the antibacterial performance is effectively exhibited, but it takes a long time to deodorize, and the deodorization performance is slightly deteriorated. Was.
【００５４】また、金属粒子の付着量が０．１重量％と
少ない参考例２のものでは、逆に脱臭性能は有効に発揮
されるが、ＭＩＣ値が高く、抗菌性能はさほど良くない
ものであった。On the other hand, in the case of Reference Example 2 in which the adhesion amount of metal particles is as small as 0.1% by weight, the deodorizing performance is effectively exhibited, but the MIC value is high and the antibacterial performance is not so good. there were.
【００５５】逆に、金属粒子の付着量が７重量％と多す
ぎる参考例３のものでは、抗菌性能は有効に発揮される
が、金属粒子が酸化チタンの表面を覆う割合が増加する
ため、脱臭性能はあまりよくないものとなっていた。On the other hand, in the case of Reference Example 3 in which the adhesion amount of the metal particles is too large at 7% by weight, the antibacterial performance is effectively exhibited, but the ratio of the metal particles covering the surface of the titanium oxide increases. The deodorizing performance was not so good.
【００５６】更に、酸化チタンの表面に金属粒子を付着
させない比較例１のものでは、ＭＩＣ値が高く、抗菌性
能も劣るものであった。Furthermore, in the case of Comparative Example 1 in which no metal particles were attached to the surface of titanium oxide, the MIC value was high and the antibacterial performance was poor.
【００５７】次に、このようにして得られたアナターゼ
型酸化チタン粒子に金属銀若しくは金属銅粒子を分散付
着させた抗菌脱臭性粒子材料をフィルタ基材の表面に分
散担持させる方法について説明する。Next, a method of dispersing and carrying an antibacterial deodorizing particle material in which metallic silver or metallic copper particles are dispersed and adhered to the thus obtained anatase type titanium oxide particles will be described.
【００５８】これについては、この抗菌脱臭性粒子材料
のバインダ溶剤としてチタニウムアルコキシドとシラン
系アルコキシドを５０：５０の等モル比でグリコールエ
ーテル溶媒に５〜３０重量％混合したものを用意し、こ
れに前述のアナターゼ型酸化チタン粒子に金属銀等の金
属粒子を分散付着させた抗菌脱臭性粒子材料を０．１〜
５０重量％（通常は、３重量％程度）分散懸濁させ、更
に疎水性セグメントと親水性からなる親疎水性ブロック
共重合体（日本油脂（株）製「モディパーＨシリー
ズ」）を５〜２０重量％配合するものである。For this, a mixture of titanium alkoxide and silane-based alkoxide in an equimolar ratio of 50:50 to a glycol ether solvent in an amount of 5 to 30% by weight was prepared as a binder solvent for the antibacterial deodorizing particle material. The antibacterial deodorizing particle material in which metal particles such as metal silver are dispersed and attached to the anatase type titanium oxide particles described above is 0.1 to 0.1%.
50% by weight (usually about 3% by weight) is dispersed and suspended, and 5 to 20% by weight of a hydrophobic / hydrophobic block copolymer ("MODIPA H series" manufactured by NOF Corporation) composed of a hydrophobic segment and hydrophilicity. %.
【００５９】この光触媒型酸化チタンの液中分散懸濁方
法としては、前述のバインダ溶媒にアナターゼ型酸化チ
タン粒子に金属銀粒子を付着させた抗菌脱臭性粒子を配
合した後、ボールミルにより３〜５時間粉砕分散を行
う。コンクマスター（濃縮液）の場合はボールミルによ
る分散終了後、適切な量の溶媒にて希釈する。次いでホ
モジナイザーで１０〜１５分激しく攪拌し、その後５０
０メッシュの濾布で濾過を行う。この状態で濾過が不十
分なときは軽く手で凝集を解きながら濾過する。そし
て、濾過したスラリー溶液に前述の「モディパー」を規
定量混合し、通常攪拌することにより、光触媒の常温塗
布型の酸化チタンや金属銀（若しくは金属銅）のコーテ
ィング液が得られる。As a method for dispersing and suspending the photocatalytic titanium oxide in a liquid, antibacterial deodorizing particles obtained by adhering metallic silver particles to anatase type titanium oxide particles are blended in the above-mentioned binder solvent, and then mixed by a ball mill. Perform time grinding dispersion. In the case of a conc master (concentrated solution), after the dispersion by a ball mill is completed, the concentrate is diluted with an appropriate amount of a solvent. The mixture was then vigorously stirred with a homogenizer for 10 to 15 minutes.
Filter with a 0 mesh filter cloth. If the filtration is insufficient in this state, the filtration is carried out by lightly dissolving the coagulation by hand. Then, a prescribed amount of the above-mentioned “MODIPA” is mixed with the filtered slurry solution, and the mixture is usually stirred to obtain a coating solution of titanium oxide or metal silver (or metal copper) of a photocatalyst that is applied at room temperature.
【００６０】次いで、この光触媒性の抗菌脱臭性粒子の
コーティング液をフィルタ基材の表面にコーティング
し、常温又は１５０℃以下の低温乾燥により、この抗菌
脱臭性粒子材料がフィルタ基材の表面に分散担持される
ものである。このコーティング方法としては、ここでは
スプレーを採用したが、浸漬法、流しかけ法、刷毛塗り
法、電着塗装法、ロールコート法等を用いてもよい。Next, the coating solution of the photocatalytic antibacterial deodorizing particles is coated on the surface of the filter substrate, and the antibacterial deodorizing particle material is dispersed on the surface of the filter substrate by drying at room temperature or at a low temperature of 150 ° C. or lower. It is carried. As the coating method, spray is used here, but a dipping method, a flowing method, a brush coating method, an electrodeposition coating method, a roll coating method, or the like may be used.
【００６１】そして、このようにして光触媒性アナター
ゼ型酸化チタン＋金属銀（若しくは金属銅）の抗菌脱臭
性粒子がフィルタ基材の表面に分散担持されるメカニズ
ムとしては、次の化２に示した（１）乾燥による脱アル
コール反応（２）微量水分存在下に於ける脱アルコール
反応（３）脱水重合反応により抗菌脱臭性粒子材料が無
機酸化物系結合により堅固にフィルタ基材表面に結合付
着された状態が得られる。The mechanism by which antibacterial and deodorizing particles of photocatalytic anatase-type titanium oxide and metallic silver (or metallic copper) are dispersed and supported on the surface of the filter substrate is shown in the following chemical formula 2. (1) Dealcoholization reaction by drying (2) Dealcoholization reaction in the presence of trace water (3) Antibacterial deodorizing particle material is firmly bonded and attached to the surface of the filter substrate by inorganic oxide bonding by dehydration polymerization reaction State is obtained.
【００６２】[0062]
【化２】 Embedded image
【００６３】次に各種の測定試験を行ったので、その結
果について説明する。初めに図１及び図２は、抗菌性能
を調べたものである。図１「大腸菌」に対する抗菌性能
の試験結果であり、フィルタ表面のアナターゼ型酸化チ
タン粒子に対する金属銀（Ａｇ）粒子の付着量を、０．
１％、１．０％、１０％の３段階としている。酸化チタ
ンの粒子の平均粒径は０．０２μｍである。Next, various measurement tests were performed, and the results will be described. First, FIGS. 1 and 2 examine the antibacterial performance. FIG. 1 shows the test results of the antibacterial performance against “Escherichia coli”.
There are three levels of 1%, 1.0% and 10%. The average particle size of the titanium oxide particles is 0.02 μm.
【００６４】この図１の結果より、アナターゼ型酸化チ
タン粒子に分散付着されるＡｇ粒子の付着量が多いほ
ど、大腸菌の生菌数の減少の度合いが大きいことが分か
る。From the results shown in FIG. 1, it can be seen that the greater the amount of Ag particles dispersed and attached to the anatase type titanium oxide particles, the greater the degree of reduction in the viable number of E. coli.
【００６５】次に図２は、「ＭＲＳＡ（メチシリン耐性
黄色ぶどう球菌）」に対する抗菌性能の試験結果である
が、この場合にもアナターゼ型酸化チタン粒子にＡｇ粒
子を付着させたことにより効果が現れており、やはりＡ
ｇ粒子の付着量が多いほどその効果が大きいことが分か
る。FIG. 2 shows the test results of the antibacterial performance against “MRSA (methicillin-resistant Staphylococcus aureus)”. In this case also, the effect is exhibited by attaching the Ag particles to the anatase type titanium oxide particles. A
It can be seen that the greater the amount of g particles attached, the greater the effect.
【００６６】次の表２は、更に（１）ブランク材（２）
バインダのみ（３）スプレー品（４）ディッピング品の
４種類の試験片を用いて、抗菌試験を行った結果を示し
ている。細菌の種類としては「大腸菌」と「黄色ぶどう
球菌」とを用いている。ここに「ブランク材」とはガラ
ス基板そのままのもので、酸化チタンもＡｇ粒子も付着
されていないものをいう。また「バインダのみ」という
のはガラス基板の表面に前述のチタニウムアルコキシド
とシラン系アルコキシドの混合溶液を塗布し、常温乾燥
したものをいう。「スプレー品」とは、ガラス基板の表
面にアナターゼ型酸化チタン粒子に金属銀若しくは金属
銅を各々３重量％分散付着させた抗菌脱臭性粒子材料を
スプレーを用いて１ｇ／ｍ２程度担持させたものであ
る。そして、ディッピング品とは、前述の抗菌脱臭性粒
子材料を浸漬法により、ガラス基板に担持させたもので
ある。The following Table 2 further shows (1) blank material (2)
The results of an antibacterial test performed using four types of test specimens, binder only (3) spray product (4) dipping product, are shown. "Escherichia coli" and "Staphylococcus aureus" are used as types of bacteria. Here, "blank material" refers to a glass substrate as it is, to which neither titanium oxide nor Ag particles are attached. The term "binder only" means that the above-mentioned mixed solution of titanium alkoxide and silane-based alkoxide is applied to the surface of a glass substrate, and dried at normal temperature. The “sprayed product” refers to carrying about 1 g / m 2 of an antibacterial deodorizing particle material in which 3% by weight of metallic silver or metallic copper is dispersed and attached to anatase-type titanium oxide particles on a surface of a glass substrate by spraying. Things. The dipping product is a product in which the above-mentioned antibacterial deodorizing particle material is supported on a glass substrate by a dipping method.
【００６７】[0067]
【表２】 [Table 2]
【００６８】この表２の結果より、大腸菌を用いた抗菌
試験において、ブランク材及びバインダのみとしたもの
は、２４時間後の生菌数が増加しているのに対し、スプ
レー品及びディッピング品は共に２４時間後にはほぼ死
滅することが分かる。また、黄色ぶどう球菌を用いた抗
菌試験において、ブランク材及びバインダのみとしたも
のも２４時間後の生菌数は減少しているものの、その減
少は僅かなものであるのに対し、スプレー品及びディッ
ピング品は共に、やはり２４時間後にはほぼ死滅するこ
とが分かる。以上の結果から、抗菌脱臭性粒子材料のコ
ーティング方法に拘わらず、優れた抗菌性を示すことが
分かる。From the results shown in Table 2, in the antibacterial test using Escherichia coli, the number of viable bacteria after 24 hours was increased in the case of using only the blank material and the binder, while in the case of the spray product and the dipping product, It can be seen that both are almost dead after 24 hours. In addition, in the antibacterial test using Staphylococcus aureus, the number of viable bacteria after 24 hours also decreased in the case of using only the blank material and the binder. It can be seen that both the dipping products almost die after 24 hours. From the above results, it can be seen that excellent antibacterial properties are exhibited irrespective of the method of coating the antibacterial deodorizing particle material.
【００６９】次に、本発明品の脱臭性能を調べるため
に、図３に示す脱臭性能測定装置を用いたので説明す
る。この装置は、パイレックスガラス製のセパラブルフ
ラスコ（３ｌ）であり、その上部には開閉可能な蓋を有
し、その蓋を閉じた場合には容器内を密閉することがで
きる。また、この蓋にはガス注入採取口が設けられ、ア
セトアルデヒド等の悪臭ガスを注入できるようにしてい
る。更に、この蓋には純空気を取り入れる管と真空ポン
プより容器内の気体を脱気するための管が設けられてい
る。そして、容器内には、試料をのせるための金網が設
けられている。そして更に、このセパラブルフラスコの
底部には、試料に紫外線を照射するための１００Ｗブラ
ックライトが設置されているが、試料からこのブラック
ライトまでの距離は、試料をセットしたときに試料表面
の紫外線強度が２．０ｍＷ／ｃｍ２になるように調節さ
れている。Next, in order to examine the deodorizing performance of the product of the present invention, a deodorizing performance measuring device shown in FIG. 3 was used. This apparatus is a separable flask (31) made of Pyrex glass, and has a lid that can be opened and closed at the top, and when the lid is closed, the inside of the container can be sealed. Further, the lid is provided with a gas injection sampling port so that an odorous gas such as acetaldehyde can be injected. Further, the lid is provided with a pipe for taking in pure air and a pipe for degassing the gas in the container with a vacuum pump. In addition, a wire mesh for mounting a sample is provided in the container. Further, at the bottom of the separable flask, a 100 W black light for irradiating the sample with ultraviolet light is installed, and the distance from the sample to the black light depends on the ultraviolet light on the sample surface when the sample is set. The intensity is adjusted to be 2.0 mW / cm 2 .
【００７０】この装置を用いた測定方法は次の手順で行
う。まず、ブラックライトを１０分以上点灯させて安定
化させる。そして、試料（５ｃｍ×５ｃｍ）を金網にの
せる。測定開始までは、試料に紫外線を当てないように
ＳＵＳ製筒をかぶせておく。次に真空ポンプで減圧して
から、ボンベ入り純空気を入れ容器内の気体を置換す
る。この置換操作を３回繰り返す。そして、悪臭ガスを
容器内に注入し、この悪臭ガスの初期濃度を１００ｐｐ
ｍに調整する。これらの一連の操作終了後、紫外線の照
射を開始とともに脱臭性能試験を開始させる。A measuring method using this apparatus is performed in the following procedure. First, the black light is turned on for 10 minutes or more to be stabilized. Then, the sample (5 cm × 5 cm) is placed on a wire net. Until the start of the measurement, the sample is covered with a SUS cylinder so as not to be irradiated with ultraviolet rays. Next, after reducing the pressure with a vacuum pump, pure air in a cylinder is introduced to replace the gas in the container. This replacement operation is repeated three times. Then, a malodorous gas is injected into the container, and the initial concentration of the malodorous gas is set to 100 pp.
Adjust to m. After these series of operations are completed, irradiation with ultraviolet rays is started, and a deodorizing performance test is started.
【００７１】図４及び図５に示したグラフは、酸化チタ
ンの粒径の大小に依存した脱臭性能について対比したも
のである。この測定は図３に示した脱臭性能測定装置を
用いて、悪臭ガスとして図４ではメチルメルカプタンを
注入した場合、図５ではアンモニアを注入した場合の測
定結果を示している。The graphs shown in FIGS. 4 and 5 compare the deodorizing performance depending on the particle size of titanium oxide. In this measurement, the deodorizing performance measuring apparatus shown in FIG. 3 was used, and FIG. 4 shows the measurement results when methyl mercaptan was injected as a malodorous gas, and FIG. 5 shows the measurement results when ammonia was injected.
【００７２】図４のグラフから酸化チタンの粒径が０．
００７μの方が０．０２μのものに比べて脱臭性能が高
いことが分かる。測定開始から９０分間において、その
脱臭性能の差は縮まることがなく、粒径の小さなものの
方が優れた効果を示している。この理由としては、酸化
チタンの表面積が大きく、触媒性能が高いことによるも
のである。According to the graph of FIG.
It can be seen that 007μ has higher deodorizing performance than 0.02μ. In 90 minutes from the start of the measurement, the difference in the deodorizing performance does not decrease, and the smaller the particle size, the better the effect. This is because the surface area of titanium oxide is large and the catalytic performance is high.
【００７３】図５に示したグラフから、メチルメルカプ
タンの場合と同様、粒径の小さなものの方が優れた脱臭
性能を示すが、この場合は時間を経るごとに脱臭性能の
差は広がっている。つまり、酸化チタンの粒径を大とし
た場合は脱臭時間を長くしてもある程度の脱臭効果しか
得られないのに対し、酸化チタンの粒径を小とした場合
は短時間で著しい効果が得られる。From the graph shown in FIG. 5, as in the case of methyl mercaptan, one having a smaller particle size shows better deodorizing performance, but in this case, the difference in deodorizing performance increases with time. In other words, when the particle size of titanium oxide is large, only a certain degree of deodorizing effect can be obtained even when the deodorizing time is lengthened, while when the particle size of titanium oxide is small, a remarkable effect can be obtained in a short time. Can be
【００７４】次に、図６は脱臭性能における金属銀付着
量依存性を調べたものである。用意した試料は３種類
で、それぞれには同量の酸化チタン粒子が配合されてお
り、金属銀の付着量はそれぞれ０％、１％、５％とした
ものである。そして、図６に示したグラフは悪臭ガスと
してアセトアルデヒドを用いて脱臭性能の測定結果を示
したものである。FIG. 6 shows the dependence of the deodorizing performance on the amount of deposited metal silver. Three kinds of samples were prepared, each containing the same amount of titanium oxide particles, and the adhesion amounts of metallic silver were set to 0%, 1%, and 5%, respectively. The graph shown in FIG. 6 shows the measurement results of the deodorizing performance using acetaldehyde as the malodorous gas.
【００７５】図６の結果より、金属銀の付着量を増すと
脱臭効果が若干増大する傾向も見受けられるが、その傾
向は僅少であり、脱臭性能にそれ程大きな違いは認めら
れなかった。上述の抗菌試験でも示した通り、金属銀は
抗菌性能を発現させるためのものであるから、この図６
の試験結果は、むしろ金属銀の付着により脱臭性能が劣
るのではないかとの懸念に対して、そのような傾向はな
いとの確認が得られたことを示している。From the results shown in FIG. 6, it can be seen that the deodorizing effect tends to slightly increase as the amount of deposited metal silver increases, but the tendency is slight, and no significant difference in the deodorizing performance was recognized. As shown in the antibacterial test described above, metallic silver is used to exhibit antibacterial performance.
The test results indicated that it was confirmed that there was no such tendency in spite of the concern that the deodorizing performance might be inferior due to adhesion of metallic silver.
【００７６】図７は本発明品のバインダと従来のバイン
ダとの脱臭性能の比較である。このグラフでバインダＡ
とは、上述したチタニウムアルコキシドとシラン系アル
コキシドを混合し、フィルタ基材の表面に塗布し、常温
乾燥させたものである。そして、バインダＢは従来のシ
リカ系バインダを用いている。FIG. 7 is a comparison of the deodorizing performance of the binder of the present invention and the conventional binder. In this graph, binder A
The term refers to a mixture of the titanium alkoxide and the silane-based alkoxide described above, applied to the surface of the filter substrate, and dried at room temperature. As the binder B, a conventional silica-based binder is used.
【００７７】図７の結果から、まず初期脱臭効果におい
て、本発明品のバインダＡの方が優れた脱臭効果がみら
れる。そして、アルデヒド追加後においては、バインダ
Ａ及びバインダＢ共に初期に比べると、その効果は稍劣
ってしまう。これらは消耗品である以上劣化することは
避けられないが、その劣化の度合いがバインダＢでは大
きくなっているのに対し、バインダＡは非常に小さくな
っていることから、バインダＡは耐久性に優れたもので
あるといえる。From the results shown in FIG. 7, it can be seen that the binder A of the present invention has a superior deodorizing effect in the initial deodorizing effect. Then, after the addition of the aldehyde, the effect of both the binder A and the binder B is slightly inferior to the initial stage. Since these are consumables, it is inevitable that they deteriorate, but the degree of the deterioration is large in the binder B, while the binder A is very small. It can be said that it is excellent.
【００７８】以上、本実施例を順に説明したが、要する
に本願発明は、酸化チタン粒子に金属銀若しくは金属銅
を分散付着させた抗菌脱臭性粒子材料をフィルタ基材の
表面に分散担持させたものであることから、酸化チタン
粒子により脱臭性能を発揮し、更に金属銀若しくは金属
銅により抗菌性をも有するものとなる。The present embodiment has been described in the above order. In short, the invention of the present application is a device in which an antibacterial deodorizing particle material obtained by dispersing and attaching metallic silver or metallic copper to titanium oxide particles is dispersed and supported on the surface of a filter substrate. Therefore, the titanium oxide particles exhibit a deodorizing performance, and the metallic silver or metallic copper also has antibacterial properties.
【００７９】本発明は、上記した実施例に何等限定され
るものではなく、本発明の趣旨を逸脱しない範囲で種々
の改変が可能である。例えば、酸化チタンの平均粒径は
０．０４μｍ未満、金属銀若しくは金属銅の粒径は４ｎ
ｍ未満であれば何等限定されることなく適用することが
できる。The present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the present invention. For example, the average particle size of titanium oxide is less than 0.04 μm, and the particle size of metallic silver or metallic copper is 4n.
If it is less than m, it can be applied without any limitation.
【００８０】また、フィルタ基材の表面に担持される抗
菌脱臭性粒子材料の担持量は、１ｇ／ｍ２以上であれば
限定されず、またその抗菌脱臭性粒子材料において、酸
化チタン粒子に分散付着される金属粒子の付着量は、酸
化チタン粒子単位重量当り０．１重量％以上５０重量％
以下であれば何等限定されることはないが、好ましくは
０．５重量％以上５重量％以下である。The amount of the antibacterial and deodorizing particulate material supported on the surface of the filter substrate is not limited as long as it is 1 g / m 2 or more. The amount of metal particles to be deposited is 0.1% by weight or more and 50% by weight per unit weight of titanium oxide particles.
There is no particular limitation as long as it is below, but it is preferably 0.5% by weight or more and 5% by weight or less.
【００８１】更に、上述の抗菌脱臭性粒子材料には、酸
化チタンの触媒作用を高める白金触媒やパラジウム触媒
等をも混合させて、その触媒性能を高めることもでき
る。Further, the above antibacterial deodorizing particle material may be mixed with a platinum catalyst or a palladium catalyst which enhances the catalytic action of titanium oxide to enhance the catalytic performance.
【００８２】また更に、フィルタ基材には、その機能を
果たすものであれば何等限定されることはなく、繊維、
発泡樹脂、セラミックス多孔質体又はハニカム形状のも
の、金属メッシュ等が挙げられる。The filter substrate is not particularly limited as long as it fulfills its function.
Examples thereof include a foamed resin, a porous ceramic body or a honeycomb shape, and a metal mesh.
【００８３】[0083]
【発明の効果】本発明による抗菌脱臭性光触媒型フィル
タは、酸化チタン粒子に金属銀若しくは金属銅の金属粒
子を分散付着させた抗菌脱臭性粒子材料をフィルタ基材
の表面に分散担持させてなるものであるから、この抗菌
脱臭性粒子材料にブラックライトにより紫外線を照射す
ることにより、その抗菌脱臭性粒子材料中のアナターゼ
型酸化チタン粒子が活性化し、このフィルタ基材に吸引
される空気中の細菌を死滅させ、また空気中の悪臭成分
を分解することができる。そして、この抗菌脱臭性粒子
材料の酸化チタン粒子に分散担持されている金属銀若し
くは金属銅粒子が活性助剤として機能し、空気中の細菌
や悪臭の除去性能が高められ、また繰り返しの利用にも
高性能が持続されることになる。更にまた、紫外線を照
射しない状態においても金属銀若しくは金属銅粒子が抗
菌性を維持し、フィルタでの細菌の増殖がないものとな
る。The antibacterial deodorizing photocatalytic filter according to the present invention is obtained by dispersing and supporting an antibacterial deodorizing particle material in which metal particles of metallic silver or metallic copper are dispersed and attached to titanium oxide particles on the surface of a filter substrate. Since the antibacterial deodorizable particle material is irradiated with ultraviolet light by black light, the anatase type titanium oxide particles in the antibacterial deodorant particle material are activated, and the air in the air sucked by the filter substrate is removed. It can kill bacteria and break down odorous components in the air. And the silver or copper metal particles dispersed and supported on the titanium oxide particles of this antibacterial deodorizing particle material function as an active aid, and the performance of removing bacteria and bad odors in the air is enhanced. High performance will be maintained. Furthermore, the metal silver or metal copper particles maintain the antibacterial property even in a state where no ultraviolet light is irradiated, and no bacteria grow on the filter.
【００８４】また、この抗菌脱臭性光触媒型フィルタ
は、酸化チタン粒子の平均粒径、金属粒子の粒径、酸化
チタン粒子に分散付着される金属粒子の付着量、フィル
タ基材の表面に分散担持される抗菌脱臭性粒子材料の担
持量、バインダ溶液の粘度、フィルタ基材表面のバイン
ダ厚等が適正な範囲にあることから、優れた抗菌脱臭効
果を発揮できるものとなる。The antibacterial deodorizing photocatalytic filter has an average particle diameter of titanium oxide particles, a particle diameter of metal particles, an amount of metal particles dispersed and adhered to the titanium oxide particles, and a dispersion support on the surface of the filter substrate. Since the carried amount of the antibacterial deodorizing particle material, the viscosity of the binder solution, the thickness of the binder on the surface of the filter substrate, and the like are within appropriate ranges, an excellent antibacterial deodorizing effect can be exhibited.
【００８５】一方、本発明に係る抗菌脱臭性光触媒型フ
ィルタの製造方法は、アナターゼ型酸化チタン粒子に金
属銀若しくは金属銅の金属粒子を分散付着させた抗菌脱
臭性粒子材料を無機系アルコキシドの溶媒に分散懸濁
し、これをフィルタ基材の表面に塗着し、その無機系ア
ルコキシドの溶媒の常温での脱アルコール及び脱水重合
反応により抗菌脱臭性粒子材料をフィルタ基材の表面に
分散担持させるようにしたものであるから、抗菌脱臭性
粒子材料がフィルタ基材の表面に無機酸化物系結合によ
り堅固に結合付着されたものとなり、有機系バインダの
ような光触媒反応の影響は回避され、しかも常温乾燥で
の処理であるため製造しやすいものとなっている。On the other hand, the method for producing an antibacterial deodorizing photocatalytic filter according to the present invention is a method for preparing an antibacterial deodorizing particle material obtained by dispersing and attaching metallic silver or metallic copper particles to anatase type titanium oxide particles. The inorganic alkoxide solvent is applied to the surface of the filter substrate by de-alcoholization and dehydration polymerization at room temperature so that the antibacterial deodorizing particle material is dispersed and supported on the surface of the filter substrate. As a result, the antibacterial deodorizing particle material is firmly bonded and attached to the surface of the filter substrate by an inorganic oxide-based bond, so that the influence of a photocatalytic reaction such as an organic binder is avoided, and at room temperature. Since the treatment is performed by drying, it is easy to manufacture.
【００８６】この方法で製造された抗菌脱臭性光触媒型
フィルタは、抗菌脱臭性粒子材料とフィルタ基材とがＴ
ｉ−Ｓｉ−Ｏ結合により結着されているものであるか
ら、フィルタとしての柔軟性が維持され、ひび割れ等の
クラックも起きにくいものとなり、更に、親疎水性ブロ
ック共重合体を配合していることから、親疎水性ブロッ
ク共重合体のうち疎水性セグメントによる抗菌脱臭性粒
子材料のフィルタ基材への接着性及び親水性セグメント
によるフィルタ基材の表面親水性が高いものとなること
から、耐久性の高いものとなる。The antibacterial and deodorizing photocatalytic filter manufactured by this method has a Tb material and a filter base material of T.
Since it is bound by i-Si-O bonds, flexibility as a filter is maintained, cracks such as cracks are unlikely to occur, and a hydrophobic / hydrophobic block copolymer is further compounded. From, the adhesion of the antibacterial deodorizing particle material to the filter substrate by the hydrophobic segment of the hydrophilic-hydrophobic block copolymer and the surface hydrophilicity of the filter substrate by the hydrophilic segment become high, so that the durability is improved. It will be expensive.
【００８７】以上のようなことから、本発明に係る抗菌
脱臭性光触媒型フィルタ及びその製造方法は、医療・衛
生、精密電子機器製造作業、一般家庭等の様々な環境に
おける空気清浄等に優れた効果を示すことから、産業上
極めて有用なものとなる。As described above, the antibacterial and deodorizing photocatalytic filter according to the present invention and the method for producing the same are excellent in air purification in various environments such as medical and hygiene, precision electronic device production, and general households. Since it shows an effect, it becomes extremely useful industrially.
【図１】大腸菌を用いたフィルタの抗菌試験結果を示し
た図である。FIG. 1 is a diagram showing the results of an antibacterial test on a filter using Escherichia coli.
【図２】ＭＲＳＡを用いたフィルタの抗菌試験結果を示
した図である。FIG. 2 is a diagram showing an antibacterial test result of a filter using MRSA.
【図３】本発明品の脱臭性能を測定するための脱臭性能
測定装置の概略を示した図である。FIG. 3 is a diagram schematically showing a deodorizing performance measuring device for measuring the deodorizing performance of the product of the present invention.
【図４】悪臭ガスとしてメチルメルカプタンを用いた場
合の本発明品に係る抗菌脱臭性光触媒型フィルタの酸化
チタンの粒径の違いによる脱臭性能試験の結果を示した
図である。FIG. 4 is a diagram showing the results of a deodorizing performance test of the antibacterial deodorizing photocatalytic filter according to the present invention, in which methyl mercaptan is used as a malodorous gas, depending on the difference in the particle size of titanium oxide.
【図５】悪臭ガスとしてアンモニアを用いた場合の本発
明品に係る抗菌脱臭性光触媒型フィルタの酸化チタンの
粒径の違いによる脱臭性能試験の結果を示した図であ
る。FIG. 5 is a diagram showing the results of a deodorizing performance test of the antibacterial deodorizing photocatalytic filter according to the present invention when ammonia is used as a malodorous gas, depending on the difference in the particle size of titanium oxide.
【図６】悪臭ガスとしてアセトアルデヒドを用いた場合
の本発明品に係る抗菌脱臭性光触媒型フィルタの金属銀
の含有量の違いによる脱臭性能試験の結果を示した図で
ある。FIG. 6 is a diagram showing the results of a deodorizing performance test based on differences in the content of metallic silver in an antibacterial deodorizing photocatalytic filter according to the present invention when acetaldehyde is used as a malodorous gas.
【図７】異なるバインダの耐久性への影響を調べた図で
ある。FIG. 7 is a diagram illustrating the effect of different binders on durability.
───────────────────────────────────────────────────── 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） Ｂ０１Ｊ 23/72 Ｂ０１Ｊ 23/72 Ｍ 23/89 23/89 Ｍ Ｂ０１Ｄ 53/36 Ｈ (72)発明者 貴田 昇司 愛知県岩倉市大地町上千８−１ 三興石油 工業株式会社内 Ｆターム(参考） 4C058 AA19 BB07 JJ04 JJ05 JJ23 4C080 AA07 BB02 BB05 BB08 CC01 CC12 CC13 CC15 JJ03 JJ09 KK08 LL03 LL10 MM02 MM04 MM05 MM07 MM19 MM29 NN01 NN02 NN22 NN29 QQ03 4D019 AA01 AA10 BA02 BA05 BA13 BB02 BB03 BB06 BB07 BC05 BC06 BC07 BC10 BC20 CA01 CB06 4D048 AA19 AA22 AB03 BA05X BA07X BA11Y BA13X BA34X BA35X BA39X BA41X BB02 BB07 BB08 BB09 CA01 CD05 EA01 EA10 4G069 AA03 AA08 AA09 BA03B BA04A BA04B BA07A BA08A BA13A BA14B BA17 BA21C BA22A BA48A BB02A BB02B BC31A BC31B BC32A BC32B BC50C BC72A BC75A BD05C BE06C BE32A BE34A CA01 CA11 CA17 DA05 EA08 EA09 EA12 EA18 EB11 EB18X EB18Y EB19 EC22X ED05 FB06 FB11 FB23 FB24 FB57 FC02 FC04 FC08 FC10 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B01J 23/72 B01J 23/72 M 23/89 23/89 M B01D 53/36 H (72) Inventor Kida Noboru F-1 term (reference) in Sanko Sekiyu Kogyo Co., Ltd. 4-8 NN01 NN02 NN22 NN29 QQ03 4D019 AA01 AA10 BA02 BA05 BA13 BB02 BB03 BB06 BB07 BC05 BC06 BC07 BC10 BC20 CA01 CB06 4D048 AA19 AA22 AB03 BA05X BA07X BA11Y BA13X BA34X BA35X BA39A04 BB02 A07 BB02 A04 BB02 A04 BB02 BA08A BA13A BA14B BA17 BA21C BA22A BA48A BB02A BB02B BC31A BC31B BC32A BC32B BC50C BC72A BC75A BD05C BE06C BE32A BE34A CA01 CA11 CA17 DA0 5 EA08 EA09 EA12 EA18 EB11 EB18X EB18Y EB19 EC22X ED05 FB06 FB11 FB23 FB24 FB57 FC02 FC04 FC08 FC10
Claims (15)
の金属粒子を分散付着させた抗菌脱臭性粒子材料をフィ
ルタ基材の表面に分散担持させてなることを特徴とする
抗菌脱臭性光触媒型フィルタ。1. An antibacterial deodorizing photocatalytic filter characterized in that an antibacterial deodorizing particle material in which metal particles of metallic silver or metallic copper are dispersed and attached to titanium oxide particles is dispersed and supported on the surface of a filter substrate. .
晶構造のものであることを特徴とする請求項１に記載の
抗菌脱臭性光触媒型フィルタ。2. The antibacterial deodorizing photocatalytic filter according to claim 1, wherein the titanium oxide particles have an anatase crystal structure.
４μｍ未満であり、前記金属粒子の粒径は４ｎｍ未満で
あることを特徴とする請求項１又は２に記載の抗菌脱臭
性光触媒型フィルタ。3. The titanium oxide particles have an average particle size of 0.0
The antibacterial deodorizing photocatalytic filter according to claim 1 or 2, wherein the diameter of the metal particles is less than 4 µm and the particle size of the metal particles is less than 4 nm.
属粒子の付着量は、前記酸化チタン粒子の単位重量当り
０．１重量％以上５０重量％以下であることを特徴とす
る請求項１乃至３に記載の抗菌脱臭性光触媒型フィル
タ。4. The method according to claim 1, wherein the amount of the metal particles dispersed and attached to the titanium oxide particles is 0.1% by weight or more and 50% by weight or less per unit weight of the titanium oxide particles. 4. The antibacterial and deodorizing photocatalytic filter according to 3.
る抗菌脱臭性粒子材料の担持量は、１ｇ／ｍ２以上であ
ることを特徴とする請求項１乃至４に記載の抗菌脱臭性
光触媒型フィルタ。5. The antibacterial deodorizing photocatalyst according to claim 1, wherein the amount of the antibacterial deodorizing particulate material dispersed and supported on the surface of the filter substrate is 1 g / m 2 or more. Type filter.
系結着剤によりフィルタ基材表面に結合付着されている
ことを特徴とする請求項１乃至５に記載の抗菌脱臭性光
触媒型フィルタ。6. The antibacterial deodorizing photocatalytic filter according to claim 1, wherein the antibacterial deodorizing particle material is bonded and attached to a surface of the filter substrate by an inorganic oxide binder. .
属銅粒子を分散付着させた抗菌脱臭性粒子材料には、更
に酸化チタン粒子の触媒性能を高める白金触媒若しくは
パラジウム触媒が含まれていることを特徴とする請求項
１乃至６に記載の抗菌脱臭性光触媒型フィルタ。7. The antibacterial and deodorizing particle material in which metal silver or metal copper particles are dispersed and attached to the titanium oxide particles, further comprising a platinum catalyst or a palladium catalyst for improving the catalytic performance of the titanium oxide particles. An antibacterial and deodorizing photocatalytic filter according to any one of claims 1 to 6.
属銅粒子を分散付着させた抗菌脱臭性粒子材料には、酸
化チタン粒子に金属銀及び金属銅が付着されていない単
独酸化チタン粒子が混合されていることを特徴とする請
求項１乃至７に記載の抗菌脱臭性光触媒型フィルタ。8. An antibacterial and deodorizing particle material in which metallic silver or metallic copper particles are dispersed and adhered to the titanium oxide particles, titanium oxide particles are mixed with individual titanium oxide particles to which metallic silver and metallic copper are not adhered. The antibacterial and deodorizing photocatalytic filter according to any one of claims 1 to 7, wherein:
セラミックス多孔質体又はハニカム形状のもの、金属メ
ッシュからなることを特徴とする請求項１乃至８に記載
の抗菌脱臭性光触媒型フィルタ。9. The filter base material is made of a fiber, a foamed resin,
The antibacterial deodorizing photocatalytic filter according to any one of claims 1 to 8, wherein the filter is made of a porous ceramic body or a honeycomb shape, and a metal mesh.
はゼオライト等の吸着活性剤を担持させ、該吸着活性剤
に前記抗菌脱臭性粒子材料が分散担持されてなることを
特徴とする請求項１乃至９に記載の抗菌脱臭性光触媒型
フィルタ。10. The filter substrate according to claim 1, wherein an adsorbent such as activated carbon or zeolite is supported on the surface of the filter base material, and the antibacterial deodorizing particle material is dispersed and supported on the adsorbent. 10. The antibacterial deodorizing photocatalytic filter according to 9.
若しくは金属銅の金属粒子を分散付着させた抗菌脱臭性
粒子材料を無機系アルコキシドの溶媒に分散懸濁し、こ
れをフィルタ基材の表面に塗着し、前記溶媒の常温での
脱アルコール及び脱水重合反応により前記抗菌脱臭性粒
子材料をフィルタ基材の表面に分散担持させるようにし
た抗菌脱臭性光触媒型フィルタの製造方法。11. An antibacterial and deodorizing particle material in which metallic silver or metallic copper particles are dispersed and attached to anatase-type titanium oxide particles is dispersed and suspended in a solvent of an inorganic alkoxide, and this is applied to the surface of a filter substrate. A method for producing an antibacterial deodorizing photocatalytic filter, wherein the antibacterial deodorizing particle material is dispersed and supported on the surface of the filter substrate by a dealcoholization and dehydration polymerization reaction of the solvent at normal temperature.
ムアルコキシド及びシラン系アルコキシドの混合溶媒で
あることを特徴とする請求項１１に記載される抗菌脱臭
性光触媒型フィルタの製造方法。12. The method according to claim 11, wherein the inorganic alkoxide is a mixed solvent of a titanium alkoxide and a silane alkoxide.
疎水性セグメントと親水性セグメントからなる親疎水性
ブロック共重合体を配合してなることを特徴とする請求
項１１又は１２に記載の抗菌脱臭性光触媒型フィルタの
製造方法。13. The solvent for the inorganic alkoxide includes:
The method for producing an antibacterial deodorizing photocatalytic filter according to claim 11 or 12, wherein a hydrophobic-hydrophobic block copolymer comprising a hydrophobic segment and a hydrophilic segment is blended.
前記フィルタ基材の表面に空気中の汚染物質が付着する
のを防止するための防汚剤を配合してなることを特徴と
する請求項１１乃至１３に記載の抗菌脱臭性光触媒型フ
ィルタの製造方法。14. The solvent for the inorganic alkoxide includes:
The antibacterial deodorizing photocatalyst filter according to any one of claims 11 to 13, wherein an antifouling agent for preventing a contaminant in the air from adhering to the surface of the filter substrate is blended. Method.
くはシリコン基を含む疎水性ポリマーであることを特徴
とする請求項１１乃至１４に記載の抗菌脱臭性光触媒型
フィルタの製造方法。15. The method for producing an antibacterial deodorizing photocatalytic filter according to claim 11, wherein the antifouling agent is a hydrophobic polymer containing a fluoroalkyl group or a silicon group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10249585A JP2000070673A (en) | 1998-09-03 | 1998-09-03 | Antibacterial deodorizing photocatalyst type filter and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10249585A JP2000070673A (en) | 1998-09-03 | 1998-09-03 | Antibacterial deodorizing photocatalyst type filter and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000070673A true JP2000070673A (en) | 2000-03-07 |
Family
ID=17195212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10249585A Pending JP2000070673A (en) | 1998-09-03 | 1998-09-03 | Antibacterial deodorizing photocatalyst type filter and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000070673A (en) |
Cited By (18)
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|---|---|---|---|---|
| JP2002146453A (en) * | 2000-11-08 | 2002-05-22 | Furuya Kinzoku:Kk | Silver alloy material and antibacterial material |
| JP2003251195A (en) * | 2002-03-01 | 2003-09-09 | Tayca Corp | Titanium oxide photocatalyst having excellent nitrogen oxide removing capacity |
| JP2004105958A (en) * | 2002-08-30 | 2004-04-08 | Sk Kaken Co Ltd | Method for manufacturing porous photocatalyst composite powder |
| JP2005318999A (en) * | 2004-05-07 | 2005-11-17 | Catalysts & Chem Ind Co Ltd | Antibacterial deodorant and its manufacturing method |
| KR100628667B1 (en) | 2005-04-22 | 2006-09-26 | (주)엔피씨 | Filter comprising antimicrobial nano metal components and process for preparing the same |
| JP2006257070A (en) | 2005-02-16 | 2006-09-28 | Nippon Soda Co Ltd | Liquid antimicrobial agent composition |
| JP2006334494A (en) * | 2005-06-01 | 2006-12-14 | Yoshinori Kanno | Filter, air washing apparatus, refrigeration equipment, and water purification apparatus |
| JP2009011905A (en) * | 2007-07-03 | 2009-01-22 | Panasonic Corp | Sterilization filter, and method for producing the same |
| JP2010104963A (en) * | 2008-10-31 | 2010-05-13 | Toho Titanium Co Ltd | Sulfur-containing titanium oxide compound, method for manufacturing sulfur-containing titanium oxide compound, and dispersion of sulfur-containing titanium oxide compound |
| WO2010073738A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社Ｎｂｃメッシュテック | Anti-viral member |
| JP2010234062A (en) * | 2010-06-02 | 2010-10-21 | Jgc Catalysts & Chemicals Ltd | Method for producing antibacterial deodorizer |
| WO2011078203A1 (en) * | 2009-12-24 | 2011-06-30 | 国立大学法人 東京大学 | Virus inactivator |
| WO2013008807A1 (en) * | 2011-07-11 | 2013-01-17 | 住友化学株式会社 | Anti-viral agent capable of inactivating virus, and method for inactivating virus |
| JP2014133199A (en) * | 2013-01-09 | 2014-07-24 | Nippon Pillar Packing Co Ltd | Method for manufacturing photocatalytic filter material and photocatalyst carrying composition |
| US20150351387A1 (en) * | 2012-08-10 | 2015-12-10 | Tsukasa Sakurada | Sterilizing Agents, Their Method of Manufacture and Uses |
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|---|---|---|---|---|
| JP2002146453A (en) * | 2000-11-08 | 2002-05-22 | Furuya Kinzoku:Kk | Silver alloy material and antibacterial material |
| JP2003251195A (en) * | 2002-03-01 | 2003-09-09 | Tayca Corp | Titanium oxide photocatalyst having excellent nitrogen oxide removing capacity |
| JP2004105958A (en) * | 2002-08-30 | 2004-04-08 | Sk Kaken Co Ltd | Method for manufacturing porous photocatalyst composite powder |
| JP2005318999A (en) * | 2004-05-07 | 2005-11-17 | Catalysts & Chem Ind Co Ltd | Antibacterial deodorant and its manufacturing method |
| JP2006257070A (en) | 2005-02-16 | 2006-09-28 | Nippon Soda Co Ltd | Liquid antimicrobial agent composition |
| KR100628667B1 (en) | 2005-04-22 | 2006-09-26 | (주)엔피씨 | Filter comprising antimicrobial nano metal components and process for preparing the same |
| JP2006334494A (en) * | 2005-06-01 | 2006-12-14 | Yoshinori Kanno | Filter, air washing apparatus, refrigeration equipment, and water purification apparatus |
| JP2009011905A (en) * | 2007-07-03 | 2009-01-22 | Panasonic Corp | Sterilization filter, and method for producing the same |
| JP2010104963A (en) * | 2008-10-31 | 2010-05-13 | Toho Titanium Co Ltd | Sulfur-containing titanium oxide compound, method for manufacturing sulfur-containing titanium oxide compound, and dispersion of sulfur-containing titanium oxide compound |
| WO2010073738A1 (en) * | 2008-12-26 | 2010-07-01 | 株式会社Ｎｂｃメッシュテック | Anti-viral member |
| WO2011078203A1 (en) * | 2009-12-24 | 2011-06-30 | 国立大学法人 東京大学 | Virus inactivator |
| US9572347B2 (en) | 2009-12-24 | 2017-02-21 | The University Of Tokyo | Method for inactivating a virus |
| JP2010234062A (en) * | 2010-06-02 | 2010-10-21 | Jgc Catalysts & Chemicals Ltd | Method for producing antibacterial deodorizer |
| WO2013008807A1 (en) * | 2011-07-11 | 2013-01-17 | 住友化学株式会社 | Anti-viral agent capable of inactivating virus, and method for inactivating virus |
| JP2013018736A (en) * | 2011-07-11 | 2013-01-31 | Sumitomo Chemical Co Ltd | Anti-viral agent capable of inactivating virus, and method for inactivating virus |
| US20150351387A1 (en) * | 2012-08-10 | 2015-12-10 | Tsukasa Sakurada | Sterilizing Agents, Their Method of Manufacture and Uses |
| US10051859B2 (en) * | 2012-08-10 | 2018-08-21 | Tsukasa Sakurada | Sterilizing agents, their method of manufacture and uses |
| US11033026B2 (en) | 2012-08-10 | 2021-06-15 | Tsukasa Sakurada | Sterilizing agents, their method of manufacture and uses |
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| US20210107804A1 (en) * | 2019-10-15 | 2021-04-15 | Geraldo Roberto Silveira | Waste water filtration compositions, systems and methods |
| WO2023079766A1 (en) * | 2021-11-03 | 2023-05-11 | アンデス電気株式会社 | Photocatalyst antibacterial deodorizing material, method for producing same, antibacterial deodorizing material, and antibacterial deodorizing filter |
| JP2023068678A (en) * | 2021-11-03 | 2023-05-18 | アンデス電気株式会社 | Photocatalytic antibacterial deodorant, manufacturing method thereof, antibacterial deodorant, and antibacterial deodorant filter |
| JP7436992B2 (en) | 2021-11-03 | 2024-02-22 | アンデス電気株式会社 | Photocatalytic antibacterial deodorizing material, its manufacturing method, antibacterial deodorizing material, and antibacterial deodorizing filter |
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