JP4619075B2 - Method for producing antibacterial and deodorant titanium oxide colloidal solution - Google Patents
Method for producing antibacterial and deodorant titanium oxide colloidal solution Download PDFInfo
- Publication number
- JP4619075B2 JP4619075B2 JP2004272776A JP2004272776A JP4619075B2 JP 4619075 B2 JP4619075 B2 JP 4619075B2 JP 2004272776 A JP2004272776 A JP 2004272776A JP 2004272776 A JP2004272776 A JP 2004272776A JP 4619075 B2 JP4619075 B2 JP 4619075B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- titanium oxide
- deodorant
- solution
- colloidal solution
- 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.)
- Expired - Lifetime
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 133
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 112
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 106
- 239000002781 deodorant agent Substances 0.000 title claims description 89
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000243 solution Substances 0.000 claims description 89
- 239000007864 aqueous solution Substances 0.000 claims description 31
- 239000000084 colloidal system Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 150000003608 titanium Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000001877 deodorizing effect Effects 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 241000282994 Cervidae Species 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000588747 Klebsiella pneumoniae Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000191940 Staphylococcus Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- VCSZKSHWUBFOOE-UHFFFAOYSA-N dioxidanium;sulfate Chemical compound O.O.OS(O)(=O)=O VCSZKSHWUBFOOE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 tile Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 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
- 239000000123 paper Substances 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Colloid Chemistry (AREA)
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
本発明は、抗菌・消臭性酸化チタンコロイド溶液の製造方法に関し、さらに詳しくは、樹脂、塗料、繊維、紙、不織布、皮革、化粧品やガラス、タイル、コンクリートなどに添加または塗布して優れた抗菌性、消臭性などの効果を発揮する、長期間安定したコロイド溶液を維持する抗菌・消臭性酸化チタンコロイド溶液の製造方法に関する。 The present invention relates to a method for producing an antibacterial / deodorant titanium oxide colloid solution, and more particularly, it is excellent when added to or applied to a resin, paint, fiber, paper, nonwoven fabric, leather, cosmetics, glass, tile, concrete, etc. The present invention relates to a method for producing an antibacterial and deodorant titanium oxide colloidal solution that maintains an antibacterial and deodorant effects and maintains a long-term stable colloidal solution.
近年、高温多湿のわが国に於いては、細菌による食中毒等が多発しており、またマンション等の乱立による居住環境の変化に伴い細菌、黴、悪臭、汚れなどの生活環境の悪化が社会問題となっていることから、これらの環境の清浄化が強く求められている。そしてこのような生活環境を清浄化するために、光触媒作用を有する酸化チタンを含む種々の抗菌剤や消臭剤およびそれらの製造方法が提案されている。 In recent years, food poisoning due to bacteria has frequently occurred in Japan, which is hot and humid, and the deterioration of the living environment due to changes in the living environment due to the confusion of condominiums, etc. is a social problem. Therefore, there is a strong demand for cleaning these environments. In order to clean such a living environment, various antibacterial agents and deodorants containing titanium oxide having a photocatalytic action and methods for producing them have been proposed.
例えば、本出願人の出願にかかる特開平７−３３６１６号公報（特許文献１）には、抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とから構成される微粒子が分散してなる抗菌性無機酸化物コロイド溶液であって、当該コロイド溶液中の抗菌性金属成分の重量をＡ、該コロイド溶液を超遠心分離処理して遊離した抗菌性金属成分の重量をＢとしたとき、Ｂ／Ａで表される抗菌性金属の結合力指数Ｉの値が１．０×１０-3以下であることを特徴とする抗菌剤が提案されており、その製造方法の一例として、含水チタン酸のゲルまたはゾルに過酸化水素を加えて得られるチタン酸水溶液と抗菌性金属成分の水溶液とを、ケイ素化合物および／またはジルコニウム化合物の存在下で加熱処理して調製する方法が記載されている。しかし、該方法で得られる抗菌剤の酸化チタンは光触媒作用の点で更なる改良が望まれていた。 For example, in Japanese Patent Application Laid-Open No. 7-33616 (Patent Document 1) according to the application of the present applicant, fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed. An antibacterial inorganic oxide colloidal solution, where A is the weight of the antibacterial metal component in the colloidal solution, and B is the weight of the antibacterial metal component released by ultracentrifugation of the colloidal solution. An antibacterial agent characterized in that the value of the binding strength index I of the antibacterial metal represented by / A is 1.0 × 10 −3 or less has been proposed. A method is described in which an aqueous titanic acid solution obtained by adding hydrogen peroxide to a gel or sol and an aqueous solution of an antibacterial metal component are prepared by heat treatment in the presence of a silicon compound and / or a zirconium compound. However, the antibacterial agent titanium oxide obtained by this method has been desired to be further improved in terms of photocatalytic action.
また、特開２００４−９１２６３号公報（特許文献２）には、ＴｉＸ4（Ｘはハロゲン化物イオンまたはアルコキシ基を示す。）で表されるチタン化合物の水性溶媒溶液と塩基性物質とを混合して水酸化チタンを生成させ、前記水酸化チタンと酸とを混合し、２０〜９０℃に加熱することを特徴とするアナターゼ型チタニアゾルの製造方法が提案されている。そして、アナターゼ型チタニアは、抗菌性、防汚性、消臭性などの光触媒作用を有することが記載されている。しかし、前記アナターゼ型チタニアゾルは抗菌・消臭性金属成分を含有していないため抗菌性、消臭性効果が小さいという問題があった。 In addition, JP 2004-91263 A (Patent Document 2) includes mixing an aqueous solvent solution of a titanium compound represented by TiX 4 (X represents a halide ion or an alkoxy group) with a basic substance. A method for producing anatase-type titania sol is proposed in which titanium hydroxide is produced, the titanium hydroxide and the acid are mixed and heated to 20 to 90 ° C. And it is described that anatase type titania has a photocatalytic action such as antibacterial properties, antifouling properties, and deodorizing properties. However, since the anatase type titania sol does not contain an antibacterial / deodorant metal component, there is a problem that the antibacterial and deodorant effects are small.
本発明の目的は、前述の問題を解決し、抗菌性、消臭性などの優れた効果を発揮し、しかも強い光触媒作用を有する、長期間安定したコロイド溶液を維持する抗菌・消臭性酸化チタンコロイド溶液の製造方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems, exhibit excellent effects such as antibacterial properties and deodorizing properties, and have a strong photocatalytic action, and maintain an antibacterial and deodorant oxidation that maintains a stable colloid solution for a long period of time It is providing the manufacturing method of a titanium colloid solution.
本発明の第１は、（１）抗菌・消臭性金属成分含有水溶液とチタン塩水溶液とを混合した水溶液にアルカリを添加して含水酸化物を生成し、（２）得られた含水酸化物を洗浄し、（３）洗浄した含水酸化物を水に懸濁し、（４）該懸濁液にシリカコロイド溶液および／または珪酸液を加えて混合し、（５）さらにアルカリを加えて該懸濁液のｐＨを７〜１３の範囲に調整し、（６）次いで、ｐＨ調整した懸濁液をオートクレーブで温度１１０〜２５０℃の範囲で加熱処理して、抗菌・消臭性酸化チタン微粒子が分散したコロイド溶液を得ることを特徴とする抗菌・消臭性酸化チタンコロイド溶液の製造方法に関する。 The first of the present invention is (1) producing an hydrated oxide by adding an alkali to an aqueous solution obtained by mixing an aqueous solution containing an antibacterial / deodorant metal component and an aqueous titanium salt, and (2) the obtained hydrated oxide. (3) Suspend the washed hydrous oxide in water, (4) Add and mix the silica colloid solution and / or silicic acid solution to the suspension, and (5) Add alkali to the suspension. The pH of the turbid liquid is adjusted to a range of 7 to 13, and (6) Next, the pH-adjusted suspension is heated in an autoclave at a temperature of 110 to 250 ° C. to obtain antibacterial / deodorant titanium oxide fine particles. The present invention relates to a method for producing an antibacterial and deodorant titanium oxide colloidal solution characterized by obtaining a dispersed colloidal solution.
本発明の第２は、前記抗菌・消臭性金属成分が、銀、銅、亜鉛、錫、ビスマス、鉄、コバルト、ニッケル、ロジウム、パラジウム、白金、マンガン、モリブデン、タングステン、バナジウム、ジルコニウムから選ばれた１種以上であることを特徴とする請求項１記載の抗菌・消臭性酸化チタンコロイド溶液の製造方法に関する。
本発明の第３は、前記抗菌・消臭性酸化チタン微粒子がアナターゼ型酸化チタンであることを特徴とする請求項１または２記載の抗菌・消臭性酸化チタンコロイド溶液の製造方法に関する。
本発明の第４は、前記抗菌・消臭性酸化チタン微粒子が、結晶子径１００Å以上であるアナターゼ型酸化チタンであることを特徴とする請求項１、２または３記載の抗菌・消臭性酸化チタンコロイド溶液の製造方法に関する。
In the second aspect of the present invention, the antibacterial / deodorant metal component is selected from silver, copper, zinc, tin, bismuth, iron, cobalt, nickel, rhodium, palladium, platinum, manganese, molybdenum, tungsten, vanadium, and zirconium. The method for producing an antibacterial / deodorant titanium oxide colloidal solution according to claim 1, wherein the antibacterial and deodorant titanium oxide colloidal solution is one or more kinds.
A third aspect of the present invention relates to the method for producing an antibacterial / deodorant titanium oxide colloidal solution according to claim 1 or 2, wherein the antibacterial / deodorant titanium oxide fine particles are anatase type titanium oxide.
The fourth aspect of the present invention is that the antibacterial and deodorant titanium oxide fine particles are anatase type titanium oxide having a crystallite diameter of 100 mm or more. The present invention relates to a method for producing a titanium oxide colloid solution.
本発明方法によれば、抗菌・消臭性に優れた酸化チタンコロイド溶液を簡易な操作によって得ることができる。即ち、本発明の方法で得られる抗菌・消臭性酸化チタンコロイド溶液は、分散質である抗菌・消臭性酸化チタン微粒子がアナターゼ型酸化チタンの結晶形を有し、しかも、アナターゼ型酸化チタンの結晶子径が大きいので抗菌作用と共に光触媒作用に優れている。 According to the method of the present invention, a titanium oxide colloid solution excellent in antibacterial and deodorant properties can be obtained by a simple operation. That is, the antibacterial / deodorant titanium oxide colloidal solution obtained by the method of the present invention has a dispersoid antibacterial / deodorant titanium oxide fine particle having a crystal form of anatase-type titanium oxide, and anatase-type titanium oxide. Since the crystallite diameter is large, it is excellent in photocatalytic action as well as antibacterial action.
以下、本発明方法を工程順に詳しく説明する。
工程（１）
本発明における抗菌・消臭性金属成分としては、一般に抗菌作用および／または消臭作用を有する金属成分が使用可能であり、具体的には、銀、銅、亜鉛、カドミウム、水銀、錫、鉛、ビスマス、鉄、コバルト、ニッケル、ロジウム、パラジウム、白金、マンガン、クロム、モリブデン、タングステン、バナジウム、ジルコニウムなどの金属成分が例示される。特に、銀、銅、亜鉛、錫、ビスマス、鉄、コバルト、ニッケル、ロジウム、パラジウム、白金、マンガン、モリブデン、タングステン、バナジウム、ジルコニウムは、抗菌・消臭作用に優れているので好ましい。さらに好ましくは、銀、銅、亜鉛、白金、パラジウムから選択される１種以上の抗菌・消臭性金属成分は、抗菌・消臭作用、変色および人体に対する安全性などの観点から望ましい。
本発明において抗菌・消臭性金属成分含有水溶液としては、前記金属成分の硝酸塩、硫酸塩、塩酸塩など、水や酸性水溶液に溶解可能な化合物の水溶液が使用される。該水溶液の金属成分の濃度は、酸化物として０．１〜５０重量％の範囲であることが望ましい。
Hereinafter, the method of the present invention will be described in detail in the order of steps.
Process (1 )
As the antibacterial / deodorant metal component in the present invention, a metal component generally having an antibacterial and / or deodorant action can be used, and specifically, silver, copper, zinc, cadmium, mercury, tin, lead And metal components such as bismuth, iron, cobalt, nickel, rhodium, palladium, platinum, manganese, chromium, molybdenum, tungsten, vanadium, and zirconium. In particular, silver, copper, zinc, tin, bismuth, iron, cobalt, nickel, rhodium, palladium, platinum, manganese, molybdenum, tungsten, vanadium, and zirconium are preferable because of their excellent antibacterial and deodorizing effects. More preferably, at least one antibacterial / deodorant metal component selected from silver, copper, zinc, platinum, and palladium is desirable from the viewpoint of antibacterial / deodorant action, discoloration, and safety to human body.
In the present invention, as the antibacterial / deodorant metal component-containing aqueous solution, an aqueous solution of a compound that is soluble in water or an acidic aqueous solution, such as nitrate, sulfate, and hydrochloride of the metal component, is used. The concentration of the metal component in the aqueous solution is desirably in the range of 0.1 to 50% by weight as an oxide.
本発明におけるチタン塩水溶液としては、硫酸チタン、硫酸チタニル、塩化チタンなどの水溶液が例示される。該チタン塩水溶液の濃度は、ＴｉＯ2として５〜５０重量％の範囲であることが望ましい。
本発明では、前述の抗菌・消臭性金属成分含有水溶液と前記チタン塩水溶液とを混合した水溶液を調製する。該抗菌・消臭性金属成分含有水溶液と該チタン塩水溶液の混合割合は、抗菌・消臭性金属成分の酸化物（ＭＯX）／ＴｉＯ2の重量比で０．１／１００〜５０／１００の範囲にあることが好ましい。該ＭＯX／ＴｉＯ2の重量比が０．１／１００より小さい場合には、抗菌・消臭性効果が小さくなることがあり、また、該ＭＯX／ＴｉＯ2の重量比が５０／１００より大きい場合には光触媒作用が弱くなることがある。該ＭＯX／ＴｉＯ2の重量比は、さらに好ましくは１／１００〜２０／１００の範囲にあることが望ましい。
前記混合した水溶液を撹拌しながら、これにアンモニア水や水酸化ナトリウム水溶液などのアルカリを添加して中和し、抗菌・消臭性金属とチタンの含水酸化物を生成する。アルカリの添加は、前記抗菌・消臭性金属成分含有水溶液と前記チタン塩水溶液とを混合した水溶液のｐＨが６．５〜７．５の範囲になるように調節するのが望ましい。
Examples of the aqueous titanium salt solution in the present invention include aqueous solutions of titanium sulfate, titanyl sulfate, titanium chloride and the like. The concentration of the titanium salt aqueous solution is desirably in the range of 5 to 50% by weight as TiO 2 .
In the present invention, an aqueous solution is prepared by mixing the aforementioned antibacterial / deodorant metal component-containing aqueous solution and the titanium salt aqueous solution. The mixing ratio of the antibacterial / deodorant metal component-containing aqueous solution and the titanium salt aqueous solution is 0.1 / 100 to 50/100 in terms of the weight ratio of the antibacterial / deodorant metal component oxide (MO x ) / TiO 2. It is preferable that it exists in the range. When the weight ratio of MO X / TiO 2 is smaller than 0.1 / 100, the antibacterial / deodorant effect may be reduced, and the weight ratio of MO X / TiO 2 is more than 50/100. If it is large, the photocatalytic action may be weakened. The MO x / TiO 2 weight ratio is more preferably in the range of 1/100 to 20/100.
While stirring the mixed aqueous solution, an alkali such as aqueous ammonia or aqueous sodium hydroxide is added to neutralize the mixed aqueous solution to produce a hydrous oxide of an antibacterial / deodorant metal and titanium. The addition of the alkali is desirably adjusted so that the pH of the aqueous solution obtained by mixing the antibacterial / deodorant metal component-containing aqueous solution and the titanium salt aqueous solution is in the range of 6.5 to 7.5.
工程（２）
工程（１）で得られた含水酸化物は、通常の方法で洗浄して副生塩を除去する。含水酸化物の洗浄は、好ましくは含水酸化物中の副生塩の量が乾量基準で１重量％以下、さらに好ましくは０．１重量％以下にすることが望ましい。含水酸化物中の副生塩の量が１重量％より多い場合にはコロイド溶液が得られないことがある。
Process (2 )
The hydrous oxide obtained in step (1) is washed by a usual method to remove by-product salts. In the washing of the hydrous oxide, the amount of by-product salt in the hydrous oxide is preferably 1% by weight or less, more preferably 0.1% by weight or less based on the dry weight. If the amount of by-product salt in the hydrous oxide is more than 1% by weight, a colloidal solution may not be obtained.
工程（３）
次いで、工程（２）で洗浄した含水酸化物を水に懸濁して懸濁液（スラリー）にする。該懸濁液の濃度は、酸化物として１〜２０重量％の範囲に調整するのが望ましい。
Process (3 )
Next, the hydrous oxide washed in step (2) is suspended in water to form a suspension (slurry). The concentration of the suspension is desirably adjusted to a range of 1 to 20% by weight as an oxide.
工程（４）
次に、前記懸濁液にシリカコロイド溶液および／または珪酸液を加えて混合する。シリカコロイド溶液を使用する場合には、シリカコロイド粒子の平均粒子径が３０ｎｍ以下、好ましくは１５ｎｍ以下であることが望ましい。前記懸濁液に該シリカコロイド溶液および／または珪酸液を加えることにより、耐光性に優れた、高濃度の長期間にわたって安定な抗菌・消臭性酸化チタンコロイド溶液が得られる。また、添加するシリカコロイド溶液および／または珪酸液のシリカ（ＳｉＯ2）量により、得られる抗菌・消臭性酸化チタンコロイド溶液の酸化チタンコロイド粒子の粒子径を制御することが可能である。該シリカの添加量が増すと該酸化チタンコロイド粒子の粒子径は小さくなり、添加量が少なくなると該酸化チタンコロイド粒子の粒子径は大きくなる。
本発明では、好ましくは前記シリカコロイド溶液および／または珪酸液のシリカ量は、ＳｉＯ2／（ＭＯX＋ＴｉＯ2）の重量比で０．５／１００〜３０／１００の範囲、さらに好ましくは１／１００〜２０／１００の範囲にあることが望ましい。
Process (4 )
Next, a silica colloid solution and / or a silicic acid solution is added to the suspension and mixed. When a silica colloid solution is used, it is desirable that the silica colloid particles have an average particle size of 30 nm or less, preferably 15 nm or less. By adding the silica colloid solution and / or silicic acid solution to the suspension, an antibacterial / deodorant titanium oxide colloid solution having excellent light resistance and stable for a long period of time can be obtained. Moreover, the particle diameter of the titanium oxide colloid particles of the obtained antibacterial / deodorant titanium oxide colloid solution can be controlled by the amount of silica (SiO 2 ) in the silica colloid solution and / or silicic acid solution to be added. When the addition amount of the silica increases, the particle diameter of the titanium oxide colloidal particles decreases, and when the addition amount decreases, the particle diameter of the titanium oxide colloidal particles increases.
In the present invention, the silica amount of the silica colloid solution and / or the silicic acid solution is preferably in the range of 0.5 / 100 to 30/100, more preferably 1/2, in terms of the weight ratio of SiO 2 / (MO x + TiO 2 ). It is desirable to be in the range of 100-20 / 100.
工程（５）
工程（４）の混合懸濁液に、さらにアルカリを加えて該懸濁液のｐＨを７〜１３の範囲に調整する。該懸濁液のｐＨが７〜１３の範囲を外れると抗菌・消臭性酸化チタン微粒子が分散したコロイド溶液の生成が起こらないことがある。該懸濁液のｐＨは好ましくは８〜１２の範囲、さらに好ましくは８〜１０の範囲である。
Process (5 )
An alkali is further added to the mixed suspension in step (4) to adjust the pH of the suspension to a range of 7 to 13. When the pH of the suspension is outside the range of 7 to 13, a colloidal solution in which antibacterial / deodorant titanium oxide fine particles are dispersed may not occur. The pH of the suspension is preferably in the range of 8-12, more preferably in the range of 8-10.
工程（６）
次いで、前記ｐＨ調整した懸濁液をオートクレーブで温度１１０〜２５０℃の範囲で加熱処理する。加熱処理温度が１１０℃より低い場合には、抗菌・消臭性酸化チタン微粒子が生成しないことがあり、また、該温度が２５０℃より高い場合には、オートクレーブ処理の設備費が高くなり経済的でない。
また、加熱処理は抗菌・消臭性酸化チタン微粒子が分散したコロイド溶液の生成が起こるまで行い、通常前記温度範囲で１〜２４時間、好ましくは１０〜２０時間行うのが望ましい。
なお、前述の方法で得られる抗菌・消臭性酸化チタンコロイド溶液はアルカリ性であるが、抗菌・消臭性酸化チタンコロイド溶液の用途によってアルカリ性が好ましくない場合には、さらに、該抗菌・消臭性酸化チタンコロイド溶液を限外濾過膜装置などで洗浄してアルカリ分を除去することもできる。
Process (6 )
Next, the suspension whose pH has been adjusted is heat-treated in an autoclave at a temperature in the range of 110 to 250 ° C. When the heat treatment temperature is lower than 110 ° C., antibacterial / deodorant titanium oxide fine particles may not be formed. When the temperature is higher than 250 ° C., the equipment cost for the autoclave treatment becomes high and economical. Not.
The heat treatment is carried out until formation of a colloidal solution in which antibacterial and deodorant titanium oxide fine particles are dispersed, and it is usually carried out in the above temperature range for 1 to 24 hours, preferably 10 to 20 hours.
The antibacterial / deodorant titanium oxide colloidal solution obtained by the above-mentioned method is alkaline, but if the alkalinity is not preferred depending on the use of the antibacterial / deodorant titanium oxide colloidal solution, the antibacterial / deodorant The alkaline content can also be removed by washing the colloidal titanium oxide solution with an ultrafiltration membrane device or the like.
前述の方法で得られる抗菌・消臭性酸化チタンコロイド溶液の抗菌・消臭性酸化チタン微粒子はアナターゼ型酸化チタンの結晶形であることが好ましい。アナターゼ型酸化チタンは、光触媒作用が強いので好適である。なお、結晶形の測定は、該抗菌・消臭性酸化チタンコロイド溶液を１１０℃で１６時間乾燥させた試料についてＸ線回折することにより行われる。 It is preferable that the antibacterial / deodorant titanium oxide fine particles of the antibacterial / deodorant titanium oxide colloidal solution obtained by the above-described method have a crystalline form of anatase type titanium oxide. Anatase-type titanium oxide is suitable because of its strong photocatalytic action. The crystal form is measured by X-ray diffraction of a sample obtained by drying the antibacterial / deodorant titanium oxide colloid solution at 110 ° C. for 16 hours.
前述のアナターゼ型酸化チタンは、結晶子の大きさが１００Å以上であることが好ましい。該アナターゼ型酸化チタンの結晶子の大きさが１００Åより小さい場合には酸化チタンに基づく光触媒作用が弱いことがある。該アナターゼ型酸化チタンの結晶子の大きさは、さらに好ましくは１１０〜３５０Åの範囲にあることが望ましい。なお、該酸化チタンの結晶子の大きさは、Ｘ線回折による（１０１）面の面間隔ｄ＝３．５２Å（２θ＝２５．３°）（ＣｕＫα）の半値幅からデバイ−シエラー（Ｄｅｂｙｅ−Ｓｈｅｒｒｅｒ）の式により求めた値である。
以下に実施例を示し、本発明を更に具体的に説明する。
The aforementioned anatase type titanium oxide preferably has a crystallite size of 100 mm or more. When the crystallite size of the anatase-type titanium oxide is smaller than 100 mm, the photocatalytic action based on titanium oxide may be weak. The size of the crystallites of the anatase-type titanium oxide is more preferably in the range of 110 to 350cm. The crystallite size of the titanium oxide is determined from the half width of the (101) plane spacing d = 3.52３．５ (2θ = 25.3 °) (CuKα) by X-ray diffraction. This is a value obtained by the equation of (Sherler).
Hereinafter, the present invention will be described more specifically with reference to examples.
硫酸チタニル２水塩結晶（テイカ（株）製：ＴＭ結晶）２．５ｋｇに水２．５ｋｇを加え、攪拌溶解して硫酸チタニル水溶液を調製した。次いで、直ちに該硫酸チタニル水溶液の５４３８ｇに硫酸亜鉛（関東化学（株）鹿１級ＺｎＳＯ4・７Ｈ2Ｏ）３５４．６ｇを加え、さらに水１４ｋｇを加えて硫酸チタニルと硫酸亜鉛の混合水溶液を調製した。さらに、該混合水溶液に１５重量％アンモニア水を添加して、混合水溶液のｐHを７．０にして含水酸化物を生成させた。
該含水酸化物を平板フィルターにて濾過し、１００ｋｇの純水で掛水洗浄して副生塩を除去した含水酸化物を得た。なお、該含水酸化物中のＳＯ4の量は０．１重量％（乾量基準）であった。
次いで、洗浄した含水酸化物を水で希釈して固形分濃度５重量％の懸濁液２０．１ｋｇを調製した。該懸濁液にシリカ濃度１６重量％のシリカゾル（触媒化成工業（株）製：Ｃａｔａｌｏｉｄ−ＳＮ３５０）９４０ｇを加え、さらに３重量％カセイソーダ水を加えて該懸濁液のｐＨを１０．５に調整し、該ｐＨ調整した懸濁液をオートクレーブにて１６０℃で１６時間加熱処理を行って、亜鉛含有酸化チタンコロイド粒子が分散した抗菌・消臭性酸化チタンコロイド溶液（Ａ）を得た。
2.5 kg of water was added to 2.5 kg of titanyl sulfate dihydrate crystals (manufactured by Teika Co., Ltd .: TM crystal), and dissolved by stirring to prepare a titanyl sulfate aqueous solution. Next, immediately after adding 354.6 g of zinc sulfate (Kanto Chemical Co., Ltd. Deer grade 1 ZnSO 4 .7H 2 O) to 5438 g of the aqueous solution of titanyl sulfate, 14 kg of water is added to prepare a mixed aqueous solution of titanyl sulfate and zinc sulfate. did. Furthermore, 15 wt% aqueous ammonia was added to the mixed aqueous solution to adjust the pH of the mixed aqueous solution to 7.0, thereby producing a hydrous oxide.
The hydrated oxide was filtered with a flat plate filter and washed with 100 kg of pure water to obtain a hydrated oxide from which by-product salts had been removed. The amount of SO 4 in the hydrated oxide was 0.1% by weight (on a dry basis).
Next, the washed hydrous oxide was diluted with water to prepare 20.1 kg of a suspension having a solid content concentration of 5% by weight. 940 g of silica sol (Catalyst Kasei Kogyo Co., Ltd .: Cataloid-SN350) with a silica concentration of 16% by weight was added to the suspension, and further 3% by weight of caustic soda water was added to adjust the pH of the suspension to 10.5. The pH-adjusted suspension was heat-treated at 160 ° C. for 16 hours in an autoclave to obtain an antibacterial / deodorant titanium oxide colloidal solution (A) in which zinc-containing titanium oxide colloidal particles were dispersed.
該抗菌・消臭性酸化チタンコロイド溶液（Ａ）は、ｐＨが１０．２で、固形分濃度が４．９重量％で、固形分中のＺｎＯの含有量は、９．０重量％であった。また、該抗菌・消臭性酸化チタンコロイド溶液（Ａ）の亜鉛含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）を、超遠心式自動粒度分布測定装置(堀場製作所製：ＣＡＰＡ―７００)で測定）したところ、２０．０ｎｍであった。
該抗菌・消臭性酸化チタンコロイド溶液（Ａ）の一部を１１０℃で１６時間乾燥させた試料をＸ線回折装置 (リガク（株）製：ＲＩＮＴ−１４００)によりＸ線回折測定した結果、アナターゼ型酸化チタンのＸ線回折図を示し、結晶子径の大きさは１５０Åであった。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ａ）は１ケ月間放置しても安定なコロイド状態を維持していた。
The antibacterial / deodorant titanium oxide colloidal solution (A) had a pH of 10.2, a solid content concentration of 4.9% by weight, and a ZnO content in the solid content of 9.0% by weight. It was. In addition, the average particle diameter (Dp) of the zinc-containing titanium oxide colloidal particles in the antibacterial / deodorant titanium oxide colloidal solution (A) is measured with an ultracentrifugal automatic particle size distribution analyzer (Horiba Seisakusho: CAPA-700). ) To 20.0 nm.
A sample obtained by drying a part of the antibacterial / deodorant titanium oxide colloid solution (A) at 110 ° C. for 16 hours was subjected to X-ray diffraction measurement using an X-ray diffractometer (RINT-1400, manufactured by Rigaku Corporation). The X-ray diffraction pattern of anatase-type titanium oxide was shown, and the crystallite size was 150 mm. The antibacterial / deodorant titanium oxide colloidal solution (A) maintained a stable colloidal state even when left for 1 month.
実施例１において、オートクレーブでの処理を１２０℃で１６時間加熱処理したこと以外は実施例１と同様にして、亜鉛含有酸化チタンコロイド粒子が分散した抗菌・消臭性酸化チタンコロイド溶液（Ｂ）を調製した。
該抗菌・消臭性酸化チタンコロイド溶液（Ｂ）は、ｐＨが１０．０で、固形分濃度が４．８重量％で、固形分中のＺｎＯの含有量は、９．１重量％であった。
また、該抗菌・消臭性酸化チタンコロイド溶液（Ａ）の亜鉛含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）は、２１．０ｎｍで、アナターゼ型酸化チタンのＸ線回折図を示し、結晶子径の大きさは１０５Åであった。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ｂ）は１ケ月間放置しても安定なコロイド状態を維持していた。
In Example 1, an antibacterial / deodorant titanium oxide colloidal solution (B) in which zinc-containing titanium oxide colloidal particles are dispersed is the same as in Example 1 except that the treatment in the autoclave is heat-treated at 120 ° C. for 16 hours. Was prepared.
The antibacterial / deodorant titanium oxide colloidal solution (B) had a pH of 10.0, a solid content concentration of 4.8% by weight, and a ZnO content in the solid content of 9.1% by weight. It was.
The average particle diameter (Dp) of the zinc-containing titanium oxide colloidal particles of the antibacterial / deodorant titanium oxide colloidal solution (A) is 21.0 nm, and shows an X-ray diffraction diagram of anatase-type titanium oxide. The diameter was 105 mm. The antibacterial / deodorant titanium oxide colloidal solution (B) maintained a stable colloidal state even when left for 1 month.
実施例１において、硫酸亜鉛の代わりに、硫酸銅（関東化学（株）鹿１級、ＣｕＳＯ4・５Ｈ2Ｏ）３１２．５ｇを加えたこと以外は実施例１と同様にして、銅含有酸化チタンコロイド粒子が分散した抗菌・消臭性酸化チタンコロイド溶液（Ｃ）を調製した。
該抗菌・消臭性酸化チタンコロイド溶液（Ｃ）は、ｐＨが１０．２で、固形分濃度が５．０重量％で、固形分中のＣｕＯの含有量は、９．０重量％であった。
また、該抗菌・消臭性酸化チタンコロイド溶液（Ｃ）の銅含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）は、２２．０ｎｍで、アナターゼ型酸化チタンのＸ線回折図を示し、結晶子径の大きさは１４８Åであった。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ｃ）は１ケ月間放置しても安定なコロイド状態を維持していた。
In Example 1, instead of zinc sulfate, copper-containing oxidation was carried out in the same manner as in Example 1 except that 312.5 g of copper sulfate (Kanto Chemical Co., Ltd. Deer grade 1, CuSO 4 .5H 2 O) was added. An antibacterial / deodorant titanium oxide colloidal solution (C) in which titanium colloid particles were dispersed was prepared.
The antibacterial / deodorant titanium oxide colloidal solution (C) had a pH of 10.2, a solid content concentration of 5.0% by weight, and a CuO content in the solid content of 9.0% by weight. It was.
Moreover, the average particle diameter (Dp) of the copper-containing titanium oxide colloidal particles of the antibacterial / deodorant titanium oxide colloidal solution (C) is 22.0 nm, and shows an X-ray diffraction diagram of anatase type titanium oxide, The diameter was 148 mm. The antibacterial / deodorant titanium oxide colloidal solution (C) maintained a stable colloidal state even when left for 1 month.
実施例１において、硫酸亜鉛の代わりに、硝酸銀（関東化学（株）製、鹿１級ＡｇＮＯ3）７３．５ｇを加えたこと以外は実施例１と同様にして銀含有酸化チタンコロイド粒子が分散した抗菌・消臭性酸化チタンコロイド溶液（Ｄ）を調製した。該抗菌・消臭性酸化チタンコロイド溶液（Ｄ）は、ｐＨが１０．０で、固形分濃度が４．８重量％で、固形分中のＡｇ2Ｏの含有量は、４．５重量％であった。
該抗菌・消臭性酸化チタンコロイド溶液（ｄ）を限外濾過膜装置で固形分に対して２００倍の純水で洗浄後、濃縮して銀含有酸化チタンコロイド粒子が分散した抗菌・消臭性酸化チタンコロイド溶液（Ｄ）を得た。
In Example 1, silver-containing titanium oxide colloidal particles were dispersed in the same manner as in Example 1 except that 73.5 g of silver nitrate (manufactured by Kanto Chemical Co., Ltd., deer grade 1 AgNO 3 ) was added instead of zinc sulfate. An antibacterial / deodorant titanium oxide colloidal solution (D) was prepared. The antibacterial and deodorant titanium oxide colloidal solution (D) has a pH of 10.0, a solid content concentration of 4.8% by weight, and the content of Ag 2 O in the solid content is 4.5% by weight. Met.
The antibacterial / deodorant titanium oxide colloidal solution (d) is washed with 200 times pure water with respect to the solid content with an ultrafiltration membrane device and concentrated to disperse the silver-containing titanium oxide colloidal particles. Titanium oxide colloidal solution (D) was obtained.
該抗菌・消臭性酸化チタンコロイド溶液（Ｄ）は、ｐＨが９．３で、固形分濃度が４．９重量％であった。
また、該抗菌・消臭性酸化チタンコロイド溶液（Ｄ）の銀含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）は、１８．５ｎｍで、アナターゼ型酸化チタンのＸ線回折図を示し、結晶子径の大きさは１５２Åであった。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ｄ）は１ケ月間放置しても安定なコロイド状態を維持していた。
The antibacterial / deodorant titanium oxide colloidal solution (D) had a pH of 9.3 and a solid content concentration of 4.9% by weight.
The average particle diameter (Dp) of the silver-containing titanium oxide colloidal particles of the antibacterial / deodorant titanium oxide colloidal solution (D) is 18.5 nm, and shows an X-ray diffraction pattern of anatase-type titanium oxide. The diameter was 152 mm. The antibacterial / deodorant titanium oxide colloidal solution (D) maintained a stable colloidal state even when left for 1 month.
硫酸チタニル２水塩結晶（テイカ（株）製：ＴＭ結晶）２．５ｋｇに水２．５ｋｇを加え、攪拌溶解して硫酸チタニル水溶液を調製した。次いで、該硫酸チタニル水溶液の２．５ｋｇに、さらに水５．５ｋｇを加えて希釈した後、この水溶液に１５重量％アンモニア水を添加して、水溶液のｐHを７．０にして含水酸化物を生成させた。
該含水酸化物を平板フィルターにて濾過し、４０ｋｇの純水で掛水洗浄して副生塩を除去した含水酸化物を得た。なお、該含水酸化物中のＳＯ4の量は０．２重量％（乾量基準）であった。
次いで、洗浄した含水酸化物を水で希釈して固形分濃度１重量％の懸濁液１００ｋｇを調製した。
該懸濁液の４０ｋｇに、濃度３５重量％の過酸化水素２．８ｋｇを添加し、９０℃で２時間加熱して固形分濃度１重量％の酸化チタンコロイド溶液を得た。
2.5 kg of water was added to 2.5 kg of titanyl sulfate dihydrate crystals (manufactured by Teika Co., Ltd .: TM crystal), and dissolved by stirring to prepare a titanyl sulfate aqueous solution. Next, after adding 5.5 kg of water to 2.5 kg of the aqueous solution of titanyl sulfate and diluting, 15 wt% aqueous ammonia is added to the aqueous solution to adjust the pH of the aqueous solution to 7.0, and the hydrous oxide. Generated.
The hydrated oxide was filtered through a flat plate filter and washed with 40 kg of pure water to obtain a hydrated oxide from which by-product salts had been removed. The amount of SO 4 in the hydrated oxide was 0.2% by weight (on a dry basis).
Next, the washed hydrous oxide was diluted with water to prepare 100 kg of a suspension having a solid content concentration of 1% by weight.
To 40 kg of the suspension, 2.8 kg of hydrogen peroxide having a concentration of 35% by weight was added and heated at 90 ° C. for 2 hours to obtain a titanium oxide colloid solution having a solid content of 1% by weight.
一方、硝酸銅（関東化学（株）試薬鹿１級、（Ｃｕ（ＮＯ3）2・３Ｈ2Ｏ）１２．３３ｇに水３６４８ｇを加えて、濃度０．５重量％の硝酸銅水溶液を調整した。
前記酸化チタンコロイド溶液４．０ｋｇをビーカーに採取し、これを攪拌しながら５０℃に加温した。この時の酸化チタンコロイド溶液のｐＨは７．９であった。該チタンコロイド溶液に前記硝酸銅水溶液をペリスターポンプにて１０ｇ／ｍｉｎの速度で添加した。硝酸銅水溶液の添加でコロイド溶液のｐＨが低下し始めたところで、陰イオン交換樹脂（三菱化学製）を最初のｐＨ７．９を維持するように少量ずつ添加し、全硝酸銅水溶液の添加が終了するまで、この操作を継続した。
陰イオン交換樹脂の全使用量は３１０ｇであり、また、コロイド溶液の最終ｐＨは８．１であった。
On the other hand, 3648 g of water was added to 12.33 g of copper nitrate (Kanto Chemical Co., Ltd., reagent deer grade 1, (Cu (NO 3 ) 2 .3H 2 O) to prepare an aqueous copper nitrate solution having a concentration of 0.5% by weight. .
4.0 kg of the titanium oxide colloidal solution was collected in a beaker and heated to 50 ° C. while stirring. At this time, the pH of the titanium oxide colloidal solution was 7.9. The aqueous copper nitrate solution was added to the titanium colloid solution at a rate of 10 g / min with a peristaltic pump. When the pH of the colloidal solution began to drop due to the addition of the aqueous copper nitrate solution, anion exchange resin (Mitsubishi Chemical) was added in small portions so as to maintain the initial pH of 7.9, and the addition of the total aqueous copper nitrate solution was completed. This operation was continued until
The total amount of anion exchange resin used was 310 g, and the final pH of the colloidal solution was 8.1.
該コロイド水溶液を限外濾過膜装置でＴｉＯ2重量に対して２００倍の純水で洗浄した後、濃縮して、銅含有酸化チタンコロイド粒子が分散した固形分濃度１０重量％の安定な抗菌・消臭性酸化チタンコロイド溶液（Ｅ）を調製した。該抗菌・消臭性酸化チタンコロイド溶液（Ｅ）の固形分中のＣｕＯの含有量は、９．８重量％であった。
また、該抗菌・消臭性酸化チタンコロイド溶液（Ｅ）の銅含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）は１２．０ｎｍで、無定形のＸ線回折図を示した。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ｅ）は１ケ月間放置しても安定なコロイド状態を維持していた。
The colloidal aqueous solution is washed with 200 times pure water with respect to TiO 2 weight by an ultrafiltration membrane device, and then concentrated, and stable antibacterial / solid content concentration 10% by weight in which copper-containing titanium oxide colloid particles are dispersed. A deodorant titanium oxide colloidal solution (E) was prepared. The CuO content in the solid content of the antibacterial / deodorant titanium oxide colloidal solution (E) was 9.8% by weight.
Further, the average particle diameter (Dp) of the copper-containing titanium oxide colloid particles of the antibacterial / deodorant titanium oxide colloid solution (E) was 12.0 nm, and an amorphous X-ray diffraction diagram was shown. The antibacterial / deodorant titanium oxide colloidal solution (E) maintained a stable colloidal state even when left for 1 month.
比較例１において、硝酸銅の代わりに硝酸亜鉛（関東化学（株）試薬鹿１級、（Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ））１４．６ｇを用いた他は比較例１と同様にして、亜鉛含有酸化チタンコロイド粒子が分散した固形分濃度１０重量％の安定な抗菌・消臭性酸化チタンコロイド溶液（Ｆ）を調製した。該抗菌・消臭性酸化チタンコロイド溶液（Ｆ）の固形分中のＺｎＯの含有量は、９．１重量％であった。
また、該抗菌・消臭性酸化チタンコロイド溶液（Ｆ）の亜鉛含有酸化チタンコロイド粒子の平均粒子径（Ｄｐ）は１５．０ｎｍで、無定形のＸ線回折図を示した。なお、該抗菌・消臭性酸化チタンコロイド溶液（Ｆ）は１ケ月間放置しても安定なコロイド状態を維持していた。
Comparative Example 1 was the same as Comparative Example 1 except that 14.6 g of zinc nitrate (Kanto Chemical Co., Ltd., reagent deer grade 1, (Zn (NO 3 ) 2 .6H 2 O)) was used instead of copper nitrate. Thus, a stable antibacterial / deodorant titanium oxide colloidal solution (F) having a solid content concentration of 10% by weight in which zinc-containing titanium oxide colloidal particles were dispersed was prepared. The ZnO content in the solid content of the antibacterial / deodorant titanium oxide colloidal solution (F) was 9.1% by weight.
Moreover, the average particle diameter (Dp) of the zinc-containing titanium oxide colloid particles of the antibacterial / deodorant titanium oxide colloid solution (F) was 15.0 nm, and an amorphous X-ray diffraction pattern was shown. The antibacterial / deodorant titanium oxide colloidal solution (F) maintained a stable colloidal state even when left for 1 month.
実施例１〜４で得られた抗菌・消臭性酸化チタンコロイド溶液（Ａ）〜（Ｄ）の各々の一部を採取し、それぞれ固形分濃度３０００ｐｐｍの溶液に調整して、それぞれの溶液にポリエステル繊維を室温にて５分間浸漬、ピックアップ１００％になるように絞り、８０℃で乾燥して、抗菌・消臭性酸化チタンコロイド粒子を担持したポリエステル繊維の試料（ＡＦ）〜（ＤＦ）を調製した。 A part of each of the antibacterial / deodorant titanium oxide colloidal solutions (A) to (D) obtained in Examples 1 to 4 was collected and adjusted to a solution with a solid content of 3000 ppm. Polyester fiber samples (AF) to (DF) carrying antibacterial and deodorant titanium oxide colloidal particles are immersed in polyester fiber for 5 minutes at room temperature, squeezed to 100% pickup and dried at 80 ° C. Prepared.
比較例１および２で得られた抗菌・消臭性酸化チタンコロイド溶液（Ｅ）および（Ｆ）の各々の一部を採取し、それぞれ固形分濃度３０００ｐｐｍの溶液に調整して、それぞれの溶液にポリエステル繊維を室温にて５分間浸漬、ピックアップ１００％になるように絞り、８０℃で乾燥して、抗菌・消臭性酸化チタンコロイド粒子を担持したポリエステル繊維の試料（ＥＦ）および（ＦＦ）を調製した。 A part of each of the antibacterial / deodorant titanium oxide colloidal solutions (E) and (F) obtained in Comparative Examples 1 and 2 was collected and adjusted to a solution with a solid content of 3000 ppm. Polyester fiber samples (EF) and (FF) loaded with antibacterial and deodorant titanium oxide colloidal particles are immersed in polyester fiber for 5 minutes at room temperature, squeezed to 100% pickup and dried at 80 ° C. Prepared.
抗菌性の評価試験１
実施例１〜４および比較例１〜２で得られた抗菌・消臭性酸化チタンコロイド溶液（Ａ）〜（Ｄ）および（Ｅ）、（Ｆ）の一部を１１０℃で３時間乾燥して、それぞれの抗菌・消臭性酸化チタン粉末試料（ＡＰ）〜（ＤＰ）および（ＥＰ）、（ＦＰ）を調製した。
これらの抗菌・消臭性酸化チタン粉末試料について、次の抗菌性の評価試験を行った。即ち、試験菌には、大腸菌(Escherichia coli NBRC 3972)と、黄色ぶどう球菌(Staphylococcus aureuse NBRC 12732)とを用い、５０ｍｌのリン酸緩衝液に試験菌を懸濁させ、前記粉末試料（ＡＰ）〜（ＤＰ）および（ＥＰ）、（ＦＰ）を０．１ｇ添加して、室温で１時間、３３０ｒｐｍで攪拌した後、生菌数を測定した。空試験の１時間後の生菌数（Ａ）と、抗菌剤添加試験の１時間後の生菌数（Ｂ）とを測定し、増減値差（Log．Ａ−Log．Ｂ）により評価を行った。評価結果を表１に示す。
Antibacterial evaluation test 1
Part of the antibacterial / deodorant titanium oxide colloidal solutions (A) to (D) and (E) and (F) obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were dried at 110 ° C. for 3 hours. The antibacterial and deodorant titanium oxide powder samples (AP) to (DP), (EP), and (FP) were prepared.
The antibacterial and deodorant titanium oxide powder samples were subjected to the following antibacterial evaluation test. Specifically, Escherichia coli NBRC 3972 and Staphylococcus aureuse NBRC 12732 are used as test bacteria, and the test bacteria are suspended in 50 ml of a phosphate buffer, and the powder sample (AP) to After adding 0.1 g of (DP), (EP), and (FP) and stirring at 330 rpm for 1 hour at room temperature, the viable cell count was measured. Measure the viable cell count (A) 1 hour after the blank test and the viable cell count (B) 1 hour after the antibacterial agent addition test, and evaluate by the difference between the increase and decrease values (Log.A-Log.B). went. The evaluation results are shown in Table 1.
［表１］ 抗菌性評価結果１
粉末試料 増 減 値 差
大腸菌 黄色ぶどう球菌
ＡＰ ３．３ ４．０
ＢＰ ２．９ ３．０
ＣＰ ＞５ ４．５
ＤＰ ＞５ ＞５
ＥＰ ０．５ ０．６
ＦＰ ０．９ ０．８
[Table 1] Antibacterial evaluation result 1
Powder sample increase / decrease value difference
E. coli Staphylococcus aureus AP 3.3 4.0
BP 2.9 3.0
CP> 5 4.5
DP>5> 5
EP 0.5 0.6
FP 0.9 0.8
前記リン酸緩衝液とは、リン酸２水素カリウム３４ｇを１０００ｍｌの精製水に溶解し、水酸化ナトリウムでｐＨを７．２に調整した後、これを０．８５％塩化ナトリウム溶液で８００倍に希釈したものである。
表１から、ベースがアナターゼ型結晶の酸化チタン粉末試料は、無定形酸化チタン粉末試料より高い抗菌性を示し、中でも、アナターゼ型結晶子径の大きいものがさらに高い抗菌性を示すことが分かる。
The phosphate buffer solution is obtained by dissolving 34 g of potassium dihydrogen phosphate in 1000 ml of purified water, adjusting the pH to 7.2 with sodium hydroxide, and then increasing this to 800 times with 0.85% sodium chloride solution. Diluted.
From Table 1, it can be seen that the titanium oxide powder sample whose base is anatase type crystal shows higher antibacterial properties than the amorphous titanium oxide powder sample, and among them, those having a larger anatase type crystallite diameter show higher antibacterial properties.
抗菌性の評価試験２
実施例５および比較例３で調製したポリエステル繊維の試料（ＡＦ）〜（ＤＦ）および（ＥＦ）、（ＦＦ）について抗菌性の評価試験を行った。評価試験は“繊維製品の定量的抗菌性試験方法 JIS L 1902”に従って行った。
・試験菌 ：肺炎桿菌(Klebsiella pneumoniae NBRC13277)
黄色ぶどう球菌(Staphylococcus aureuse NBRC12732)
・栄養 ：１／２０濃度のニュートリエントブロス*1)
（＊１）150mg/Lの肉エキス＋250mg/Lのペプトン
・測定方法：バイアル瓶に試料０．４ｇ入れて、菌懸濁液（界面活性剤Tween80を0.05%添加）０．２ｍｌを滴下し、３７℃で１８時間培養後、洗い出し、生菌数を測定した。評価結果を表２に示す。
表２から、ベースがアナターゼ型結晶の酸化チタンコロイド粒子を担持した繊維試料は、無定形酸化チタンコロイド粒子を担持した繊維試料より高い抗菌性を示すことが分かる。
Antibacterial evaluation test 2
The antibacterial evaluation test was performed on the polyester fiber samples (AF) to (DF), (EF), and (FF) prepared in Example 5 and Comparative Example 3. The evaluation test was performed according to “Quantitative antibacterial test method JIS L 1902 for textile products”.
-Test bacteria: Klebsiella pneumoniae (Klebsiella pneumoniae NBRC13277)
Staphylococcus aureuse NBRC12732
・ Nutrition: 1/20 concentration of nutrient broth * 1)
(* 1) 150 mg / L meat extract + 250 mg / L peptone Measurement method: Put 0.4 g of sample in a vial and add 0.2 ml of the bacterial suspension (added with 0.05% of surfactant Tween80) After culturing at 37 ° C. for 18 hours, the cells were washed out and the viable cell count was measured. The evaluation results are shown in Table 2.
From Table 2, it can be seen that the fiber sample carrying the titanium oxide colloidal particles whose base is anatase type crystal shows higher antibacterial properties than the fiber sample carrying the amorphous titanium oxide colloidal particles.
［表２］ 抗菌性評価結果２
繊維試料 増 減 値 差
肺炎桿菌 黄色ぶどう球菌
ＡＦ ４．５ ４．５
ＢＦ ３．０ ２．９
ＣＦ ５．０ ＞５
ＤＦ ＞５ ＞５
ＥＦ −０．２ ０．０
ＦＦ −０．３ ０．３
[Table 2] Antibacterial evaluation result 2
Fiber sample increase / decrease value difference
S. pneumoniae Staphylococcus aureus AF 4.5 4.5
BF 3.0 2.9
CF 5.0> 5
DF>5> 5
EF -0.2 0.0
FF -0.3 0.3
光触媒効果試験
抗菌性の評価試験１で使用した抗菌・消臭性酸化チタン粉末試料（ＡＰ）〜（ＥＰ）および（ＥＰ）、（ＦＰ）を用いて光による消臭試験を行った。
それぞれ１Ｌパックに抗菌・消臭性酸化チタン粉末試料２ｇとアセトアルデヒド濃度４００ｐｐｍの溶液１Ｌを入れたものを、ブラックライト(20W×2本)にて２５℃で３時間照射した後、検知管でアセトアルデヒドとＣＯ2の濃度を測定した。測定結果を表３に示す。
表３から、ベースがアナターゼ型結晶の酸化チタン粉末試料は、無定形酸化チタン粉末試料より高い光触媒効果を示し、中でも、アナターゼ型結晶子径の大きいものがさらに高い光触媒効果を示すことが分かる。
Photocatalytic effect test Antibacterial and deodorant titanium oxide powder samples (AP) to (EP), (EP), (EP) and (FP) used in the antibacterial evaluation test 1 were used to perform a deodorization test by light.
Each 1L pack containing 2g of antibacterial and deodorant titanium oxide powder sample and 1L of acetaldehyde concentration 400ppm solution was irradiated with black light (20W x 2) for 3 hours at 25 ° C, and then acetaldehyde in a detector tube And the concentration of CO 2 were measured. Table 3 shows the measurement results.
From Table 3, it can be seen that the titanium oxide powder sample whose base is an anatase type crystal shows a higher photocatalytic effect than the amorphous titanium oxide powder sample, and among them, those having a larger anatase type crystallite diameter show a higher photocatalytic effect.
［表３］ 光触媒効果試験結果
粉末試料 ＣＯ 2 （ｐｐｍ）
ＡＰ ６００
ＢＰ ３００
ＣＰ ６５０
ＤＰ ４００
ＥＰ １００
ＦＰ ５０
[Table 3] Photocatalytic effect test results
Powder sample CO 2 (ppm )
AP 600
BP 300
CP 650
DP 400
EP 100
FP 50
消臭性評価試験１
抗菌性の評価試験１で使用した抗菌・消臭性酸化チタン粉末試料（ＡＰ）〜（ＥＰ）および（ＥＰ）、（ＦＰ）を用いて消臭性評価試験を行った。
それぞれ、５Ｌテトラバックに抗菌・消臭性酸化チタン粉末試料１ｇと、初期濃度１００ｐｐｍのアンモニア試験臭３Ｌおよび初期濃度４ｐｐｍの硫化水素試験臭３Ｌを封入して２時間放置した後、検知管にて試験臭濃度を測定した。測定結果を表４に示す。
表４から、ベースがアナターゼ型結晶の酸化チタン粉末試料は、無定形酸化チタン粉末試料より高い消臭効果を示し、中でも、アナターゼ型結晶子径の大きいものがさらに高い消臭効果を示すことが分かる。
Deodorant evaluation test 1
The antibacterial and deodorant titanium oxide powder samples (AP) to (EP), (EP), and (FP) used in the antibacterial evaluation test 1 were used to perform a deodorant evaluation test.
1 g of antibacterial / deodorant titanium oxide powder sample, 3 L of ammonia test odor with an initial concentration of 100 ppm, and 3 L of hydrogen sulfide test odor with an initial concentration of 4 ppm were placed in a 5 L tetrabag and left for 2 hours, and then in a detector tube The test odor concentration was measured. Table 4 shows the measurement results.
From Table 4, the titanium oxide powder sample whose base is anatase type crystal shows a higher deodorizing effect than the amorphous titanium oxide powder sample, and among them, those having a larger anatase type crystallite size show a higher deodorizing effect. I understand.
［表４］ 消臭性評価試験結果１
粉末試料 消 臭 率（％）
アンモニア 硫化水素
ＡＰ １００ １００
ＢＰ ９８ ９５
ＣＰ １００ １００
ＤＰ ９５ ８５
ＥＰ ７０ ５０
ＦＰ ６０ ４０
[Table 4] Deodorant evaluation test result 1
Powder sample deodorization rate (% )
Ammonia hydrogen sulfide AP 100 100
BP 98 95
CP 100 100
DP 95 85
EP 70 50
FP 60 40
消臭性評価試験２
実施例５および比較例３で調製したポリエステル繊維の試料（ＡＦ）〜（ＤＦ）および（ＥＦ）（ＦＦ）について消臭性評価試験を行った。
それぞれ、５Ｌテトラバックにポリエステル繊維の試料試験布１０×１０ｃｍと、初期濃度１００ｐｐｍのアンモニア試験臭３Ｌおよび初期濃度４ｐｐｍの硫化水素試験臭３Ｌを封入して２時間放置した後、検知管にて試験臭濃度を測定した。結果を表５に示す。
繊維に加工しても表４の場合と同様に、ベースがアナターゼ型結晶の酸化チタンコロイド粒子を担持した繊維試料は、無定形酸化チタンコロイド粒子を担持した繊維試料より高い消臭効果を示した。
Deodorant evaluation test 2
The polyester fiber samples (AF) to (DF) and (EF) (FF) prepared in Example 5 and Comparative Example 3 were subjected to a deodorizing evaluation test.
A polyester fiber sample test cloth 10 × 10 cm, an ammonia test odor 3 L with an initial concentration of 100 ppm, and a hydrogen sulfide test odor 3 L with an initial concentration of 4 ppm were sealed in a 5 L tetraback, and left for 2 hours, and then tested with a detector tube. The odor concentration was measured. The results are shown in Table 5.
As in Table 4, the fiber sample carrying the titanium oxide colloidal particles whose base is anatase type crystal showed a higher deodorizing effect than the fiber sample carrying amorphous titanium oxide colloidal particles, as in Table 4. .
［表５］ 消臭性評価試験結果２
繊維試料 消 臭 率（％）
アンモニア 硫化水素
ＡＦ １００ １００
ＢＦ ８５ ８０
ＣＦ １００ １００
ＤＦ ８０ ７０
ＥＦ ６０ ３０
ＦＦ ４０ ２０
[Table 5] Deodorant evaluation test result 2
Fiber sample deodorization rate (% )
Ammonia hydrogen sulfide AF 100 100
BF 85 80
CF 100 100
DF 80 70
EF 60 30
FF 40 20
Claims (2)
（２）得られた含水酸化物を洗浄し、
（３）洗浄した含水酸化物を水に懸濁し、
（４）該懸濁液にシリカコロイド溶液および／または珪酸液を加えて混合し、
（５）さらにアルカリを加えて該懸濁液のｐＨを７〜１３の範囲に調整し、
（６）次いで、ｐＨ調整した懸濁液をオートクレーブで温度１１０〜２５０℃の範囲で加熱処理して、抗菌・消臭性酸化チタン微粒子が分散したコロイド溶液を得る
ことを特徴とする抗菌・消臭性酸化チタンコロイド溶液の製造方法。 (1) An alkali is added to an aqueous solution obtained by mixing an aqueous solution containing an antibacterial / deodorant metal component and an aqueous titanium salt solution to produce a hydrous oxide,
(2) Washing the obtained hydrous oxide,
(3) Suspend the washed hydrous oxide in water,
(4) Add a silica colloid solution and / or silicic acid solution to the suspension and mix,
(5) Further alkali is added to adjust the pH of the suspension to a range of 7 to 13,
(6) Next, the pH-adjusted suspension is heat-treated in an autoclave at a temperature in the range of 110 to 250 ° C. to obtain a colloidal solution in which antibacterial / deodorant titanium oxide fine particles are dispersed. A method for producing an odorous titanium oxide colloidal solution.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004272776A JP4619075B2 (en) | 2004-09-21 | 2004-09-21 | Method for producing antibacterial and deodorant titanium oxide colloidal solution |
| US11/117,329 US8486433B2 (en) | 2004-05-07 | 2005-04-29 | Antibacterial deodorant |
| KR1020050037526A KR101233570B1 (en) | 2004-05-07 | 2005-05-04 | Antibacterial deodorant and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004272776A JP4619075B2 (en) | 2004-09-21 | 2004-09-21 | Method for producing antibacterial and deodorant titanium oxide colloidal solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006089380A JP2006089380A (en) | 2006-04-06 |
| JP4619075B2 true JP4619075B2 (en) | 2011-01-26 |
Family
ID=36230698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004272776A Expired - Lifetime JP4619075B2 (en) | 2004-05-07 | 2004-09-21 | Method for producing antibacterial and deodorant titanium oxide colloidal solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4619075B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007313141A (en) * | 2006-05-29 | 2007-12-06 | Hitachi Appliances Inc | Filter for decomposing odor component, washing/drying machine, electric vacuum cleaner, air-conditioning equipment and refrigerator |
| JP4542601B2 (en) * | 2009-01-29 | 2010-09-15 | 株式会社スギノマシン | Photocatalyst coating liquid manufacturing method, antibacterial deodorant dry cleaning coating liquid, and photocatalyst-processed clothing. |
| JP5361533B2 (en) * | 2009-05-25 | 2013-12-04 | 日揮触媒化成株式会社 | Environmental agent |
| US9604198B2 (en) * | 2012-09-19 | 2017-03-28 | Shin-Etsu Chemical Co., Ltd. | Visible light-responsive photocatalytic nanoparticle dispersion liquid, method for producing same, and member having photocatalytic thin film on surface |
| RU2552467C1 (en) * | 2013-11-15 | 2015-06-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Юго-Западный государственный университет(ФГБОУВПО "ЮЗГУ") | Method of modifying textile materials by metal nanoparticles |
| JP6953965B2 (en) | 2017-09-29 | 2021-10-27 | 信越化学工業株式会社 | A member having a photocatalyst / alloy fine particle dispersion having antibacterial / antifungal properties, a method for producing the same, and a photocatalyst / alloy thin film on the surface. |
| JP6993846B2 (en) * | 2017-11-01 | 2022-01-14 | 株式会社ファンケル | Antibacterial agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270620A (en) * | 1986-12-12 | 1988-11-08 | Catalysts & Chem Ind Co Ltd | Cosmetic and production thereof |
| JPH0733616A (en) * | 1993-07-16 | 1995-02-03 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JP2002068915A (en) * | 2000-08-25 | 2002-03-08 | Taki Chem Co Ltd | Sol |
-
2004
- 2004-09-21 JP JP2004272776A patent/JP4619075B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270620A (en) * | 1986-12-12 | 1988-11-08 | Catalysts & Chem Ind Co Ltd | Cosmetic and production thereof |
| JPH0733616A (en) * | 1993-07-16 | 1995-02-03 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
| JP2002068915A (en) * | 2000-08-25 | 2002-03-08 | Taki Chem Co Ltd | Sol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006089380A (en) | 2006-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8486433B2 (en) | Antibacterial deodorant | |
| CA2667024C (en) | Photocatalytic titanium oxide sol, and coating composition and member using the same | |
| JP5669367B2 (en) | Antibacterial deodorant and method for producing the same | |
| JP5354852B2 (en) | Deodorant antibacterial composition | |
| JP6154036B1 (en) | Coating agent containing antibacterial catalyst and method for producing the same | |
| CN104824020A (en) | Preparation method of nanometer titanium dioxide composite nanometer silver sol | |
| JP2003137549A (en) | Method for manufacturing tubular titanium oxide grain and tubular titanium oxide | |
| JP5317432B2 (en) | Deodorant antibacterial composition and method for producing dispersion thereof | |
| JP4619075B2 (en) | Method for producing antibacterial and deodorant titanium oxide colloidal solution | |
| JP4849778B2 (en) | Antibacterial deodorant and method for producing the same | |
| JP4355835B2 (en) | Photocatalytic material | |
| JP5925081B2 (en) | Titanium oxide antibacterial deodorant, dispersion thereof, and product provided with titanium oxide antibacterial deodorant | |
| JP4964331B2 (en) | Method for producing antibacterial deodorant | |
| CN111908887A (en) | Composite metal calcium phosphate antibacterial organic artificial stone and preparation method of antibacterial agent thereof | |
| JP2015097989A (en) | Virus removing agent and virus removing method | |
| JP3371460B2 (en) | Antibacterial agent and antibacterial resin composition | |
| JP5400439B2 (en) | Antibacterial composition | |
| JP4807916B2 (en) | Antibacterial and antifungal composition | |
| JP2013123591A (en) | Titanium oxide-based antibacterial deodorant, dispersion liquid of the titanium oxide-based antibacterial deodorant, and fiber or cloth with titanium oxide-based antibacterial deodorant | |
| JPH09227319A (en) | Antimicrobial powder and production thereof | |
| JP5224425B2 (en) | Paint composition | |
| JP7288709B2 (en) | Visible light responsive photocatalyst tungsten compound and paint | |
| JP5483853B2 (en) | Deodorant antibacterial agent for human or animal | |
| EP2614037B1 (en) | Tin tungstate-based photocatalyst and production thereof | |
| KR100453446B1 (en) | Process of preparing a dispersed solution of photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070612 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100723 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100803 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100927 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20101026 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20101026 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131105 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4619075 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |