JPH08117556A - Photo-reactive harmful matter-removing material and production thereof - Google Patents
Photo-reactive harmful matter-removing material and production thereofInfo
- Publication number
- JPH08117556A JPH08117556A JP6254034A JP25403494A JPH08117556A JP H08117556 A JPH08117556 A JP H08117556A JP 6254034 A JP6254034 A JP 6254034A JP 25403494 A JP25403494 A JP 25403494A JP H08117556 A JPH08117556 A JP H08117556A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- removing material
- woven fabric
- titania sol
- nonwoven fabric
- 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
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 149
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 71
- 239000000126 substance Substances 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 239000003365 glass fiber Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 11
- -1 polyethylene Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 235000019645 odor Nutrition 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XRPZVNIXPWZPCA-UHFFFAOYSA-N ethenyl acetate;styrene Chemical compound CC(=O)OC=C.C=CC1=CC=CC=C1 XRPZVNIXPWZPCA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 229920006215 polyvinyl ketone Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241001453636 Salvinia Species 0.000 description 1
- 206010041925 Staphylococcal infections Diseases 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PVOXCLVRHYZZEP-UHFFFAOYSA-M [OH-].[O-2].[Ti+3] Chemical compound [OH-].[O-2].[Ti+3] PVOXCLVRHYZZEP-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、酸化チタンの光触媒能
力を利用し、悪臭や細菌等の有害物が除去できる光反応
性有害物除去材及びその製造方法に関するものであり、
更に詳しくは光触媒能が最適に発現する酸化チタンを効
率良く不織布に担持させた光反応性有害物除去材及びそ
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 a photoreactive harmful substance removing material capable of removing harmful substances such as malodor and bacteria by utilizing the photocatalytic ability of titanium oxide, and a method for producing the same.
More specifically, the present invention relates to a photoreactive harmful substance removing material in which a non-woven fabric is efficiently loaded with titanium oxide exhibiting the optimum photocatalytic ability, and a method for producing the same.
【0002】[0002]
【従来の技術】環境問題に対する関心の高まりに伴い、
日常生活に於ても手軽に悪臭が除去できる悪臭除去材や
除去装置の開発の要求が増えている。また、MRSAの
院内感染の防止やプール等の水処理等に対して抗菌性が
高くてしかも人体には安全な抗菌材の開発の要求も急速
に増えてきている。2. Description of the Related Art With increasing interest in environmental issues,
There is an increasing demand for development of odor removing materials and odor removing devices that can easily remove odors in daily life. In addition, there is a rapidly increasing demand for the development of an antibacterial material which has a high antibacterial property against MRSA nosocomial infections and water treatment of pools and the like and is safe for the human body.
【0003】このような特殊であり、困難な要求に対
し、近年酸化チタンが注目を集めている。酸化チタンは
従来、白色顔料として塗料や填料、化粧品として古くか
ら使用されている。また酸化チタンは半導体として、そ
の光触媒能力の研究も古くから行われていた。例えば
J.Oil.Chem.Assoc.,61、351
(1978)には水アルコール混合溶液中で懸濁した酸
化チタン微粉末によるアルコールの光分解が報告されて
おり、特公昭57−47753号公報には水の光分解が
報告されている。更に近年に及んで、特開昭61−13
5669号公報では硫化物の分解や、特公平2−622
97号公報では窒素酸化物の光分解、また特開平3−6
9695号及び同6−256540号公報では抗(殺)
菌作用や水苔の活性抑制が開示されている。In response to such special and difficult requirements, titanium oxide has been attracting attention in recent years. Titanium oxide has been used as a white pigment for a long time in paints, fillers, and cosmetics. As a semiconductor, titanium oxide has been studied for a long time for its photocatalytic ability. For example, J. Oil. Chem. Assoc. , 61 , 351
(1978) reported photodecomposition of alcohol by titanium oxide fine powder suspended in a hydroalcoholic mixed solution, and Japanese Patent Publication No. 57-47753 reported photodecomposition of water. Furthermore, in recent years, JP-A-61-13
Japanese Patent No. 5669 discloses decomposition of sulfide and Japanese Patent Publication No. 2-622.
No. 97, photodecomposition of nitrogen oxides, and JP-A-3-6.
In 9695 and 6-256540 gazettes, anti (kill)
Bacterial action and inhibition of water moss activity are disclosed.
【0004】脱臭や抗菌性の諸データがそろって後、特
開平5−253544号公報では光触媒である酸化チタ
ンをタイル表面に焼結によって固定して使用しようとす
る試みが述べられている。しかし、この様な方法では加
熱処理にコストがかかる問題と、担持体の表面積により
固定する酸化チタンの量が規制され、更にバインダーに
よって有効な表面積を減ぜられ、その能力が減少してし
まう問題があった。After collecting various data on deodorization and antibacterial properties, Japanese Patent Laid-Open No. 253544/1993 describes an attempt to fix titanium oxide as a photocatalyst on the surface of a tile by sintering and use it. However, in such a method, the heat treatment is costly, and the amount of titanium oxide to be fixed is regulated by the surface area of the support, and further, the effective surface area is reduced by the binder, and the ability is reduced. was there.
【0005】酸化チタンを充分量担持させるには、担持
体の表面積を大きくすることが必要であり、例えば特開
平3−94814号公報には酸化チタンを担持させた担
持体を波板状に加工して用いる方法が述べられいる。し
かし、この方法でも光触媒である酸化チタンは担持体と
共に焼結によって成形固定化されるため、コストが高く
なるり、また後加工がしにくい問題があった。In order to carry a sufficient amount of titanium oxide, it is necessary to increase the surface area of the carrier. For example, in JP-A-3-94814, a carrier carrying titanium oxide is processed into a corrugated plate. The method to be used is described. However, even in this method, since titanium oxide, which is a photocatalyst, is molded and fixed together with the carrier by sintering, there is a problem that the cost becomes high and post-processing is difficult.
【0006】[0006]
【発明が解決しようとする課題】本発明の課題は、酸化
チタンの光触媒能力を利用し、悪臭や細菌等の有害物が
除去できる光反応性有害物除去材及びその製造方法を提
供するものであり、詳しくは光触媒能が最適に発現する
酸化チタンを不織布に担持させた光反応性有害物除去材
及び光触媒能に優れる酸化チタンを不織布に効率的に担
持させる光反応性有害物除去材の製造方法を提供するも
のである。更に本発明では、意匠性、風合いや肌触り等
のシートとして他の機能を持たせるために、別の不織布
やフィルムと張り合わせることもできる光反応性有害物
除去材を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a photoreactive harmful substance removing material capable of removing harmful substances such as malodor and bacteria by utilizing the photocatalytic ability of titanium oxide, and a method for producing the same. Yes, specifically, the production of photoreactive toxic substance removal material in which titanium oxide that optimally exhibits photocatalytic activity is supported on the non-woven fabric and photoreactive toxic substance removal material that efficiently supports titanium oxide in the non-woven fabric with excellent photocatalytic ability. It provides a method. Another object of the present invention is to provide a photoreactive harmful substance removing material which can be laminated with another non-woven fabric or film in order to have other functions as a sheet such as design, texture and touch.
【0007】[0007]
【課題を解決するための手段】本発明者らは上記課題を
解決するため検討した結果、アルカリ処理によりチタニ
アゾルから析出された酸化チタンを不織布に担持させる
ことによって、優れた光触媒能を有する酸化チタンの析
出と不織布への担持が同時に可能となり、その結果低コ
ストで優れた性能の光反応性有害物除去材が得られるこ
とを見出し、本課題を解決するに到った。Means for Solving the Problems As a result of studies conducted by the present inventors to solve the above problems, the titanium oxide precipitated from a titania sol by an alkali treatment is carried on a non-woven fabric, whereby titanium oxide having excellent photocatalytic activity is obtained. It has been found that the precipitation of the above can be carried out at the same time as the deposition on the non-woven fabric, and as a result, a photoreactive harmful substance removing material with excellent performance can be obtained at low cost, and the present problem has been solved.
【0008】以下に本発明の光反応性有害物除去材の構
成要素及びその製造方法を詳細に説明する。本発明の光
反応性有害物除去材は、チタニアゾルから析出させた酸
化チタンと不織布で構成され、不織布は好ましくは少な
くとも熱可塑性樹脂繊維かガラス繊維かの何れか一方を
含有してなる。本発明に係わるチタニアゾルは、天然に
産するチタン源から酸化チタンを製造する過程に於て得
られる含水酸化チタンの沈澱をアルカリ洗浄し、塩酸や
硝酸等の強酸で解膠した半透明の酸性水系の分散ゾルを
云う。含水酸化チタンとは「酸化チタン」(清野学著、
技報堂出版 1991年発行)に詳細に述べられている
が、一般的には硫酸法酸化チタンの製造工程において硫
酸チタン溶液を熱加水分解して得られる。The components of the photoreactive harmful substance removing material of the present invention and the method for producing the same will be described in detail below. The photoreactive harmful substance removing material of the present invention is composed of titanium oxide precipitated from titania sol and a non-woven fabric, and the non-woven fabric preferably contains at least either thermoplastic resin fiber or glass fiber. The titania sol according to the present invention is a semi-transparent acidic water system obtained by alkali-cleaning the precipitate of hydrous titanium oxide obtained in the process of producing titanium oxide from a naturally occurring titanium source, and deflocculating with a strong acid such as hydrochloric acid or nitric acid. Of dispersed sol. What is hydrous titanium oxide? "Titanium oxide" (Gaku Seino,
It is described in detail in Gihodo Shuppan (published in 1991), but generally, it is obtained by thermally hydrolyzing a titanium sulfate solution in the production process of titanium oxide by the sulfuric acid method.
【0009】本発明に係わるこの様なチタニアゾルの一
次粒子は、含水酸化チタンと同様に数nm程度の大きさ
のアナターゼ型の微結晶であるといわれており、溶液が
酸性側からpHが変化するに従って凝集して析出する。
従って、チタニアゾル凝集時に本発明に係わる不織布を
包含する被担持体を共存させれば、担持体である不織布
上に酸化チタンが担持される。析出した酸化チタンを1
00℃以下程度で乾燥させると、粒子径が0.01μm
以下で200m2/g以上の比表面積を有する光触媒能
ある酸化チタンが得られる。The primary particles of such a titania sol according to the present invention are said to be anatase type microcrystals having a size of about several nm like the hydrous titanium oxide, and the pH of the solution changes from the acidic side. According to.
Therefore, if a supported body including the nonwoven fabric according to the present invention is made to coexist during titania sol aggregation, titanium oxide is supported on the nonwoven fabric as the carrier. 1 for the precipitated titanium oxide
When dried at a temperature below 00 ° C, the particle size will be 0.01 μm.
The photocatalytically active titanium oxide having a specific surface area of 200 m 2 / g or more is obtained below.
【0010】以上の様にして形成される酸化チタンを不
織布上で凝集析出して担持する。不織布に用いられる原
料としては、ポリエチレン及びポリプロピレン等のオレ
フィン系樹脂、ポリスチレン、ポリ-p-キシリレン、デ
クロン等のポリエステル系樹脂、エポリ酢酸ビニル、チ
レン酢酸ビニル共重合体樹脂、ナイロン等のポリアミド
系樹脂、ポリアクリロニトリル、アクリル系樹脂、ポリ
塩化ビニル、ポリ塩化ビニリデン、ポリビニルエーテ
ル、ポリビニルケトン、ポリエーテル、ポリビニルアル
コール系樹脂、ジエン系樹脂、及びポリウレタン系樹脂
等からなる熱可塑性樹脂繊維、フェノール樹脂、フラン
樹脂、ケトン・ホルムアルデヒド樹脂、キシレン・ホル
ムアルデヒド樹脂、尿素樹脂、メラミン樹脂、アニリン
樹脂、不飽和ポリエステル樹脂、アルキド樹脂、及びエ
ポキシ樹脂等の熱硬化性樹脂繊維の他、シリコーン系繊
維、フッ素系繊維、ステンレスウール等の金属繊維、各
種ガラス繊維、セルロース系繊維、及びタンパク質系繊
維等が挙げられる。The titanium oxide formed as described above is agglomerated and deposited on the non-woven fabric and carried. Raw materials used for the non-woven fabric include olefin resins such as polyethylene and polypropylene, polyester resins such as polystyrene, poly-p-xylylene and declone, epolyvinyl acetate, styrene vinyl acetate copolymer resins, polyamide resins such as nylon. , Thermoplastic resin fiber made of polyacrylonitrile, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether, polyvinyl ketone, polyether, polyvinyl alcohol resin, diene resin, polyurethane resin, etc., phenol resin, furan Thermosetting resin fiber such as resin, ketone / formaldehyde resin, xylene / formaldehyde resin, urea resin, melamine resin, aniline resin, unsaturated polyester resin, alkyd resin, and epoxy resin, as well as silicone type Wei, fluorine-based fibers, metal fibers stainless steel wool, various glass fibers, cellulosic fibers, and protein-based fibers or the like.
【0011】本発明に係わる不織布に用いられる原料繊
維の形状は特に制限はなく、その断面形状は円形のみな
らず楕円形、三角形、星型、T型、Y型、或は葉状等の
所謂異型断面形状のものでも良い。更に、表面に空隙を
有するものや枝分かれした構造、また繊維の外側と内側
で異なった樹脂を用いた芯鞘構造を有するものも使用す
ることができる。これら樹脂繊維の繊維長は繊維により
多少異なるが、一般的に1〜50mmが良く、より好ま
しくは5〜50mmが良い。また、繊維径としては一般
的に5〜20μmが適当である。The shape of the raw material fibers used in the nonwoven fabric according to the present invention is not particularly limited, and the cross-sectional shape is not only circular but also oval, triangular, star-shaped, T-shaped, Y-shaped or so-called atypical shape such as leaf-shaped. It may have a sectional shape. Further, those having a void on the surface, a branched structure, and a core-sheath structure using different resins on the outside and inside of the fiber can also be used. Although the fiber length of these resin fibers is somewhat different depending on the fiber, it is generally 1 to 50 mm, and more preferably 5 to 50 mm. In addition, as the fiber diameter, generally 5 to 20 μm is suitable.
【0012】本発明の係わる不織布に於ては、特にポリ
エチレン及びポリプロピレン等のオレフィン系樹脂、ポ
リスチレン、ポリ-p-キシリレン、デクロン等のポリエ
ステル系樹脂、エポリ酢酸ビニル、チレン酢酸ビニル共
重合体樹脂、ナイロン等のポリアミド系樹脂、ポリアク
リロニトリル、アクリル系樹脂、ポリ塩化ビニル、ポリ
塩化ビニリデン、ポリビニルエーテル、ポリビニルケト
ン、ポリエーテル、ポリビニルアルコール系樹脂、ジエ
ン系樹脂、及びポリウレタン系樹脂等からなる熱可塑性
樹脂繊維及び各種ガラス繊維が好適に用いられる。In the non-woven fabric according to the present invention, olefin resins such as polyethylene and polypropylene, polyester resins such as polystyrene, poly-p-xylylene and declone, epolyvinyl acetate, styrene vinyl acetate copolymer resin, Thermoplastic resin composed of polyamide resin such as nylon, polyacrylonitrile, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether, polyvinyl ketone, polyether, polyvinyl alcohol resin, diene resin, polyurethane resin, etc. Fibers and various glass fibers are preferably used.
【0013】本発明に係わる不織布に用いられるガラス
繊維とは、ガラスを繊維状に加工したもので、最も代表
的なものはE−ガラスであり、更に耐酸性に優れたC−
ガラス、低誘電損失のD−ガラス、高強度のS−ガラ
ス、高弾性のM−ガラス等各種ガラスを用いることがで
きる。ガラス繊維径は3〜10μm程度のものが代表的
であるが、1μm以下の極細繊維も用いても良い。The glass fiber used in the non-woven fabric according to the present invention is a glass fiber processed into a fibrous form, the most typical of which is E-glass, and C- which has excellent acid resistance.
Various glasses such as glass, low dielectric loss D-glass, high strength S-glass, and high elasticity M-glass can be used. The glass fiber diameter is typically about 3 to 10 μm, but ultrafine fibers of 1 μm or less may be used.
【0014】少なくともガラス繊維を含有する不織布
は、張り強度が極めて大きくなり、寸法安定性、耐湿
性、及び耐熱性等も向上する他、チタニアゾルや酸化チ
タンとの親和性も改良される。ガラス繊維は長繊維の状
態で乾式でウェブにできる他、短繊維の状態で湿式にて
抄造できる。また、この時に熱可塑性樹脂繊維やパル
プ、レーヨン等と混合できる。The non-woven fabric containing at least glass fibers has extremely high tensile strength, improved dimensional stability, moisture resistance, heat resistance and the like, and also improved affinity with titania sol and titanium oxide. The glass fiber can be made into a web by a dry method in a state of long fiber, and can be wet-processed in a state of short fiber. Further, at this time, it can be mixed with thermoplastic resin fibers, pulp, rayon and the like.
【0015】本発明に係わる不織布は、上記繊維を水に
懸濁し抄紙法によりシート状する湿式法、樹脂接着によ
るレジンボンド、針による交錯を利用したニードルパン
チ、糸により編み上げたステッチボンド、或は熱により
接着させるサーマルボンド等の所謂乾式法、高圧水をノ
ズルから噴射して繊維同士を交絡させる水流交絡法、直
接紡糸しながらシート化するスパンボンド、直接紡糸す
る際に霧吹きの原理を応用して微細繊維を作りながらシ
ート化するメルトブロー法等によって製造することがで
きる。The non-woven fabric according to the present invention is a wet method in which the above fibers are suspended in water to form a sheet by a paper making method, a resin bond by resin adhesion, a needle punch utilizing interlacing with needles, a stitch bond knitted by a thread, or Applying the so-called dry method such as thermal bonding to bond by heat, the hydroentangling method of injecting high-pressure water from a nozzle to entangle fibers with each other, spunbond to form a sheet while directly spinning, and the principle of spraying when directly spinning It can be manufactured by a melt blow method or the like in which a sheet is formed while making fine fibers.
【0016】不織布の厚み、空隙率、空隙の形状、開孔
度、柔軟性、弾力性、毛羽立ち、及び風合い等は、上記
製造方法を選択することで調整することができる。特に
本発明に係わる不織布は、あまり薄手にすると強度が出
ないし、逆に不織布を厚くすると、例え単位面積当りの
酸化チタン担持量は増加できでもその全てが受光できな
いため、目付け量は平米当り10〜80g程度が好まし
い。また、本発明では水系処理を施すため、不織布にあ
る程度の水濡れ性が必要となり、親水性繊維によりウェ
ブを製造したものが好ましい。更に、シート強度の点か
らスパンボンドやスパンレース法にて不織布を加工する
ことが好ましい。The thickness, porosity, void shape, porosity, flexibility, elasticity, fluffiness, and texture of the non-woven fabric can be adjusted by selecting the above manufacturing method. In particular, the non-woven fabric according to the present invention does not have strength if it is too thin, and conversely if the non-woven fabric is thick, the amount of titanium oxide supported per unit area can be increased, but all of it cannot receive light. About 80 g is preferable. Further, in the present invention, since the water-based treatment is performed, the non-woven fabric needs to have water wettability to some extent, and it is preferable that the web is made of hydrophilic fibers. Further, from the viewpoint of sheet strength, it is preferable to process the nonwoven fabric by a spunbond or spunlace method.
【0017】次に、本発明に係わるチタニアゾルからの
不織布への酸化チタンの担持方法を述べる。本発明に係
わるチタニアゾルは、ゾル状態で浸漬や塗布等により不
織布に含浸する。浸漬の場合はゾルの濃度及び絞りの程
度により、塗布の場合はゾル濃度及び塗布量で含浸量を
調整する。水濡れ性が劣る不織布を用いる場合は、酸化
チタン含浸に先立って、コロナ処理、グロー放電処理、
プラズマ処理、電子線照射処理、遠紫外線照射処理、オ
ゾン処理、及び界面活性剤等の物理的化学的処理により
水濡れ性を改善しておくことが好ましい。また、チタニ
アゾル含浸後に湿潤状態のまま以降の処理を行なっても
良いが、一旦乾燥させても良い。Next, a method for supporting titanium oxide on the nonwoven fabric from the titania sol according to the present invention will be described. The titania sol according to the present invention is impregnated into a nonwoven fabric in a sol state by dipping or coating. In the case of dipping, the impregnation amount is adjusted by the concentration of the sol and the degree of squeezing. When using a non-woven fabric with poor water wettability, corona treatment, glow discharge treatment,
It is preferable to improve water wettability by plasma treatment, electron beam irradiation treatment, far ultraviolet ray irradiation treatment, ozone treatment, and physical / chemical treatment such as surfactant. Further, after impregnation with the titania sol, the following treatment may be carried out in a wet state, but may be once dried.
【0018】チタニアゾルを含浸した不織布は、次にア
ルカリ処理して酸化チタンを不織布に凝集析出させて担
持する。チタニアゾルからの酸化チタンの凝集析出に係
わるアルカリ処理に用いるアルカリ剤としては、アルカ
リ金属及びアルカリ土類金属の水酸化物または含水酸化
物、及び炭酸、リン酸、ホウ酸、及び珪酸等の酸との
塩、及び炭酸及びリン酸等の塩基性アンモニウム塩等の
水溶性無機物質や、アルコールアミン類、アルキルアミ
ン類、アルキレンジアミン類、モルホリン、及び塩基性
グアニジン塩類等が挙げられる。これらは単一種でも、
または2種以上を組合わせて用いても良い。The non-woven fabric impregnated with the titania sol is then treated with an alkali to coagulate and deposit titanium oxide on the non-woven fabric and carry it. As the alkaline agent used in the alkaline treatment relating to the cohesive precipitation of titanium oxide from titania sol, hydroxides or hydrous oxides of alkali metals and alkaline earth metals, and acids such as carbonic acid, phosphoric acid, boric acid, and silicic acid are used. And water-soluble inorganic substances such as basic ammonium salts such as carbonic acid and phosphoric acid, alcohol amines, alkylamines, alkylenediamines, morpholine, and basic guanidine salts. These are single species,
Alternatively, two or more kinds may be used in combination.
【0019】上記アルカリ剤のうち、リチウム、ナトリ
ウム、及びカリウム等のアルカリ金属の水酸化物や炭酸
塩の水溶液を用いると、酸化チタンの凝集速度が速く担
持できるために好適に用いられる。アルカリ処理に於け
る処理液のpHは14以下、好ましくは8〜12程度で
ある。このようなアルカリの水溶液をチタニアゾルを含
浸させた不織布に作用させると、チタニアゾルの分散安
定性が阻害され、酸化チタンが凝集析出して不織布の繊
維表面に一様に吸着し、チタニアゾルを凝集析出してか
ら不織布に担持させるより接着力及び含浸の均一性共に
向上する。Of the above-mentioned alkaline agents, the use of an aqueous solution of a hydroxide or carbonate of an alkali metal such as lithium, sodium and potassium is preferably used because the aggregation rate of titanium oxide can be carried quickly. The pH of the treatment liquid in the alkali treatment is 14 or less, preferably about 8-12. When an aqueous solution of such an alkali is applied to a non-woven fabric impregnated with titania sol, the dispersion stability of the titania sol is impaired, titanium oxide is coagulated and deposited uniformly on the fiber surface of the non-woven fabric, and the titania sol is cohesively deposited. Both the adhesive strength and the uniformity of impregnation are improved by supporting it on a non-woven fabric afterwards.
【0020】アルカリ処理により酸化チタンは不織布繊
維表面を覆うが、チタニアゾルの含浸量が高かったり上
記アルカリ液の絞りが充分ではなかったりすると、酸化
チタンの凝集体が大きくなり、吸着による担持だけでは
充分でなくなり、不織布から酸化チタンの粉体が脱離し
てしまう。このため、担持した酸化チタン凝集体の大き
さは10μm以下が、好ましくは5μm以下になる様に
担持条件を調整することが肝要である。この状態では酸
化チタンは脱離せずに不織布に担持される。Titanium oxide covers the surface of the non-woven fabric fiber by the alkali treatment. However, if the amount of the titania sol impregnated is high or if the above alkaline solution is not sufficiently squeezed, the titanium oxide agglomerates become large, and adsorption alone is sufficient. The titanium oxide powder is desorbed from the non-woven fabric. Therefore, it is important to adjust the supporting conditions so that the size of the supported titanium oxide aggregate is 10 μm or less, preferably 5 μm or less. In this state, titanium oxide is supported on the nonwoven fabric without being detached.
【0021】[0021]
【作用】本発明の光反応性有害物除去材及びその製造方
法では、光反応性有害物除去剤である酸化チタンをゾル
から析出と同時に担持させるので、酸化チタンが均一に
かつ強固に不織布に担持されるばかりでなく、増粒させ
ないため比表面積が大きいまま担持でき、紫外光含む光
を照射することで、悪臭や細菌等の空気中に浮遊する有
害物を分解して除去することができる優れた効果を有す
る酸化チタンが不織布上に得られる。In the photoreactive harmful substance removing material and the method for producing the same of the present invention, titanium oxide, which is a photoreactive harmful substance removing agent, is carried simultaneously with deposition from the sol, so that the titanium oxide is uniformly and firmly formed on the nonwoven fabric. Not only is it carried, but since it does not increase the particle size, it can be carried with a large specific surface area, and by irradiating with light including ultraviolet light, it is possible to decompose and remove harmful substances such as malodors and bacteria floating in the air. Titanium oxide having an excellent effect is obtained on a nonwoven fabric.
【0022】また、不織布にガラス繊維を含有させてお
けば、担持以降の後加工時の強度等も向上すると同時に
チタニアゾルや酸化チタンとの親和性も向上する。一
方、熱可塑性を有する原料繊維を含有させておけば、低
コストで別の不織布やフィルム等との張り合わせや積層
化ができるなど加工性に優れおり、全体としてはシート
状であるので取扱いにも優れている。更に、本発明の光
反応性有害物除去材を他の特徴を持つ不織布との組み合
わせることよって、意匠性や風合い、また肌触り等の諸
特性をも付加することができる。Further, if the non-woven fabric contains glass fiber, the strength at the time of post-processing after supporting is improved and at the same time the affinity with titania sol and titanium oxide is improved. On the other hand, if the raw material fiber having thermoplasticity is contained, it is excellent in processability such as being able to be laminated or laminated with another non-woven fabric or film at a low cost. Are better. Furthermore, by combining the photoreactive harmful substance removing material of the present invention with a non-woven fabric having other characteristics, it is possible to add various characteristics such as designability, texture and touch.
【0023】[0023]
【実施例】以下、実施例により更に本発明を詳細に説明
するが、無論これらに限定されるものではない。The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited thereto.
【0024】実施例1 (A)チタニアゾルの作製 通常の硫酸法酸化チタンの製造工程中に得られる含水酸
化チタンを水酸化ナトリウム水溶液で中和洗浄し、塩酸
により解膠して酸化チタン換算で40重量%でpH1の
チタニアゾル原液を得た。このチタニアゾル原液を10
倍に希釈した後に、ブチンジオール系ノニオン界面活性
剤のメタノール溶液を1000ppm添加してチタニア
ゾル含浸液とした。Example 1 (A) Preparation of titania sol Titanium oxide hydroxide obtained in the usual production process of titanium oxide by the sulfuric acid method was neutralized and washed with an aqueous solution of sodium hydroxide, peptized with hydrochloric acid and converted into titanium oxide of 40. A titania sol stock solution with a pH of 1 in weight% was obtained. 10 parts of this titania sol stock solution
After doubling the dilution, 1000 ppm of a methanol solution of butynediol-based nonionic surfactant was added to obtain a titania sol impregnation liquid.
【0025】(B)酸化チタンの含浸 水流交絡法により強度を増強したポリプロピレン繊維よ
りなる不織布(目付け量:40g/m2)をコロナ処理し
た後、上記チタニアゾル含浸液に浸漬して軽く絞った。
一方、炭酸水素ナトリウムを水に溶解してpH8のアル
カリ処理用水溶液を作製し、このアルカリ処理用水溶液
にチタニアゾルを含浸させた不織布を浸漬して酸化チタ
ンを不織布に担持し、80℃で3分間風乾して光反応性
有害物除去材とした。作製されたシートは酸化チタンの
粉落ちは観られなかった。。(B) Impregnation of Titanium Oxide A nonwoven fabric made of polypropylene fibers having an increased strength by the hydroentangling method (weight per unit area: 40 g / m 2 ) was corona treated, then dipped in the above titania sol impregnating solution and squeezed lightly.
On the other hand, sodium hydrogen carbonate was dissolved in water to prepare an aqueous solution for alkali treatment having a pH of 8, and a non-woven fabric impregnated with titania sol was immersed in this aqueous solution for alkali treatment to support titanium oxide on the non-woven fabric, and at 80 ° C. for 3 minutes. Air-dried to obtain a photoreactive harmful substance removing material. No powder of titanium oxide was observed in the produced sheet. .
【0026】(C)シートの観察 作製した光反応性有害物除去材は、蛍光X線分析装置に
よって酸化チタンの存在が確認できた。酸化チタンの付
着量は含浸前後の重量差より4.3g/m2であった。ま
た、このシートの表面を電子顕微鏡で観察したところ、
酸化チタンの凝集体の大きさは5μm以下であった。(C) Observation of Sheet The presence of titanium oxide was confirmed by the fluorescent X-ray analyzer in the prepared photoreactive harmful substance removing material. The amount of titanium oxide deposited was 4.3 g / m 2 based on the weight difference before and after impregnation. Also, when observing the surface of this sheet with an electron microscope,
The size of the titanium oxide aggregate was 5 μm or less.
【0027】(D)光触媒能の測定 このシートを120cm2の大きさに裁断し、5.6リッ
トルの密閉できる容器に入れた。この容器内に、タバコ
や汗の悪臭の代表的化合物であるアセトアルデヒドを約
200ppm注入し、ブラックランプ(6W)を照射し
ながら容器内のアセトアルデヒドの濃度の変化を時間を
追って測定した。同様にして、上記で作製した酸化チタ
ン担持不織布をアセトアルデヒドと共に密閉容器に入
れ、光照射しなかった。更に、酸化チタンを担持してい
ない不織布を別容器に入れた後にアセトアルデヒドを注
入し、ブラックランプを照射した。その結果、酸化チタ
ン担持不織布にブラックランプを照射した場合、30分
後にアセトアルデヒドは50ppmまで低下したが、光
を照射しなかった方は180ppmであった。更に、酸
化チタン未担持不織布の場合は数ppmしか低下しなか
った。従って、担持された酸化チタンに光照射すること
よって、アセトアルデヒドが分解されると云う光触媒能
力が観察された。(D) Measurement of photocatalytic activity This sheet was cut into a size of 120 cm 2 and placed in a 5.6 liter hermetic container. About 200 ppm of acetaldehyde, which is a typical compound having a bad odor of cigarettes or sweat, was injected into this container, and the change in the concentration of acetaldehyde in the container was measured over time while irradiating with a black lamp (6 W). Similarly, the titanium oxide-supported non-woven fabric prepared above was placed in a closed container together with acetaldehyde and was not irradiated with light. Furthermore, a non-woven fabric not supporting titanium oxide was put in another container, and then acetaldehyde was injected and irradiated with a black lamp. As a result, when the titanium oxide-supported non-woven fabric was irradiated with a black lamp, acetaldehyde was reduced to 50 ppm after 30 minutes, but 180 ppm was obtained for those not irradiated with light. Further, in the case of the titanium oxide-unsupported nonwoven fabric, it decreased by only a few ppm. Therefore, the photocatalytic ability that the acetaldehyde is decomposed by irradiating the supported titanium oxide with light was observed.
【0028】実施例2 実施例1で作製したチタニアゾル原液を10倍希釈した
界面活性剤入りチタニアゾル含浸液をポリビニルアルコ
ールをバインダーとしたE−ガラスより成るガラス繊維
不織布に含浸させ、軽く絞った。一方、水酸化ナトリウ
ムを水に溶解させpH10のアルカリ水溶液を作製し
た。チタニアゾルを含浸させたこのガラス繊維不織布
を、アルカリ水溶液に浸漬して酸化チタンを析出担持
し、60℃で10分間乾燥した。ガラス繊維不織布表面
の付着物を実施例1同様に分析計量したところ、付着物
は酸化チタンで、その付着量は5.4g/m2であった。Example 2 The titania sol stock solution prepared in Example 1 was diluted 10 times and a titania sol impregnating solution containing a surfactant was impregnated into a glass fiber non-woven fabric made of E-glass using polyvinyl alcohol as a binder and squeezed lightly. On the other hand, sodium hydroxide was dissolved in water to prepare an alkaline aqueous solution having a pH of 10. This glass fiber non-woven fabric impregnated with titania sol was immersed in an alkaline aqueous solution to deposit and carry titanium oxide, and dried at 60 ° C. for 10 minutes. When the deposit on the surface of the glass fiber non-woven fabric was analyzed and weighed in the same manner as in Example 1, the deposit was titanium oxide, and the deposit amount was 5.4 g / m 2 .
【0029】このシートを120cm2の大きさに裁断
して5.6リットルの密閉できる容器に入れ、実施例1
と同条件でアセトアルデヒドの光分解能力を測定したと
ころ、初期濃度200ppmが30分後には40ppm
まで減少した。This sheet was cut into a size of 120 cm 2 and placed in a 5.6 liter hermetically sealed container.
When the photodecomposition ability of acetaldehyde was measured under the same conditions as above, the initial concentration of 200 ppm was 40 ppm after 30 minutes.
Decreased to.
【0030】比較例1 ルチル型酸化チタン(堺化学製;Titon R-3L)
をブチンジオール系ノニオン界面活性剤のメタノール溶
液を1000ppm添加した水に4重量%で分散して酸
化チタン含浸液とした。実施例2で作製したガラス繊維
不織布シートを2枚用い、この酸化チタン含浸液に浸漬
後、1枚は実施例2で用いたアルカリ液で処理し、もう
1枚はアルカリ液で処理しないまま、2枚共実施例2と
同条件で乾燥し、酸化チタン担持不織布を作製した。こ
の2枚の酸化チタン担持不織布をの光触媒能力を実施例
1と同様にして測定したところ、ブラックランプ照射3
0分後のアセトアルデヒド分解量は何れも20ppm以
下であった。Comparative Example 1 Rutile type titanium oxide (Saton Chemical Co .; Titon R-3L)
Was dispersed in water containing 1000 ppm of a methanol solution of butynediol-based nonionic surfactant at 4% by weight to prepare a titanium oxide impregnated solution. Two glass fiber nonwoven fabric sheets prepared in Example 2 were used. After being immersed in the titanium oxide impregnating solution, one sheet was treated with the alkaline solution used in Example 2 and the other sheet was not treated with the alkaline solution. The two sheets were dried under the same conditions as in Example 2 to prepare a titanium oxide-supported nonwoven fabric. The photocatalytic ability of the two titanium oxide-supported nonwoven fabrics was measured in the same manner as in Example 1, and the black lamp irradiation 3
The acetaldehyde decomposition amount after 0 minutes was 20 ppm or less in all cases.
【0031】実施例3 ポリプロピレン樹脂とセルロース繊維を等量混合し、湿
式方法で製造した目付け量40g/m2の不織布に、実
施例1で調製したチタニアゾル含浸液を用いて実施例1
と同様な方法で酸化チタンを担持させた。これとは別
に、ポリプロピレン樹脂繊維よりなる通気性不織布(目
付け量20g/m2)をエンボス加工を施した熱ロール
でヒートシール加工を行ない、光反応性有害物除去材を
作製した。この除去材を25cm2に裁断し、大腸菌濃
度が1万個/mlの水溶液、50ccに浸漬させた。こ
の状態で20wの蛍光灯を30cmの距離から照射した
ところ、5時間後に大腸菌濃度は250個/mlまで減
少した。一方、チタニアゾルから酸化チタンを担持した
が光照射しなかった場合、及び光照射したが未含浸の不
織布を用いた場合は、大腸菌濃度は減少するどころか若
干増加した。Example 3 Using the titania sol impregnating solution prepared in Example 1 in a non-woven fabric having a basis weight of 40 g / m 2 produced by a wet method by mixing polypropylene resin and cellulose fibers in equal amounts, Example 1
Titanium oxide was supported in the same manner as in. Separately from this, heat-sealing was performed on a breathable non-woven fabric made of polypropylene resin fiber (weight per unit area: 20 g / m 2 ) with an embossed hot roll to prepare a photoreactive harmful substance removing material. This removing material was cut into 25 cm 2 and immersed in 50 cc of an aqueous solution containing 10,000 E. coli / ml. When a 20 w fluorescent lamp was irradiated from a distance of 30 cm in this state, the E. coli concentration decreased to 250 cells / ml after 5 hours. On the other hand, when the titanium oxide was loaded from the titania sol but was not irradiated with light, or when a non-woven fabric that was irradiated with light but was not impregnated was used, the Escherichia coli concentration was increased rather than decreased.
【0032】実施例4 実施例1で作製したチタニアゾル原液を酸化チタン濃度
20重量%に希釈し、更に実施例1で用いた界面活性剤
を添加してチタニアゾル含浸液を作製した。このゾルを
実施例1で作製した不織布に含浸させ、水酸化ナトリウ
ムを溶解させたpH13のアルカリ水溶液に浸漬した
後、60℃で5分間乾燥した。不織布に担持できた酸化
チタン量は19.5g/m2であったが、取扱中に若干酸
化チタンが粉落ちした。作製された光反応性有害物除去
材を電子顕微鏡で観察したところ、50μm以上の酸化
チタンの凝集物が確認された。Example 4 A titania sol impregnated solution was prepared by diluting the titania sol stock solution prepared in Example 1 to a titanium oxide concentration of 20% by weight and further adding the surfactant used in Example 1. The non-woven fabric prepared in Example 1 was impregnated with this sol, immersed in an alkaline aqueous solution of pH 13 in which sodium hydroxide was dissolved, and then dried at 60 ° C. for 5 minutes. The amount of titanium oxide that could be supported on the non-woven fabric was 19.5 g / m 2 , but some titanium oxide fell off during handling. When the produced photoreactive harmful substance removing material was observed with an electron microscope, aggregates of titanium oxide of 50 μm or more were confirmed.
【0033】このシートを実施例1と同様に120cm
2の大きさに裁断し、5.6リットルの密閉できる容器に
入れた。この容器内にアセトアルデヒドを約200pp
m注入し、ブラックランプを照射しながら容器内のアセ
トアルデヒドの濃度の変化を時間を追って測定した。同
様にして、上記で作製した酸化チタン担持不織布をアセ
トアルデヒドと共に密閉容器に入れ、光照射しなかっ
た。その結果、酸化チタン担持不織布にブラックランプ
を照射した場合、30分後にアセトアルデヒドは40p
pmまで低下し、光を照射しなかった方は160ppm
であった。120 cm of this sheet as in Example 1
It was cut into a size of 2 and placed in a 5.6 liter sealable container. About 200 pp of acetaldehyde in this container
Then, the change in the concentration of acetaldehyde in the container was measured over time while irradiating with a black lamp. Similarly, the titanium oxide-supported non-woven fabric prepared above was placed in a closed container together with acetaldehyde and was not irradiated with light. As a result, when the titanium oxide-supported nonwoven fabric was irradiated with a black lamp, acetaldehyde was exposed to 40 p after 30 minutes.
Those who did not irradiate with light decreased to pm 160ppm
Met.
【0034】これは、光照射の有無に関係なく、酸化チ
タンには弱いガス吸着能があって、光照射しない場合は
酸化チタンの絶対量が多いために実施例1よりアセトア
ルデヒド濃度が低下した。一方、光照射すれば実施例1
と同様に充分な光触媒能を有していたが、二次凝集体の
酸化チタンのサイズが大きいためか、酸化チタンの絶対
量から比較した除去効率は実施例1より劣っていた。This is because the titanium oxide has a weak gas adsorbing ability regardless of the presence or absence of light irradiation, and the acetaldehyde concentration was lower than in Example 1 because the absolute amount of titanium oxide was large when light irradiation was not performed. On the other hand, if light irradiation is performed, Example 1
Although it had a sufficient photocatalytic ability as in Example 1, the removal efficiency compared with the absolute amount of titanium oxide was inferior to that of Example 1 probably because the size of titanium oxide in the secondary aggregate was large.
【0035】[0035]
【発明の効果】以上説明した通り、本発明によれば、光
を照射することによって、悪臭等の空気中の低濃度の有
害物が除去でき、かつ殺菌性を有するシート状の光反応
性有害物除去材を、低コストで提供できる。この光反応
性有害物除去材は、不織布に熱可塑性樹脂繊維を含有さ
せておけば、他の熱可塑性不織布との張り合わせ加工な
ども低コストで行うことができ、例えば別の意匠性や風
合い肌触りなどの優れた通気性不織布と積層することも
できる。As described above, according to the present invention, by irradiating light, a low concentration of harmful substances such as a bad odor in the air can be removed, and a sheet-like photoreactive harmful substance having a bactericidal property can be removed. An object removing material can be provided at low cost. If this non-woven fabric contains thermoplastic resin fibers, this photo-reactive harmful substance removing material can also be laminated with other thermoplastic non-woven fabrics at a low cost, for example, with another design and texture. It can also be laminated with an excellent breathable nonwoven fabric such as.
【0036】この様な光反応性有害物除去材は、適度な
大きさに切断し、有害物質を除去したい場所に置き、光
を照射するだけで容易に有害物質を除去することができ
るので、有害物質の量や設置場所に応じて手軽に、特に
低濃度の有害物質の除去にも効率よく使用できる。その
ため、本発明の光反応性有害物質除去材は、例えば、自
動車の後部座席やエアコン付近、靴箱、冷蔵庫、ロッカ
ー、及びタンス等の中に設置したり、ハンガーに掛けて
室内で、或はベッド(マットレス)の上に敷いて病院内
で手軽に使用でき、また室内や自動車内のブラインドや
カーテンとしても使用できる。更に、このような密閉さ
れた空間だけでなく、掃除機や生ゴミ乾燥機などの排出
口などの通気場所に設置してフィルターとして使用して
も効率的である。また、抗菌性等の性能もあるために上
水道の殺菌や、風呂、プール等の水質悪化防止用として
も用いることができる他、病院等の抗菌性壁紙や床シー
ト材としても利用できる。Such a photoreactive harmful substance removing material can be easily removed by simply cutting it to an appropriate size, placing it in a place where it is desired to remove the harmful substance, and irradiating it with light. It can be used easily according to the amount of harmful substances and the place of installation, especially for the removal of low-concentration harmful substances. Therefore, the photoreactive harmful substance removing material of the present invention can be installed, for example, in the back seat of an automobile or near an air conditioner, in a shoe box, a refrigerator, a locker, a closet, or on a hanger indoors or in a bed. It can be laid on a (mattress) and used easily in a hospital, or it can be used as a blind or curtain inside or in a car. Further, it is effective not only in such a sealed space but also in a ventilation place such as a discharge port of a vacuum cleaner or a garbage dryer to be used as a filter. Further, since it has antibacterial properties and the like, it can be used for sterilization of water supply and for preventing deterioration of water quality in baths, pools and the like, and also as antibacterial wallpaper and floor sheet materials for hospitals and the like.
Claims (5)
化チタンを担持させたことを特徴とする光反応性有害物
除去材。1. A photoreactive harmful substance removing material, characterized in that titanium oxide precipitated from titania sol is supported on a non-woven fabric.
10ミクロン以下の大きさで凝集し吸着して担持されて
いる請求項1記載の光反応性有害物除去材。2. The photoreactive harmful substance removing material according to claim 1, wherein the precipitated titanium oxide is carried on the surface of the non-woven fabric in a size of 10 μm or less and adsorbed and carried.
を担持させる不織布の原料繊維に、熱可塑性樹脂繊維か
ガラス繊維の少なくとも一方を含有する請求項1または
2記載の光反応性有害物除去材。3. The photoreactive harmful substance removing material according to claim 1, wherein the raw material fibers of the nonwoven fabric supporting titanium oxide precipitated from titania sol contain at least one of a thermoplastic resin fiber and a glass fiber.
アルカリ処理して酸化チタンを析出させて該不織布に酸
化チタンを担持させることを特徴とする光反応性有害物
除去材の製造方法。4. After impregnating a non-woven fabric with titania sol,
A method for producing a photoreactive harmful substance removing material, which comprises carrying out alkali treatment to deposit titanium oxide to support titanium oxide on the nonwoven fabric.
リ析出を、アルカリ金属の水酸化物または炭酸塩を含む
水溶液を用いて行なう請求項4記載の光反応性有害物除
去材の製造方法。5. The method for producing a photoreactive harmful substance removing material according to claim 4, wherein alkali precipitation of titanium oxide from the titania sol is carried out using an aqueous solution containing an alkali metal hydroxide or carbonate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6254034A JPH08117556A (en) | 1994-10-20 | 1994-10-20 | Photo-reactive harmful matter-removing material and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6254034A JPH08117556A (en) | 1994-10-20 | 1994-10-20 | Photo-reactive harmful matter-removing material and production thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08117556A true JPH08117556A (en) | 1996-05-14 |
Family
ID=17259325
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6254034A Pending JPH08117556A (en) | 1994-10-20 | 1994-10-20 | Photo-reactive harmful matter-removing material and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH08117556A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021722A1 (en) * | 1999-09-21 | 2001-03-29 | Toto Ltd. | Photocatalytic hydrophilic coating material |
JP2004125360A (en) * | 2002-01-08 | 2004-04-22 | Mitsubishi Electric Corp | Refrigerator |
JP2010051871A (en) * | 2008-08-27 | 2010-03-11 | Satoshi Yoshimura | Filtering medium for air cleaner and method of manufacturing the same |
CN102443189A (en) * | 2011-10-24 | 2012-05-09 | 山东红太阳保温材料有限公司 | Production method of photocatalyst sponge cloth |
-
1994
- 1994-10-20 JP JP6254034A patent/JPH08117556A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001021722A1 (en) * | 1999-09-21 | 2001-03-29 | Toto Ltd. | Photocatalytic hydrophilic coating material |
JP2004125360A (en) * | 2002-01-08 | 2004-04-22 | Mitsubishi Electric Corp | Refrigerator |
JP2010051871A (en) * | 2008-08-27 | 2010-03-11 | Satoshi Yoshimura | Filtering medium for air cleaner and method of manufacturing the same |
CN102443189A (en) * | 2011-10-24 | 2012-05-09 | 山东红太阳保温材料有限公司 | Production method of photocatalyst sponge cloth |
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