JP2009154061A - Photocatalyst solution having improved microbial resistance - Google Patents
Photocatalyst solution having improved microbial resistance Download PDFInfo
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- JP2009154061A JP2009154061A JP2007333045A JP2007333045A JP2009154061A JP 2009154061 A JP2009154061 A JP 2009154061A JP 2007333045 A JP2007333045 A JP 2007333045A JP 2007333045 A JP2007333045 A JP 2007333045A JP 2009154061 A JP2009154061 A JP 2009154061A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 230000000813 microbial effect Effects 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 222
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 239000010419 fine particle Substances 0.000 claims abstract description 34
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims abstract description 34
- 229940071536 silver acetate Drugs 0.000 claims abstract description 34
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 31
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 28
- 239000004332 silver Substances 0.000 claims abstract description 28
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001958 silver carbonate Inorganic materials 0.000 claims abstract description 26
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims description 93
- 230000000844 anti-bacterial effect Effects 0.000 claims description 43
- 239000002131 composite material Substances 0.000 claims description 34
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 claims description 26
- FTNNQMMAOFBTNJ-UHFFFAOYSA-M silver;formate Chemical compound [Ag+].[O-]C=O FTNNQMMAOFBTNJ-UHFFFAOYSA-M 0.000 claims description 26
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 claims description 26
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 claims description 25
- 229940071575 silver citrate Drugs 0.000 claims description 24
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- -1 alcohol amines Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 230000000845 anti-microbial effect Effects 0.000 abstract 2
- 238000001879 gelation Methods 0.000 abstract 2
- 238000004062 sedimentation Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 241000894006 Bacteria Species 0.000 description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000000499 gel Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000004083 survival effect Effects 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 238000011221 initial treatment Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241001333951 Escherichia coli O157 Species 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 206010041925 Staphylococcal infections Diseases 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
Description
本発明は、過酸化チタン又は過酸化チタン複合化合物の微粒子を含むゾルからなる光触媒溶液に関し、特に、抗菌性を向上させた光触媒溶液に関する。 The present invention relates to a photocatalyst solution comprising a sol containing fine particles of titanium peroxide or a titanium peroxide composite compound, and more particularly to a photocatalyst solution having improved antibacterial properties.
光触媒として代表的な酸化チタンは、太陽光や紫外光を照射すると、触媒作用によって強力な酸化力を発現することが知られている。その強力な酸化力は、殺菌だけでなく菌が生成する毒素分解、さらには菌の死骸までも分解することが可能であることから、抗菌剤としての利用価値が注目されている。しかしながら、機能性に優れた酸化チタン系光触媒にも、紫外光（ＵＶ）が当たらないと触媒作用が発現しないという欠点がある。そのため、その欠点を補うことを目的とした抗菌性向上を検討する必要がある。 It is known that titanium oxide, which is a typical photocatalyst, exhibits a strong oxidizing power by catalytic action when irradiated with sunlight or ultraviolet light. Its strong oxidizing power can not only sterilize but also decompose toxins produced by bacteria, and even the dead bodies of bacteria, so that it is attracting attention as an antibacterial agent. However, the titanium oxide photocatalyst having excellent functionality also has a drawback that the catalytic action is not exhibited unless it is exposed to ultraviolet light (UV). Therefore, it is necessary to study antibacterial improvement aimed at compensating for the drawbacks.
銀（Ａｇ）や銅（Ｃｕ）に抗菌作用が備わっていることは従来より知られている。そして特許文献１には、酸化チタン（ＴｉＯ２）等の無機酸化物コロイド粒子の表面に、静電気的相互作用によって銀や銅などの抗菌性金属成分を付着せしめた抗菌剤が開示されている。より詳しくは、酸化銀や酸化銅をアンモニア水に溶解させて得られるアンミン錯塩水溶液を、酸化チタン等の無機酸化物コロイド溶液に添加して抗菌剤を製造することが記載されている。このとき、抗菌性無機酸化物コロイド粒子中の付着抗菌性金属成分の量は、酸化物換算で０．１〜２５重量％にすることが記載されている。 It has been known that silver (Ag) and copper (Cu) have an antibacterial action. Patent Document 1 discloses an antibacterial agent in which an antibacterial metal component such as silver or copper is adhered to the surface of inorganic oxide colloidal particles such as titanium oxide (TiO 2 ) by electrostatic interaction. More specifically, it describes that an antibacterial agent is produced by adding an ammine complex salt aqueous solution obtained by dissolving silver oxide or copper oxide in ammonia water to an inorganic oxide colloidal solution such as titanium oxide. At this time, it is described that the amount of the attached antibacterial metal component in the antibacterial inorganic oxide colloidal particles is 0.1 to 25% by weight in terms of oxide.
しかしながら特許文献１の場合、膜組成物として材料に塗布した場合に、密着性や機械的強度が不足しており、特に加熱、焼成が困難な材料に対しては実用性に欠ける。また、結晶性の酸化チタンは塗布後、白色化するという問題があり、例えば透明性を必要とする材料には使用できないという問題がある。 However, in the case of Patent Document 1, when applied as a film composition to a material, adhesion and mechanical strength are insufficient, and in particular, it is not practical for a material that is difficult to heat and fire. In addition, crystalline titanium oxide has a problem of whitening after coating, for example, it cannot be used for a material that requires transparency.
また、特許文献２には、金属塩または金属錯体をドーピングすることにより光触媒特性を増強させた酸化チタン溶液の作製方法が開示されている。より詳しくは、銀を析出させる場合、他の可溶性の銀化合物を使用することもできるが、本出願人らは、酢酸銀か硝酸銀のいずれかを使用することを選ぶことが記載されている。さらに、その前駆体溶液は、酸化チタンのコロイドに加えてもよいし、あるいは、硬化後の触媒粒子またはフィルムに含浸させることもできると記載されている。 Patent Document 2 discloses a method for producing a titanium oxide solution in which photocatalytic properties are enhanced by doping a metal salt or a metal complex. More particularly, when depositing silver, other soluble silver compounds can be used, but the applicants have described choosing to use either silver acetate or silver nitrate. Furthermore, it is described that the precursor solution may be added to the colloid of titanium oxide or may be impregnated into the cured catalyst particles or film.
しかしながら特許文献２の場合、酸化チタンのコロイド粒子の安定剤にシュウ酸を使用するので、コーティング溶液として薄膜を形成させた時、シュウ酸が酸化チタンの酸化力で炭酸ガスに分解し、結果として薄膜からガス発生によってピンホールの発生や膜の平滑性が損なわれたり、抗菌成分の銀や銅の不溶性炭酸塩が生じ、抗菌性が低下するという問題がある。さらに当該特許文献２の実施例２で示されるシリカ・酸化チタン・酸化鉄からなるコロイド溶液は、塩化チタン（ＴｉＣｌ4）に由来する塩素根を含むため、塗膜にした場合チョーキングや錆の発生の原因となる。また、この塩素が抗菌成分の銀と反応して不動態の塩化銀になる恐れが高い。さらにはアンミン錯体の形成のために、アンモニアを使っているが、アンモニアはコロイド溶液の安定性には寄与しない。しかも量が多いと悪臭の原因にもなる。 However, in the case of Patent Document 2, since oxalic acid is used as a stabilizer for colloidal particles of titanium oxide, when a thin film is formed as a coating solution, oxalic acid is decomposed into carbon dioxide gas by the oxidizing power of titanium oxide. Gas generation from the thin film impairs the generation of pinholes and the smoothness of the film, and the antibacterial components silver and copper insoluble carbonates are produced, resulting in a decrease in antibacterial properties. Furthermore, since the colloidal solution composed of silica, titanium oxide, and iron oxide shown in Example 2 of Patent Document 2 contains a chlorine root derived from titanium chloride (TiCl 4 ), generation of choking or rust occurs when the coating film is formed. Cause. In addition, there is a high risk that this chlorine reacts with the antibacterial component silver to form passive silver chloride. Furthermore, ammonia is used to form an ammine complex, but ammonia does not contribute to the stability of the colloidal solution. Moreover, if the amount is too large, it may cause odor.
本発明が解決しようとする課題には、上述した問題が一例として挙げられる。そこで、本発明の目的としては、紫外光（ＵＶ）が当たらない環境下に置かれても抗菌作用を示す光触媒であって、かつ、沈殿やゲル化することが少なく、安定したゾルを維持することのできる抗菌性を向上させた光触媒溶液を提供することが一例として挙げられる。 The problem to be solved by the present invention includes the above-described problem as an example. Accordingly, an object of the present invention is to maintain a stable sol that is a photocatalyst exhibiting an antibacterial action even when placed in an environment that is not exposed to ultraviolet light (UV), and that is less likely to precipitate or gel. An example is to provide a photocatalyst solution with improved antibacterial properties.
本発明の抗菌性を向上させた光触媒溶液は、過酸化チタン又は過酸化チタン複合化合物を主成分とする微粒子と、酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルであることを特徴とする。 The photocatalyst solution with improved antibacterial properties of the present invention comprises fine particles mainly composed of titanium peroxide or a titanium peroxide composite compound, silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, Or it is the sol containing the silver component which is a melt | dissolution of silver lactate, or the copper component which is a melt | dissolution of copper carbonate, It is characterized by the above-mentioned.
前記光触媒溶液は、アルコールアミンをさらに含むことができ、好ましくはモノアルカノールアミン，ジアルカノールアミン，トリアルカノールアミンのうちの少なくとも１種以上のアルカノールアミンをさらに含むことができる。この場合、過酸化チタン又は過酸化チタン複合化合物のゾルに、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅を溶解させたアルコールアミンと水の混合液を加えるようにすることができる。あるいは、過酸化チタン又は過酸化チタン複合化合物の微粒子を主成分とし、さらにアナタース型の酸化チタン又は酸化チタン複合化合物の微粒子を含むゾルに、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅を溶解させたアルコールアミンと水の混合液を加えるようにすることができる。 The photocatalyst solution may further include an alcohol amine, and may preferably further include at least one alkanolamine of monoalkanolamine, dialkanolamine, and trialkanolamine. In this case, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or a mixture of alcoholamine and water in which copper carbonate is dissolved in sol of titanium peroxide or titanium peroxide composite compound Liquid can be added. Alternatively, a sol containing fine particles of titanium peroxide or a titanium peroxide composite compound as a main component and further containing fine particles of anatase-type titanium oxide or a titanium oxide composite compound is added to silver carbonate, silver formate, silver propionate, silver butyrate, citric acid. It is possible to add a mixed solution of alcoholic acid and water in which silver acid, silver lactate, or copper carbonate is dissolved.
また、前記光触媒溶液は、過酸化チタン又は過酸化チタン複合化合物のゾルに、酢酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅の粉末を加えた溶液であってもよい。あるいは、過酸化チタン又は過酸化チタン複合化合物の微粒子を主成分とし、さらにアナタース型の酸化チタン又は酸化チタン複合化合物の微粒子を含むゾルに、酢酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅の粉末を加えた溶液であってもよい。 The photocatalytic solution is a solution obtained by adding a powder of silver acetate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or copper carbonate to a sol of titanium peroxide or a titanium peroxide composite compound. It may be. Alternatively, a sol containing fine particles of titanium peroxide or titanium peroxide composite compound as a main component and further containing fine particles of anatase type titanium oxide or titanium oxide composite compound is added to silver acetate, silver formate, silver propionate, silver butyrate, citric acid. A solution to which silver acid, silver lactate, or copper carbonate powder is added may also be used.
さらにまた、前記光触媒溶液は、アモルファスチタニアの粉末を過酸化水素水に溶解させてゲル化させた後に酢酸銀の水溶液を加え、さらに過酸化水素水を加えてゾル化させた過酸化チタンのゾルであってもよい。あるいは、アモルファスチタニアの粉末とシリカ前駆体を過酸化水素水に溶解させてゲル化させた後に酢酸銀の水溶液を加え、さらに過酸化水素水を加えてゾル化させた過酸化チタン−シリカのゾルであってもよい。この場合、さらに前記過酸化チタン又は過酸化チタン−シリカのゾルを加熱処理して得られるアナタース型の酸化チタン又は酸化チタン−シリカのゾルとすることができる。 Further, the photocatalyst solution is a titanium peroxide sol obtained by dissolving an amorphous titania powder in a hydrogen peroxide solution and gelling it, adding an aqueous solution of silver acetate, and further adding a hydrogen peroxide solution to form a sol. It may be. Alternatively, an amorphous titania powder and a silica precursor are dissolved in hydrogen peroxide solution and gelled, then an aqueous solution of silver acetate is added, and then a hydrogen peroxide solution is added to form a sol of titanium peroxide-silica. It may be. In this case, an anatase-type titanium oxide or titanium oxide-silica sol obtained by further heat-treating the titanium peroxide or titanium peroxide-silica sol can be obtained.
本発明の抗菌性を向上させた光触媒溶液によれば、過酸化チタン又は過酸化チタン複合化合物を主成分とする微粒子と、酢酸銀又は炭酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルとしたことにより、紫外光（ＵＶ）が当たらない環境下に置かれても抗菌作用を示し、かつ、沈殿やゲル化することが少なく、安定したゾルを維持することが可能となる。 According to the photocatalyst solution with improved antibacterial properties of the present invention, fine particles mainly composed of titanium peroxide or a titanium peroxide composite compound, a silver component which is a solution of silver acetate or silver carbonate, or a solution of copper carbonate The sol containing a copper component, which is a product, exhibits an antibacterial effect even when placed in an environment where it is not exposed to ultraviolet light (UV), and is less likely to precipitate or gel, maintaining a stable sol. It becomes possible.
さらに、本発明においては、光触媒として過酸化チタンまたは過酸化チタン複合化合物を用いたことにより、膜組成物とした場合に、従来の酸化チタンを用いるのに比べて光触媒自体の密着性・機械的強度を向上させることができ、自然乾燥でも密着、機械強度の点で実用性に優れている。さらには、過酸化チタンまたは過酸化チタン複合化合物は、成膜性（膜の均一性）に優れているため、意匠性を損ないにくい。このため、膜組成物としても、乱反射を起こして白色に見えてしまうのを抑えることが可能である。 Furthermore, in the present invention, when titanium peroxide or a titanium peroxide composite compound is used as a photocatalyst, the adhesiveness / mechanical properties of the photocatalyst itself are higher than in the case of using conventional titanium oxide in the case of a film composition. The strength can be improved, and it is excellent in practicality in terms of adhesion and mechanical strength even in natural drying. Furthermore, since titanium peroxide or a titanium peroxide composite compound is excellent in film formability (film uniformity), it is difficult to impair design properties. For this reason, it is possible to prevent the film composition from appearing white due to irregular reflection.
また、アルカノールアミン類、特に、モノエタノールアミン，ジエタノールアミン，トリエタノールアミンのうちの少なくとも１種以上のエタノールアミンを含有するようにすれば、より確実に安定したゾルを維持することが可能となる。 In addition, a stable sol can be maintained more reliably by containing at least one ethanolamine of alkanolamines, particularly monoethanolamine, diethanolamine, and triethanolamine.
本発明の好ましい実施形態による光触媒溶液について、添付図面を参照しながら詳しく説明する。但し、以下に説明する実施形態によって本発明は何ら限定されることはない。 A photocatalyst solution according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited by the embodiments described below.
［光触媒溶液］
本実施形態による光触媒溶液は、例えば粒径が数ナノメートルから数十マイクロメーターの過酸化チタン又は過酸化チタン複合化合物（以下、ペルオキソ型のチタニア又はチタニア複合化合物と称す）を主成分とする微粒子と、有機酸銀として例えば酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは有機酸銅として例えば炭酸銅の溶解物である銅成分を含むゾルからなる。ペルオキソ型のチタニア又はチタニア複合化合物の濃度は、例えば０．０５〜３質量％に調整される。また、酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀を選択した場合の銀成分の濃度は例えば０．００１〜０．１質量％に調整される。また、炭酸銅を選択した場合の銅成分の濃度は例えば０．００１〜０．１質量％に調整される。この濃度よりも低い場合にはＪＩＳ抗菌性試験に規定されている抗菌活性値２．０以上を発揮されない場合があり、反対に濃度が高い場合には本実施形態で採用する溶媒中で析出して沈殿物となってしまう場合がある。従って前記濃度の範囲内にすることが好ましい。
[Photocatalyst solution]
The photocatalyst solution according to the present embodiment includes, for example, fine particles whose main component is titanium peroxide or a titanium peroxide composite compound (hereinafter referred to as peroxo-type titania or titania composite compound) having a particle diameter of several nanometers to several tens of micrometers. And organic acid silver such as silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate, or organic acid copper such as copper carbonate It consists of a sol containing a certain copper component. The concentration of peroxo-type titania or titania complex compound is adjusted to, for example, 0.05 to 3% by mass. Moreover, the density | concentration of the silver component at the time of selecting silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate is adjusted to 0.001-0.1 mass%, for example. Moreover, the density | concentration of the copper component at the time of selecting copper carbonate is adjusted to 0.001-0.1 mass%, for example. If it is lower than this concentration, the antibacterial activity value of 2.0 or more specified in the JIS antibacterial test may not be exhibited. On the contrary, if the concentration is high, it precipitates in the solvent used in this embodiment. May become a precipitate. Therefore, the concentration is preferably within the range.
本実施形態における光触媒は、前記ペルオキソ型のチタニア又はチタニア複合化合物を主成分としていればよく、残りの成分として、アナタース型，ルチル型あるいはブルッカイト型などのチタニア又はチタニア複合化合物を含んでいてもよい。ここでいう主成分とは、光触媒を構成する成分の例えば５〜２５％を過酸化チタン部分が占めていることをいう。その中で好ましいのはアナタース型のチタニア又はチタニア複合化合物である。アナタース型のチタニアとは、結晶性の酸化チタンである。 The photocatalyst according to the present embodiment only needs to have the peroxo titania or titania composite compound as a main component, and may contain titania or titania composite compounds such as anatase type, rutile type, or brookite type as the remaining components. . A main component here means that the titanium peroxide part occupies, for example, 5 to 25% of the components constituting the photocatalyst. Among them, anatase type titania or a titania complex compound is preferable. Anatase-type titania is crystalline titanium oxide.
さらに、前記チタニア複合化合物とは、チタニアと他の金属化合物との複合体のことであり、その一例として、チタニア−シリカ、チタニア−ジルコニア、チタニア−アルミナ、チタニア−セリア、チタニア−酸化タングステン、チタニア−酸化錫、チタニア−酸化アンチモン、チタニア−酸化鉄、チタニア−酸化マンガン、チタニア−酸化クロムなどを挙げることができる。その中でも、金属化合物が金属酸化物であり、過酸化結合によってチタニアと他の金属化合物が結合した複合化合物を形成しているものが好ましい。これらチタニアと複合体を形成する金属化合物は、当該チタニアに別の機能を付加するものであり、求める機能に応じて少なくとも１種以上の複合体を選択することができる。例えばチタニア−シリカを選択した場合、当該チタニアに超親水性の機能を付加することができる。 Further, the titania composite compound is a composite of titania and another metal compound. Examples thereof include titania-silica, titania-zirconia, titania-alumina, titania-ceria, titania-tungsten oxide, titania. -Tin oxide, titania-antimony oxide, titania-iron oxide, titania-manganese oxide, titania-chromium oxide and the like. Among them, it is preferable that the metal compound is a metal oxide and a composite compound in which titania and another metal compound are bonded by a peroxide bond. These metal compounds forming a complex with titania add another function to the titania, and at least one complex can be selected according to the desired function. For example, when titania-silica is selected, a superhydrophilic function can be added to the titania.
前記したペルオキソ型のチタニア又はチタニア複合化合物の微粒子を分散させる媒体としては、例えば水、硝酸、塩酸、硫酸、過酸化水素水などを選択することができる。本実施形態の光触媒溶液は、酢酸銀、炭酸銀または炭酸銅を含むことから、前記した媒体の中でも水か過酸化水素水を選択するのが好ましい。 As a medium for dispersing the fine particles of the peroxo type titania or titania complex compound, for example, water, nitric acid, hydrochloric acid, sulfuric acid, hydrogen peroxide water, and the like can be selected. Since the photocatalyst solution of this embodiment contains silver acetate, silver carbonate, or copper carbonate, it is preferable to select water or hydrogen peroxide water among the above-mentioned media.
また、酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅は、特に限定されることはなく、例えば市販のものを適用することが可能である。但し、溶解性を良くするため、粉末状であることが好ましい。そして粉末は乾燥させたものであってもよく、例えば水分を１０質量％程度含む湿粉であってもよい。 In addition, silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or copper carbonate is not particularly limited, and for example, commercially available products can be applied. is there. However, in order to improve the solubility, it is preferably in a powder form. The powder may be dried, for example, a moist powder containing about 10% by mass of water.
前記酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅は、前記ペルソキソ型のチタニア又はチタニア複合化合物の微粒子のゾルに対して、粉末状態で添加してもよく、予め媒体に溶解させた溶液の状態で添加してもよい。これらを予め溶解させるための媒体としては、例えば水、水―アルコール、水−有機酸などを選択することができる。この場合、前記ペルソキソ型のチタニア又はチタニア複合化合物の微粒子を分散させる媒体と同じ種類のものを選択するのが好ましい。 The silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate or copper carbonate is in a powder state with respect to the sol of fine particles of the peroxo-type titania or titania composite compound. It may be added, or may be added in the state of a solution previously dissolved in a medium. As a medium for dissolving them in advance, for example, water, water-alcohol, water-organic acid or the like can be selected. In this case, it is preferable to select the same type as the medium in which the fine particles of the persoxo type titania or titania composite compound are dispersed.
前記炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅は、前記ペルオキソ型のチタニア又はチタニア複合化合物の微粒子のゾルに対して、予め媒体に溶解させた溶液の状態で添加することができる。これらを予め溶解させるための媒体としては、アルコールアミン類を用いることができる。好ましくは、モノアルカノールアミン，ジアルカノールアミン，トリアルカノールアミンのうちの少なくとも１種以上であり、より好ましくは、モノエタノールアミン，ジエタノールアミン，トリエタノールアミンのうちの少なくとも１種以上を含むエタノールアミンを選択することができる。この場合、アルコールアミン類に適量の水を加えた混合液を媒体とするのが好ましい。但し、これに限定されることはなく、前記ペルオキソ型のチタニア又はチタニア複合化合物の微粒子のゾルに対して先にアルコールアミン類を添加し、その後に粉末状の炭酸銀や炭酸銅等を添加して溶解させるようにしてもよい。 The silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate, or copper carbonate was previously dissolved in a medium in a fine particle sol of the peroxo type titania or titania composite compound. It can be added in solution. Alcoholamines can be used as a medium for dissolving them in advance. Preferably, at least one of monoalkanolamine, dialkanolamine, and trialkanolamine is selected, and more preferably, ethanolamine containing at least one of monoethanolamine, diethanolamine, and triethanolamine is selected. can do. In this case, it is preferable to use a mixed solution obtained by adding an appropriate amount of water to alcohol amines. However, the present invention is not limited to this. Alcohol amines are first added to the fine particle sol of the peroxo type titania or titania composite compound, and then powdered silver carbonate or copper carbonate is added. May be dissolved.
炭酸銀や炭酸銅等に対してアルコールアミン類が還元剤として作用すると、銀や銅の析出が起こり得る。そのため、製品の安定性を確保する点で言えばアルコールアミン類の含有量は少なくする方が好ましい。しかしながらその反面、含有量が少ないと製造時において炭酸銀や炭酸銅等を媒体に溶解させるのが難しくなる。従って、本実施形態においては、炭酸銀や炭酸銅等と、アルコールアミン類のモル配合比を１：１０から１：１００とするのが好ましい。 When alcohol amines act as a reducing agent on silver carbonate or copper carbonate, silver or copper may be deposited. Therefore, in terms of ensuring the stability of the product, it is preferable to reduce the content of alcohol amines. However, on the other hand, if the content is small, it becomes difficult to dissolve silver carbonate, copper carbonate or the like in the medium during production. Therefore, in this embodiment, it is preferable that the molar blending ratio of silver carbonate, copper carbonate, and the like and the alcohol amine is 1:10 to 1: 100.
続いて本実施形態による光触媒溶液の製法について説明する。但し、以下に説明する製法例は好ましい一例であり、これらの製法に限定されることはない。 Next, the method for producing the photocatalyst solution according to the present embodiment will be described. However, the manufacturing method example demonstrated below is a preferable example, and is not limited to these manufacturing methods.
［光触媒溶液の製法例１］
図１に示すように、まず、チタニアの原料となるチタンテトライソプロポキシド（ＴＩＰ）とイソプロパノール（ＩＰＡ）の混合液と、ＩＰＡと水の混合液とを混合し、ＴＩＰを加水分解させてチタニアの微粒子を生成させる。配合モル比としては、例えばＴＩＰ：ＩＰＡ：Ｈ２Ｏ＝１：１０：４とすることができる。そしてこのチタニアの微粒子を濾過分離し、例えば１００℃で乾燥させてチタニアの粉末を得る。濾過して得られたチタニアが粉塊である場合には、粉砕処理を適宜行うようにする。チタニアの原料としては、ＴＩＰに限られず、例えばチタンテトラエトキシドなど、その他のチタンアルコキシド（アルコール分子のＯＨ基のＨがＴｉに置換された化合物）を用いることができる。
[Production Example 1 of Photocatalyst Solution]
As shown in FIG. 1, first, a mixed solution of titanium tetraisopropoxide (TIP) and isopropanol (IPA), which is a raw material of titania, and a mixed solution of IPA and water are mixed to hydrolyze TIP and titania. Of fine particles. The blending molar ratio can be, for example, TIP: IPA: H 2 O = 1: 10: 4. The fine particles of titania are separated by filtration and dried at, for example, 100 ° C. to obtain titania powder. When titania obtained by filtration is a powder lump, pulverization is appropriately performed. The titania raw material is not limited to TIP, and other titanium alkoxides (compounds in which H in the OH group of the alcohol molecule is substituted with Ti) such as titanium tetraethoxide can be used.
続いて前記チタニアに例えば３５質量％の過酸化水素水を加えて溶解せしめることにより、チタニアのゲル体を生成させる（これを「チタニア一次処理」と称する）。そしてさらに分散剤として例えば３５質量％の過酸化水素水を加えてゾル体にする（これを「チタニア二次処理」と称する）。これにより、ペルオキソ型のチタニアが分散されたゾルを得る。 Subsequently, for example, 35% by mass of hydrogen peroxide solution is added to the titania and dissolved therein to form a titania gel (this is referred to as “titania primary treatment”). Further, for example, 35% by mass of hydrogen peroxide is added as a dispersant to form a sol (this is referred to as “titania secondary treatment”). Thereby, a sol in which peroxo-type titania is dispersed is obtained.
さらに続いて、前記ゾルにアンモニアなどのアルカリ溶液を添加してｐＨを例えば６〜８に調整した後、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅を溶解させたアルコールアミン類と水の混合液を添加する。そして少なくとも１５〜２５℃の液温で１日以上、遮光した状態を保持することにより、ペルオキソ型のチタニアの微粒子と、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルからなる光触媒溶液を得ることができる。 Subsequently, an alkaline solution such as ammonia is added to the sol to adjust the pH to 6-8, for example, and then silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or carbonic acid. Add a mixture of alcoholamines and water in which copper is dissolved. Then, by maintaining a light-shielded state for at least 15 days at a liquid temperature of 15 to 25 ° C., peroxo-type titania fine particles and silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or lactic acid A photocatalytic solution composed of a sol containing a silver component which is a dissolved silver material or a copper component which is a dissolved copper carbonate solution can be obtained.
ここで、アナタース型のチタニアの微粒子を含む光触媒溶液を製造する場合には、チタニア二次処理により得られるゾルにアンモニアなどのアルカリ溶液を添加してｐＨを例えば６〜８に調整した後、例えば８０〜９０℃の温度で加熱処理することによってペルオキソ型のチタニアの一部をアナタース化させる。こうして得たアナタース型のチタニアを含むゾルに対して、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅を溶解させたアルコールアミン類と水の混合液を添加することにより、ペルオキソ型のチタニアを主成分とし、アナタース型のチタニアを含む微粒子と、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルからなる光触媒溶液を得ることができる。 Here, in the case of producing a photocatalyst solution containing anatase-type titania fine particles, an alkali solution such as ammonia is added to the sol obtained by the titania secondary treatment to adjust the pH to, for example, 6 to 8, for example, A part of peroxo-type titania is anatated by heat treatment at a temperature of 80 to 90 ° C. For the sol containing anatase-type titania thus obtained, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or a mixed solution of alcohol amines and water in which copper carbonate is dissolved Is a solution containing fine particles containing peroxo titania and anatase titania and silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate. The photocatalyst solution which consists of a sol containing the copper component which is a component or a melt of copper carbonate can be obtained.
上記の製法は、ペルオキソ型のチタニアの微粒子を含む光触媒溶液の製法であるが、チタニア複合化合物の微粒子を含む光触媒溶液を製造する場合には、前述のチタニア一次処理において、チタニアと複合体を形成する他の金属化合物、またはその前駆体を添加する。一例として、チタニア−シリカとする場合にはシリカ前駆体であるオルトケイ酸テトラメチル（ＴＥＯＳ）とエタノールの混合物を添加する。以降、上記のように処理することにより、ペルオキソ型のチタニア−シリカの微粒子と、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルからなる光触媒溶液を得ることができる。また、ペルオキソ型のチタニア−シリカの一部をアナタース化させることによって、ペルオキソ型のチタニア−シリカを主成分とし、アナタース型のチタニア−シリカを含む微粒子と、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルからなる光触媒溶液を得ることができる。 The above production method is a method for producing a photocatalyst solution containing fine particles of peroxo-type titania. When producing a photocatalyst solution containing fine particles of a titania composite compound, a complex is formed with titania in the above-mentioned primary titania treatment. Other metal compounds or precursors thereof are added. As an example, in the case of titania-silica, a mixture of tetramethyl orthosilicate (TEOS), which is a silica precursor, and ethanol is added. Thereafter, by treating as described above, peroxo-type titania-silica fine particles and a silver component that is a solution of silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate, or A photocatalytic solution composed of a sol containing a copper component which is a copper carbonate solution can be obtained. Further, by subjecting a part of peroxo-type titania-silica to anatase, fine particles containing peroxo-type titania-silica as a main component and containing anatase-type titania-silica, silver carbonate, silver formate, silver propionate, A photocatalytic solution comprising a sol containing a silver component that is a solution of silver butyrate, silver citrate, or silver lactate, or a copper component that is a solution of copper carbonate can be obtained.
［光触媒溶液の製法例２］
続いて製法例２について説明する。前述の製法例１では、チタニアまたはチタニア複合化合物のゾルに対して、炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅を溶解させたエタノールアミンと水の混合液を添加しているが、これに代えて、製法例２では、図２に示すように、酢酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅の粉末を添加するようにする。酢酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅の添加量は、溶液に対し、例えば銀または銅として１〜１００ｐｐｍとなるように調整するのが好ましい。なお、酢酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀、あるいは炭酸銅の粉末を添加することを除けば、その他の処理工程は製法例１と同じであるため、詳しい説明は省略する。このように、ｐＨを調整した後のゾルに対して酢酸銀の粉末を添加するようにすれば、ゾルにはアンモニアが残留しているため、水溶性の酢酸銀はもちろんのこと、炭酸銅等も直接ゾルに溶解させることができ、予めエタノールアミンと水混合液を準備する必要がないという利点がある。一方、アルカノールアミンが存在すると、コロイドゾルの安定性に寄与することが知られており、副次的な効果が期待できる。
[Production Example 2 of Photocatalyst Solution]
Next, Production Method Example 2 will be described. In the above-mentioned Production Example 1, ethanolamine and water in which silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or copper carbonate is dissolved in titania or a titania composite compound sol However, instead of this, in Production Example 2, as shown in FIG. 2, silver acetate, silver formate, silver propionate, silver butyrate, silver citrate, silver lactate, or carbonic acid Add copper powder. The addition amount of silver acetate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate, or copper carbonate is preferably adjusted to 1 to 100 ppm as silver or copper, for example, with respect to the solution. . In addition, except for adding silver acetate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate, or copper carbonate powder, other processing steps are the same as in Manufacturing Method Example 1, Detailed description is omitted. Thus, if silver acetate powder is added to the sol after adjusting the pH, since ammonia remains in the sol, not only water-soluble silver acetate but also copper carbonate, etc. Can be directly dissolved in the sol, and there is an advantage that it is not necessary to prepare a mixed solution of ethanolamine and water in advance. On the other hand, the presence of alkanolamine is known to contribute to the stability of the colloidal sol, and a secondary effect can be expected.
［光触媒溶液の製法例３］
さらに続いて製法例３について説明する。前述の製法例２では、ｐＨを調整した後のチタニアまたはチタニア複合化合物のゾルに対して、粉末状の酢酸銀を添加しているが、これに代えて、製法例３では、図３に示すように、チタニア一次処理により得られるゲル体に対して、酢酸銀の水溶液を添加するようにする。添加する酢酸銀水溶液の濃度は、例えば１００ｐｐｍ水溶液とすることができる。さらに、混合比率としては、溶液中のＴｉＯｘ粉末に対し１００ｐｐｍ酢酸銀となるように調整するのが好ましい。なお、酢酸銀の水溶液をゲル体に添加することを除けば、その他の処理工程は製法例１と同じであるため、詳しい説明は省略する。このように、チタニア一次処理により得られるゲル体に対して酢酸銀の水溶液を添加するようにすれば、抗菌成分の分散を確実に行えるという利点がある。
[Production Example 3 of Photocatalyst Solution]
Next, Production Example 3 will be described. In the manufacturing method example 2 described above, powdered silver acetate is added to the sol of titania or titania composite compound after adjusting the pH, but instead, in manufacturing method example 3, it is shown in FIG. Thus, an aqueous solution of silver acetate is added to the gel obtained by the titania primary treatment. The concentration of the aqueous silver acetate solution to be added can be, for example, a 100 ppm aqueous solution. Furthermore, the mixing ratio is preferably adjusted to 100 ppm silver acetate with respect to the TiOx powder in the solution. Except for adding an aqueous solution of silver acetate to the gel body, the other processing steps are the same as in Production Method Example 1, and detailed description thereof is omitted. Thus, if an aqueous solution of silver acetate is added to the gel obtained by the first titania treatment, there is an advantage that the antibacterial component can be reliably dispersed.
上述の実施形態によれば、ペルオキソ型のチタニア又はチタニア複合化合物を主成分とする微粒子と、酢酸銀，炭酸銀，蟻酸銀，プロピオン酸銀，酪酸銀，クエン酸銀，又は乳酸銀の溶解物である銀成分、あるいは炭酸銅の溶解物である銅成分を含むゾルで光触媒溶液を構成したことにより、後述する実施例からも明らかなように紫外光（ＵＶ）が当たらない環境下に置かれても抗菌作用を示し、かつ、沈殿やゲル化することが少なく、安定したゾルを維持することが可能となる。 According to the above-described embodiment, fine particles mainly composed of peroxo type titania or a titania composite compound, and a solution of silver acetate, silver carbonate, silver formate, silver propionate, silver butyrate, silver citrate, or silver lactate Since the photocatalyst solution is composed of a sol containing a silver component or a copper component which is a solution of copper carbonate, it is placed in an environment free from ultraviolet light (UV), as will be apparent from examples described later. However, it exhibits an antibacterial action, and is less likely to precipitate or gel, so that a stable sol can be maintained.
さらに、本実施形態によれば、ペルオキソ型のチタニアまたはチタニア複合化合物を主成分とする光触媒微粒子を用いたことにより、膜組成物とした場合に、従来の酸化チタンを用いるのに比べて光触媒自体の密着性・機械的強度を向上させることができ、自然乾燥でも密着、機械強度の点で実用性に優れている。さらには、ペルオキソ型のチタニアまたはチタニア複合化合物は、成膜性（膜の均一性）に優れているため、意匠性を損ないにくい。このため、膜組成物としても、乱反射を起こして白色に見えてしまうのを抑えることが可能である。 Furthermore, according to the present embodiment, when a photocatalyst fine particle mainly composed of peroxo-type titania or a titania composite compound is used, when the film composition is used, the photocatalyst itself is used as compared with the conventional titanium oxide. Can be improved in adhesion and mechanical strength, and is excellent in practicality in terms of adhesion and mechanical strength even in natural drying. Furthermore, the peroxo-type titania or the titania complex compound is excellent in film formability (film uniformity), and thus the design property is not easily impaired. For this reason, it is possible to prevent the film composition from appearing white due to irregular reflection.
さらに、本実施形態によれば、アルカノールアミン類、特に、モノエタノールアミン，ジエタノールアミン，トリエタノールアミンのうちの少なくとも１種以上のエタノールアミンを含有するようにすれば、抗菌成分の分散性を向上し、より確実に安定したゾルを維持することが可能となる。 Furthermore, according to the present embodiment, the dispersibility of the antibacterial component is improved by containing at least one ethanolamine of alkanolamines, particularly monoethanolamine, diethanolamine, and triethanolamine. It becomes possible to maintain a stable sol more reliably.
上述の光触媒溶液の抗菌作用が非常に大きく、大腸菌（例えば病原性大腸菌Ｏ−１５７）、黄色ブドウ球菌、レジオネラ菌、ＭＲＳＡなどの各種菌に対して有効な殺菌効果がある。しかも光触媒は、従来において主に使用されている塩素系殺菌剤に比べて環境や人体に与える影響が格段に小さい。このことからも、本実施形態の光触媒溶液が極めて有効な抗菌剤となり得ることは明らかである。 The antibacterial action of the above-mentioned photocatalyst solution is very large and has an effective bactericidal effect against various bacteria such as Escherichia coli (for example, pathogenic Escherichia coli O-157), Staphylococcus aureus, Legionella, MRSA. Moreover, the photocatalyst has a much smaller influence on the environment and the human body than the chlorine-based disinfectant mainly used in the past. Also from this, it is clear that the photocatalyst solution of this embodiment can be a very effective antibacterial agent.
上述した本実施形態による光触媒溶液の使用方法としては、例えば基材に塗布してコーティング膜としたり、循環式浴槽や冷却塔などの循環水系に添加したりすることができる。その他、フィルターやろ過材などに担持させ、大気浄化、水質浄化など様々な用途に応用することができる。 As a usage method of the photocatalyst solution by this embodiment mentioned above, it can apply to a base material, for example, can be used as a coating film, or can be added to circulating water systems, such as a circulation type bathtub and a cooling tower. In addition, it can be supported on filters, filter media, etc. and applied to various uses such as air purification and water purification.
以上、本発明の具体的な実施形態に関して説明したが、本発明の範囲を逸脱しない限り様々な変形が可能であることは、当該技術分野における通常の知識を有する者にとって自明なことである。従って、本発明の技術的範囲は、上述した実施形態に限定されるものではなく、特許請求の範囲及びこれと均等なものに基づいて定められるべきである。 Although specific embodiments of the present invention have been described above, it is obvious to those skilled in the art that various modifications are possible without departing from the scope of the present invention. Therefore, the technical scope of the present invention should not be limited to the above-described embodiments, but should be determined based on the claims and equivalents thereof.
続いて、本発明の効果を確認するために行った実施例について説明する。 Next, examples performed for confirming the effects of the present invention will be described.
上述の製法例３に従い、ペルオキソ型のチタニアを主成分とし、アナタース型のチタニアを含む微粒子と、酢酸銀の溶解物である銀成分を含むゾルからなる光触媒溶液（溶液Ａ）を調製した。 According to Production Example 3 described above, a photocatalytic solution (solution A) comprising a sol containing fine particles containing peroxo-type titania as a main component and containing anatase-type titania and a silver component dissolved in silver acetate was prepared.
比較例として、製法例３において酢酸銀を添加せず、ペルオキソ型のチタニアを主成分とし、アナタース型のチタニアを含む微粒子のみのゾルからなる光触媒溶液（溶液Ｂ）を調整した。 As a comparative example, a photocatalyst solution (solution B) composed of a sol containing only fine particles containing peroxo titania and containing anatase titania was prepared without adding silver acetate.
溶液Ａおよび溶液Ｂの各々をスライドガラスに塗布し、乾燥させてコーティング膜を形成した。これをガラス製シャーレに充填し、リン酸緩衝液（ＰＢＳ）２０ｍｌを入れた。一方で、予め培養していた大腸菌を、遠心分離機にて１０分間遠心分離（４℃，３０００ｒｐｍ）し、上澄み液を捨てた後、ＰＢＳ５ｍｌを入れ再び遠心分離し、上澄み液を捨てた。残った沈殿物（菌）に生理食塩水４．５ｍｌを加え懸濁させて菌液を得た。この菌液を２μｌ採取し、シャーレの中に注入した。菌液の入ったシャーレを振とう器上に置いてＵＶ照射し、３０分ごとに菌液をサンプリングし適度に希釈した。希釈液０．１ｍｌを寒天培地に撒き、３７℃に調整したふ卵器に一晩入れて培養した。培養した寒天培地上のコロニーを数え、以下の式により生菌数を算出した。
生菌数（cfu/ml）＝（コロニー数）／（０．１ｍｌ） ・・・式１
Each of Solution A and Solution B was applied to a glass slide and dried to form a coating film. This was filled in a glass petri dish, and 20 ml of phosphate buffer (PBS) was added. On the other hand, Escherichia coli cultured in advance was centrifuged (4 ° C., 3000 rpm) for 10 minutes with a centrifuge, and the supernatant was discarded. Then, 5 ml of PBS was added and centrifuged again, and the supernatant was discarded. To the remaining precipitate (bacteria), 4.5 ml of physiological saline was added and suspended to obtain a bacterial solution. 2 μl of this bacterial solution was collected and injected into a petri dish. The petri dish containing the bacterial solution was placed on a shaker and irradiated with UV, and the bacterial solution was sampled every 30 minutes and diluted appropriately. 0.1 ml of the diluted solution was spread on an agar medium and placed in an incubator adjusted to 37 ° C. overnight. Colonies on the cultured agar medium were counted, and the viable cell count was calculated by the following formula.
Viable count (cfu / ml) = (colony count) / (0.1 ml) Formula 1
さらに、各時間にける生菌数をＣ（cfu/ml）、初生菌数をＣ０（cfu/ml）として、以下の式により生存率（Survival Rate）（％）を算出した。
生存率（％）＝（Ｃ（cfu/ml）／Ｃ０（cfu/ml））×１００ ・・・式２
前記式２によって算出される大腸菌の生存率の変化を表１に示す。なお、表１における○Controlは、大腸菌に殺菌処理を行わす、放置したものである。また、■は、溶液Ａのコーティング膜に対してＵＶ照射を行ったものであり、□は、溶液Ａのコーティング膜に対してブラックライトによるＵＶ照射をしなかったものである。一方、◆は、溶液Ｂのコーティング膜に対してＵＶ照射を行ったものであり、◇は、溶液Ｂのコーティング膜に対してブラックライトによるＵＶ照射をしなかったものである。さらに、▲は、大腸菌に対してブラックライトによるＵＶ照射のみしたものである。
Furthermore, the survival rate (%) was calculated by the following formula, where the viable cell count at each time was C (cfu / ml) and the primary cell count was C 0 (cfu / ml).
Survival rate (%) = (C (cfu / ml) / C 0 (cfu / ml)) × 100 Equation 2
Table 1 shows the change in the survival rate of Escherichia coli calculated by the equation 2. In Table 1, ◯ Control indicates that E. coli is sterilized and left untreated. In addition, ■ indicates that the coating film of solution A was irradiated with UV, and □ indicates that the coating film of solution A was not irradiated with UV light using black light. On the other hand, ♦ indicates that the coating film of solution B was irradiated with UV, and ◇ indicates that the coating film of solution B was not irradiated with black light. Furthermore, ▲ is the result of only UV irradiation with black light on E. coli.
表１の結果からも明らかなように、殺菌処理を行わなかった○Controlは、時間が経過しても菌数に大きな変化はない。一方、ブラックライトでＵＶを照射するのみ（▲）でも菌数は減少するものの、減少割合としては充分でない。これに対し、銀を含まないチタニア光触媒にＵＶ照射した例（◆）では、２４０ｍｉｎ後には菌の生存数は１％程度まで減少した。さらに銀を含むチタニア光触媒にＵＶ照射した例（■）では、２４０ｍｉｎ後には菌の生存数は検出限界である０．１％程度まで減少し、最も高い殺菌効果を示した。また、銀を含まないチタニア光触媒でＵＶ照射しなかった例（◇）では殆ど菌は減少しなかったが、銀を含むチタニア光触媒でＵＶ照射しなかった例（□）では菌数が減少している。 As is apparent from the results in Table 1, the number of bacteria does not change greatly even when the time is elapsed in the case where the sterilization treatment was not performed. On the other hand, the number of bacteria can be reduced only by irradiating UV with black light (▲), but the reduction rate is not sufficient. In contrast, in the example (♦) in which the titania photocatalyst not containing silver was irradiated with UV, the viable number of bacteria decreased to about 1% after 240 min. Furthermore, in the example (■) in which the titania photocatalyst containing silver was irradiated with UV, the viable number of bacteria decreased to about 0.1%, which is the detection limit, after 240 minutes, showing the highest bactericidal effect. In addition, in the case where UV irradiation was not performed with the titania photocatalyst not containing silver (◇), the number of bacteria was hardly decreased, but in the case where UV irradiation was not performed with the titania photocatalyst containing silver (□), the number of bacteria was decreased. Yes.
上述の製法例2に従いペルオキソ型のチタニアの微粒子と、酢酸銀の溶解物である銀成分を含むゾルからなる光触媒溶液（溶液C）を調製した。 A photocatalyst solution (solution C) comprising a sol containing fine particles of peroxo-type titania and a silver component which is a dissolved silver acetate was prepared according to Production Example 2 described above.
比較例として、製法例2において酢酸銀を添加せず、ペルオキソ型チタニアの微粒子のみを含むゾルからなる光触媒溶液（溶液D）を調整した。 As a comparative example, a photocatalyst solution (solution D) composed of a sol containing only fine particles of peroxo-type titania was prepared without adding silver acetate in Production Method Example 2.
溶液Ｃおよび溶液Ｄの各々をガラスにスプレー塗布し、乾燥させてコーティング膜を形成した。これをJIS R 1702（ファインセラミックス-光照射下での光触媒抗菌加工製品の抗菌性試験方法・抗菌効果）に従い、暗所及び明所にて抗菌性試験を行った。ただし、明所の光源は白色蛍光灯を使用し、照度は4000〜6000lxとした。対象の菌種は黄色ブドウ球菌を使用した。 Each of solution C and solution D was spray-coated on glass and dried to form a coating film. In accordance with JIS R 1702 (Fine ceramics-Antibacterial test method and antibacterial effect of photocatalytic antibacterial processed product under light irradiation), an antibacterial test was conducted in a dark place and a light place. However, the light source in the bright place was a white fluorescent lamp, and the illuminance was 4000-6000 lx. Staphylococcus aureus was used as the target bacterial species.
評価方法は、JIS Z 2801を参考にし、抗菌活性値が2.0を超えるものを抗菌効果があると判断した。
抗菌活性値＝log[無加工試験片の8時間後の生菌数(個)
÷抗菌加工試験片の8時間後の生菌数（個）]・・・式３
試験結果を表２、表３に示す
With respect to the evaluation method, JIS Z 2801 was referred to, and an antibacterial activity value exceeding 2.0 was judged to have an antibacterial effect.
Antibacterial activity value = log [Number of viable bacteria after 8 hours of unprocessed specimen (pieces)
÷ Number of viable bacteria (pieces) after 8 hours of antibacterial processed test piece] ... Equation 3
The test results are shown in Table 2 and Table 3.
表２からも明らかなように、光触媒無し（溶液C、溶液Dともに塗布していないフィルム）は菌数が増加しているのに対し、光触媒有り（溶液C、溶液Dを塗布したガラス）は明所条件では菌数が減少しているのがわかる。暗所条件では銀を添加していない溶液Dは光触媒効果を発揮できず、初期菌数に比べ、菌数に変化がないのに対し、銀を添加している溶液Cは暗所でも菌数が10以下になっていることを示している。
表３は前記式３に従って、抗菌活性値を計算し、グラフ化した表である。表3からも明らかなように溶液Cは明所、暗所ともにJIS Z 2801に規定されている抗菌活性値2.0を超えている。
As is clear from Table 2, the number of bacteria increased without the photocatalyst (film not coated with either solution C or solution D), but with photocatalyst (glass coated with solution C or solution D). It can be seen that the number of bacteria decreased under the light conditions. Solution D without silver added under dark conditions cannot exhibit the photocatalytic effect and there is no change in the number of bacteria compared to the initial number of bacteria, whereas Solution C with silver added does not change the number of bacteria even in the dark. Is less than 10.
Table 3 is a table in which the antibacterial activity value is calculated and graphed according to the above-mentioned formula 3. As is apparent from Table 3, the solution C exceeded the antibacterial activity value 2.0 specified in JIS Z 2801 in both the light and dark places.
以上の結果から明らかなように、本発明に従う光触媒溶液は、高い殺菌効果を有し、しかも紫外光がとどかない環境下であっても殺菌効果を示すことが確認された。 As is clear from the above results, it was confirmed that the photocatalyst solution according to the present invention has a high bactericidal effect and exhibits a bactericidal effect even in an environment where ultraviolet light does not reach.
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