JP4169163B1 - Photocatalytic titanium oxide sol and coating composition using the same - Google Patents
Photocatalytic titanium oxide sol and coating composition using the same Download PDFInfo
- Publication number
- JP4169163B1 JP4169163B1 JP2008138832A JP2008138832A JP4169163B1 JP 4169163 B1 JP4169163 B1 JP 4169163B1 JP 2008138832 A JP2008138832 A JP 2008138832A JP 2008138832 A JP2008138832 A JP 2008138832A JP 4169163 B1 JP4169163 B1 JP 4169163B1
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- oxide sol
- silver
- sol
- photocatalytic titanium
- 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.)
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000008199 coating composition Substances 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 47
- 239000004332 silver Substances 0.000 claims abstract description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 claims abstract description 24
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 24
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 26
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- PVOXCLVRHYZZEP-UHFFFAOYSA-M [OH-].[O-2].[Ti+3] Chemical compound [OH-].[O-2].[Ti+3] PVOXCLVRHYZZEP-UHFFFAOYSA-M 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 52
- 238000002845 discoloration Methods 0.000 abstract description 20
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 39
- 235000011114 ammonium hydroxide Nutrition 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 239000000499 gel Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000010408 film Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000001580 bacterial effect Effects 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 11
- -1 nitrate ions Chemical class 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000010335 hydrothermal treatment Methods 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910001923 silver oxide Inorganic materials 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 6
- 239000005750 Copper hydroxide Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000008213 purified water Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000001888 Peptone Substances 0.000 description 4
- 108010080698 Peptones Proteins 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 235000019319 peptone Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
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- 229910004298 SiO 2 Inorganic materials 0.000 description 3
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- 239000002504 physiological saline solution Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
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- 230000001877 deodorizing effect Effects 0.000 description 2
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- 238000003113 dilution method Methods 0.000 description 2
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- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 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 2
- 239000002244 precipitate Substances 0.000 description 2
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- 229910001961 silver nitrate Inorganic materials 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Abstract
【課題】暗所で抗菌性を発現する光触媒酸化チタンゾルであり、殊に銀を含有させたときにおいても、光による変色を生じない安定な光触媒酸化チタンゾル及びこれを用いたコーティング組成物を得る。
【解決手段】銀および銅並びに水酸化第四アンモニウムを含有する光触媒酸化チタンゾルである。また、バインダー中にこの光触媒酸化チタンゾルを分散してなる光触媒コーティング組成物である。
この本発明の光触媒酸化チタンゾルは、銅と水酸化第四アンモニウムを巧みに利用することにより、抗菌性の高い銀を含有させることが可能となったため、暗所での銀単独での抗菌効果は勿論、従来の紫外線殺菌を行う用途等において、本発明の光触媒酸化チタンゾルとこれら紫外線殺菌装置等とを併用することにより、より有効な抗菌効果を得ることができる。
【選択図】 なしThe present invention provides a photocatalytic titanium oxide sol that exhibits antibacterial properties in a dark place, in particular, a stable photocatalytic titanium oxide sol that does not cause discoloration by light even when silver is contained, and a coating composition using the same.
A photocatalytic titanium oxide sol containing silver and copper and quaternary ammonium hydroxide. Moreover, it is a photocatalyst coating composition formed by dispersing this photocatalytic titanium oxide sol in a binder.
The photocatalytic titanium oxide sol of the present invention makes it possible to contain highly antibacterial silver by skillfully utilizing copper and quaternary ammonium hydroxide, so the antibacterial effect of silver alone in the dark is Of course, a more effective antibacterial effect can be obtained by using the photocatalytic titanium oxide sol of the present invention in combination with these ultraviolet sterilizers and the like for conventional ultraviolet sterilization.
[Selection figure] None
Description
本発明は、暗所で抗菌性を発現する光触媒酸化チタンゾルに関し、殊に銀を含有させたときにおいても、光による変色を生じない安定な光触媒酸化チタンゾル及びこれを用いたコーティング組成物に関する。 The present invention relates to a photocatalytic titanium oxide sol that exhibits antibacterial properties in a dark place, and particularly relates to a stable photocatalytic titanium oxide sol that does not cause discoloration by light even when silver is contained, and a coating composition using the same.
酸化チタンは紫外線を照射することにより酸化還元作用を発現し、有害物質を分解したり、抗菌性、超親水現象を示したりする光触媒効果を有することが知られており、この効果を利用した工業製品の開発が盛んに行われている。光触媒反応は酸化チタンの表面近傍における反応であるため、薄膜状にして利用されることが多く、酸化チタンの微粒子からなる酸化チタンゾルが薄膜形成材料として広く用いられている。
ところで、酸化チタンの光触媒効果は、その名の通り光のエネルギーによって発現することから、その効果は太陽光や紫外線ランプなどの光が照射されているときだけに限定されている。光触媒による効果の内、超親水性に起因する防汚性については連続的に紫外線が照射されずとも、間欠的な照射によって光触媒機能を有する膜表面の外観的な汚れは取り除くことができる。また、有害物質の分解においても、自然に増加しない物質であれば、間欠的な光照射で徐々に分解が進むことになる。しかしながら、抗菌性や脱臭効果については、光触媒効果が発現していない間に菌や臭気が増殖、拡大することから、効果を持続させるためには連続的な紫外線の照射が必要となる。空気清浄機や浄化装置に組み込まれた光触媒のように連続して光照射を行うことができる製品は常に光照射することができるが、屋内、屋外において用いられる建材やその他のアメニティー関連製品などは独自の光源を持たないため太陽光やランプがない暗所では光触媒が機能しないことになる。このことは、光触媒による有害物分解、防汚効果とともに抗菌性を期待する光触媒製品にとって大きな問題であり、光触媒への暗所での抗菌性や脱臭効果が強く切望されていた。
Titanium oxide is known to have a photocatalytic effect that exhibits redox action by irradiating ultraviolet rays, decomposes harmful substances, exhibits antibacterial properties, and superhydrophilic phenomena. Product development is actively underway. Since the photocatalytic reaction is a reaction near the surface of titanium oxide, it is often used in the form of a thin film, and a titanium oxide sol composed of fine particles of titanium oxide is widely used as a thin film forming material.
By the way, since the photocatalytic effect of titanium oxide is expressed by the energy of light as the name suggests, the effect is limited only when light such as sunlight or an ultraviolet lamp is irradiated. Among the effects of the photocatalyst, regarding the antifouling property due to the superhydrophilicity, even if the ultraviolet ray is not continuously irradiated, the external contamination of the film surface having the photocatalytic function can be removed by intermittent irradiation. Further, in the decomposition of harmful substances, if the substance does not increase naturally, the decomposition gradually proceeds by intermittent light irradiation. However, regarding antibacterial and deodorizing effects, bacteria and odors grow and expand while the photocatalytic effect is not manifested, so continuous ultraviolet irradiation is required to maintain the effect. Products that can continuously irradiate light, such as photocatalysts built into air purifiers and purifiers, can always irradiate, but building materials and other amenity-related products used indoors and outdoors Since it does not have its own light source, the photocatalyst does not function in the dark where there is no sunlight or lamp. This is a major problem for photocatalyst products that are expected to have antibacterial properties as well as decomposition of harmful substances and antifouling effects due to photocatalysts, and there has been a strong demand for antibacterial properties and deodorizing effects in the dark.
一方、光のない暗所で抗菌効果を発現させるには、光触媒以外の抗菌剤を光触媒と併用させることがもっとも安易で簡便な方法である。抗菌剤には各種の化合物があるが、光触媒が有機物を分解することから、光触媒と併用する場合には、無機物からなる抗菌剤を使用する必要がある。無機の抗菌性成分としては銀、銅、亜鉛等の金属が挙げられ、これらを基材表面に存在させて抗菌性を発現させる各種の工業製品が数多く開発されている。
光触媒においてもこのような抗菌性金属の効果を利用することができ、例えば光触媒と抗菌性金属を同一塗膜上に存在させることによって照射光の有無にかかわらず抗菌性を発現させることができる。例えば、酸化チタンを含む光触媒膜を予め作成し、その表面に更に抗菌性金属を含有する化合物、例えば銀や銅の各種塩の水溶液を塗布した後、熱処理したり、還元処理する等によって光触媒効果と金属イオンによる抗菌性を付与させた膜を形成することができ、暗所における抗菌性を発現させることができる。しかしながら、このような方法では塗布、乾燥の工程数が増えることになり、コストアップになることは明らかである。工業的な観点からすると、光触媒と抗菌性金属を含む一種類の薬液を一度で塗布、乾燥することにより塗膜が得られることが好ましい。そのためには、光触媒を含む塗膜形成材料に抗菌性金属である銀や銅を混合することが考えられる。
On the other hand, in order to develop an antibacterial effect in a dark place without light, it is the easiest and simplest method to use an antibacterial agent other than the photocatalyst together with the photocatalyst. There are various types of antibacterial agents, but since photocatalysts decompose organic substances, it is necessary to use antibacterial agents made of inorganic substances when used in combination with photocatalysts. Examples of the inorganic antibacterial component include metals such as silver, copper, and zinc, and various industrial products that exhibit antibacterial properties by causing them to exist on the substrate surface have been developed.
The effect of such an antibacterial metal can also be utilized in the photocatalyst. For example, the antibacterial property can be expressed regardless of the presence or absence of irradiation light by allowing the photocatalyst and the antibacterial metal to exist on the same coating film. For example, a photocatalytic film containing titanium oxide is prepared in advance, and a photocatalytic effect is obtained by applying an antibacterial metal-containing compound, such as an aqueous solution of various salts of silver and copper, to the surface, followed by heat treatment or reduction treatment. And a film imparted with antibacterial properties by metal ions can be formed, and antibacterial properties in the dark can be expressed. However, it is obvious that such a method increases the number of coating and drying steps, resulting in an increase in cost. From an industrial point of view, it is preferable to obtain a coating film by applying and drying one kind of chemical solution containing a photocatalyst and an antibacterial metal at a time. For that purpose, it is possible to mix silver and copper which are antibacterial metals with the coating-film formation material containing a photocatalyst.
塗膜形成材料としては前述の通り酸化チタンゾルが好ましく利用されており、銀や銅はそれぞれ硝酸塩水溶液の状態で混合することが考えられる。硝酸で安定化された商品名酸化チタンゾルSTS-01（石原産業株式会社製）に硝酸銀水溶液を加えた場合、硝酸銀を添加してしばらくは見かけ上安定である。しかし、やがて銀成分が還元を受けてゾルが黄色から茶色に着色し、ついには銀成分の沈殿さえ生じるようになる。ゾルに沈殿が生じると、塗膜が安定に形成できず、沈殿物により塗布後の外観に不具合が生じたり、抗菌性効果にバラツキが生じる。そこで、着色や沈殿が生じないように塗膜の製造直前にゾルに銀成分を都度添加することも考えられるが合理的ではない。そこで、本発明者らは、保存安定性に優れた抗菌性金属を含む光触媒能を有する酸化チタンゾルを製造する方法について鋭意検討を行った。
抗菌性金属の一つである銅を含有する酸化チタンゾルについては、本出願人らが既に技術を公開しており、それによれば銅はアルカノールアミンに溶解させた錯体の状態で酸化チタンゾル中に安定に分散される。（特許文献１参照）
しかし、銀を含む光触媒能を有する酸化チタンゾルについては、これまで変色なく安定に銀を含有させたゾルおよびその製造方法は報告されていない。これは銀が銅に比べて還元されやすい状態にあることに由来している。
ところで、無機系コロイド抗菌剤として、負の電荷を有する無機酸化物コロイド粒子に銀、銅、亜鉛、錫、鉛、ビスマス、カドミウム、クロム、水銀のなかから選択される一種以上の抗菌性金属成分を付着せしめた抗菌性無機酸化物コロイド溶液からなる抗菌剤が開示されている。（特許文献２参照）
As described above, titanium oxide sol is preferably used as the coating film forming material, and silver and copper may be mixed in the form of an aqueous nitrate solution. When an aqueous solution of silver nitrate is added to the product name titanium oxide sol STS-01 (Ishihara Sangyo Co., Ltd.) stabilized with nitric acid, it is apparently stable for a while after the addition of silver nitrate. Eventually, however, the silver component undergoes reduction and the sol turns from yellow to brown, and eventually the silver component precipitates. If precipitation occurs in the sol, the coating film cannot be formed stably, and the precipitate causes a defect in the appearance after application, and the antibacterial effect varies. Therefore, it may be possible to add a silver component to the sol immediately before the production of the coating so as not to cause coloring or precipitation, but this is not rational. Therefore, the present inventors diligently studied a method for producing a titanium oxide sol having a photocatalytic ability including an antibacterial metal having excellent storage stability.
Regarding the titanium oxide sol containing copper which is one of the antibacterial metals, the present applicants have already disclosed the technology, and according to this, copper is stable in the titanium oxide sol in a complex state dissolved in alkanolamine. To be distributed. (See Patent Document 1)
However, with respect to a titanium oxide sol containing silver and having a photocatalytic ability, a sol containing silver stably without discoloration and a method for producing the same have not been reported so far. This is due to the fact that silver is more easily reduced than copper.
By the way, as an inorganic colloidal antibacterial agent, one or more antibacterial metal components selected from silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, mercury and inorganic oxide colloidal particles having a negative charge Disclosed is an antibacterial agent comprising an antibacterial inorganic oxide colloid solution to which is attached. (See Patent Document 2)
この特許文献２にはTiO2の記載はあるが、光触媒能の付与を目的としたものではなく、抗菌剤の担持体としての例示である。また、この特許文献２には、チタン、ジルコニウム、および亜鉛成分を組み合わせて使用するとそれらの成分が紫外線吸収剤として作用して、銀成分の変色を防止する効果があることが記載されているが、チタンが光触媒能を有する酸化チタンゾルの場合は全く逆であり、光触媒の強い酸化還元力により光触媒能のない無定形の酸化チタンのゾルよりもよりもきわめて迅速に銀の還元による変色が認められる。
例えば、負の電荷を有するアナターゼ型酸化チタンゾルとして商品名タイノックA-6(TiO2=6質量%、pH11；多木化学株式会社製)を用い、これにアンモニアに溶解させた酸化銀を添加すると、ゾルは安定で増粘やゲル化などは発生しないものの、蛍光灯レベルの光照射によってきわめて短時間に変色し、やがて還元された黒色の銀が沈殿する。このような変色、沈殿現象は機能低下ばかりでなく、外観、使用利便性等の商品価値を大きく低下させることとなる。
Although this patent document 2 describes TiO 2 , it is not intended to impart photocatalytic activity, but is an example as a support for an antibacterial agent. In addition, Patent Document 2 describes that when titanium, zirconium, and zinc components are used in combination, these components act as an ultraviolet absorber and have an effect of preventing discoloration of the silver component. In the case of titanium oxide sol with titanium having photocatalytic activity, the opposite is true, and due to the strong redox power of photocatalyst, discoloration due to reduction of silver is recognized much faster than amorphous titanium oxide sol without photocatalytic activity .
For example, when using the trade name Tynock A-6 (TiO 2 = 6% by mass, pH 11; manufactured by Taki Chemical Co., Ltd.) as anatase-type titanium oxide sol having a negative charge, silver oxide dissolved in ammonia is added thereto. Although the sol is stable and does not increase in viscosity or gelation, it is discolored in a very short time by light irradiation at the level of a fluorescent lamp, and eventually reduced black silver is precipitated. Such discoloration and precipitation phenomenon not only deteriorates the function, but also greatly reduces the commercial value such as appearance and convenience of use.
そこで本発明者らは、抗菌性金属として銀を含んでいるにもかかわらず、光触媒である酸化チタンゾルによる変色や沈殿発生の無い安定な光触媒酸化チタンゾルについて鋭意検討を重ねた結果、以下に詳述する本発明を完成したものである。 Accordingly, the present inventors have conducted extensive studies on a stable photocatalytic titanium oxide sol that does not cause discoloration or precipitation due to the titanium oxide sol that is a photocatalyst despite containing silver as an antibacterial metal. The present invention has been completed.
前述の課題を解決するために本発明の光触媒酸化チタンゾルは、銀および銅並びに水酸化第四アンモニウムを含有することを特徴とする。 In order to solve the aforementioned problems, the photocatalytic titanium oxide sol of the present invention is characterized by containing silver and copper and quaternary ammonium hydroxide.
本発明の好ましい態様においては、光触媒酸化チタンゾルは３００〜４００ｎｍの波長閾の光照射による色質指数ΔL値が１０以下であることが特徴である。 In a preferred embodiment of the present invention, the photocatalytic titanium oxide sol is characterized by a color quality index ΔL value of 10 or less when irradiated with light having a wavelength threshold of 300 to 400 nm.
本発明の好ましい態様においては、銀が酸化チタンに対してAg2O／TiO2として０．１〜５質量％であり、銀に対する銅の割合がCuO／Ag2O（質量比）として1〜３０であることが特徴である。 In a preferred embodiment of the present invention, silver is 0.1 to 5 mass% as Ag 2 O / TiO 2 with respect to the titanium oxide, the ratio of copper to silver 1 as CuO / Ag 2 O (mass ratio) 30 is a feature.
本発明の好ましい態様としては、水酸化第四アンモニウムとして水酸化テトラメチルアンモニウムを使用することである。 In a preferred embodiment of the present invention, tetramethylammonium hydroxide is used as the quaternary ammonium hydroxide.
また、本発明の好ましい態様としては、水酸化第四アンモニウム量が酸化チタン（TiO2） 1モルに対して0.01〜0.1モルであることが特徴である。 In a preferred embodiment of the present invention, the amount of quaternary ammonium hydroxide is 0.01 to 0.1 mol with respect to 1 mol of titanium oxide (TiO 2 ).
本発明の光触媒コーティング組成物の好ましい態様としては、前記光触媒酸化チタンゾルをバインダー中に分散させることにある。 In a preferred embodiment of the photocatalytic coating composition of the present invention, the photocatalytic titanium oxide sol is dispersed in a binder.
本発明の光触媒酸化チタンゾルは、光触媒である酸化チタンと抗菌性金属として銀を含んでいるにもかかわらず、光照射による変色が僅少で、ゲル化や増粘が極めて少ないことが特徴である。本発明では銅と水酸化第四アンモニウムを巧みに利用することにより、抗菌性の高い銀を含有させることが可能となったため、暗所での銀単独での抗菌効果は勿論、従来の紫外線殺菌を行う用途等において、本発明の光触媒酸化チタンゾルとこれら紫外線殺菌装置等とを併用することにより、より有効な抗菌効果を得ることができる。 The photocatalytic titanium oxide sol of the present invention is characterized by little discoloration due to light irradiation and very little gelation and thickening despite containing titanium oxide as a photocatalyst and silver as an antibacterial metal. By skillfully using copper and quaternary ammonium hydroxide in the present invention, it becomes possible to contain silver having high antibacterial properties, so that the antibacterial effect of silver alone in a dark place as well as the conventional UV sterilization More effective antibacterial effect can be obtained by using the photocatalytic titanium oxide sol of the present invention in combination with these ultraviolet sterilizers and the like.
以下に詳細に、本発明の光触媒酸化チタンゾルについて説明を行なう。 The photocatalytic titanium oxide sol of the present invention will be described in detail below.
本発明の光触媒酸化チタンゾルの酸化チタンは、光触媒効果を有するアナターゼ型またはルチル型の結晶並びにこれらの混合物からなり、少なくともゾルを乾燥して得られる粉の粉末X線回折が明らかにアナターゼ型またはルチル型と同定されるものをいう。このようなアナターゼ型またはルチル型を示す酸化チタンは高い光触媒性能を示すことから本発明のゾルを構成する酸化チタンとして必要不可欠なものである。
光触媒酸化チタンゾルの濃度に関しては、通常の濃縮等の操作によって調整可能であるが、概ねTiO2として3〜15質量％の範囲が好ましい。下限を下廻ると塗料化して基材に塗布する際に薄膜になり過ぎるため効果が低くなる傾向にあり、場合によっては、複数回の塗布が必要となり生産的でない。逆に上限を超えるとゾルの粘度が高くなる等により操作性が悪くなる傾向にある。
本発明の光触媒酸化チタンゾルに含有させる銀の形態に関しては、酸化物、水酸化物などのイオン化していない形態が好ましい。本発明ゾル中の銀の含有量に関しては、銀が酸化チタンに対してAg2O／TiO2として０．１〜５質量％の範囲、より好ましくは、１〜３質量％の範囲が推奨される。下限を下廻ると銀の抗菌効果が期待できず、上限以上になるとゾル中に安定に分散させることが困難となる。
The titanium oxide of the photocatalytic titanium oxide sol of the present invention comprises anatase type or rutile type crystals having a photocatalytic effect and a mixture thereof, and at least powder X-ray diffraction obtained by drying the sol clearly shows anatase type or rutile type. What is identified as a mold. Such an anatase-type or rutile-type titanium oxide exhibits high photocatalytic performance, and thus is indispensable as a titanium oxide constituting the sol of the present invention.
The concentration of the photocatalytic titanium oxide sol can be adjusted by an ordinary operation such as concentration, but is preferably in the range of 3 to 15% by mass as TiO 2 . If the lower limit is not reached, the effect tends to be low because it becomes too thin when applied to a base material and tends to be less effective. In some cases, multiple applications are required, which is not productive. On the contrary, when the upper limit is exceeded, the operability tends to deteriorate due to, for example, an increase in the viscosity of the sol.
With respect to the form of silver contained in the photocatalytic titanium oxide sol of the present invention, non-ionized forms such as oxides and hydroxides are preferred. Regarding the silver content in the sol of the present invention, it is recommended that silver is in the range of 0.1 to 5% by mass, more preferably in the range of 1 to 3% by mass as Ag 2 O / TiO 2 with respect to titanium oxide. The Below the lower limit, the antibacterial effect of silver cannot be expected, and when it exceeds the upper limit, it becomes difficult to stably disperse in the sol.
次に本発明に用いる水酸化第四アンモニウムについて詳述する。水酸化第四アンモニウムは、本発明の光触媒酸化チタンゾルを安定にするための必須成分の一つである。通常、アンモニアや一級〜三級アミン類等のアルカリ化合物はいずれもアルカリ性の酸化チタンのゾル自体を安定化する成分として知られているが、一方でこれらのアルカリ化合物は銀などの抗菌性金属を溶解させる傾向にある。一般に抗菌金属成分の変色は抗菌金属のイオン化によるところが大きいと考えられ、抗菌性金属を溶解させるこれらアルカリ化合物がゾル中に存在することは好ましくない。そこで、本発明者らは、鋭意検討した結果、ゾルの分散安定化剤として水酸化第四アンモニウムを用いることにより、上記問題を解決したものである。すなわち、水酸化第四アンモニウムは抗菌金属をほとんど溶解させないため、酸化チタンゾルを安定化させながら抗菌金属の変色を抑制する傾向にあることを見出した。本発明に使用する水酸化第四アンモニウムとしては水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウムを例示することができる。特に水酸化テトラメチルアンモニウムはそれ自身安定であり、容易に入手できることから本発明のゾルの安定化剤として好適である。 Next, quaternary ammonium hydroxide used in the present invention will be described in detail. Quaternary ammonium hydroxide is one of the essential components for stabilizing the photocatalytic titanium oxide sol of the present invention. In general, alkaline compounds such as ammonia and primary to tertiary amines are all known as components that stabilize the sol of alkaline titanium oxide, but these alkaline compounds contain antibacterial metals such as silver. It tends to dissolve. In general, it is considered that the discoloration of the antibacterial metal component is largely due to ionization of the antibacterial metal, and it is not preferable that these alkali compounds that dissolve the antibacterial metal exist in the sol. Thus, as a result of intensive studies, the present inventors have solved the above problem by using quaternary ammonium hydroxide as a sol dispersion stabilizer. That is, it has been found that quaternary ammonium hydroxide hardly dissolves the antibacterial metal and therefore tends to suppress discoloration of the antibacterial metal while stabilizing the titanium oxide sol. Examples of the quaternary ammonium hydroxide used in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. In particular, tetramethylammonium hydroxide is suitable as a stabilizer for the sol of the present invention because it is stable per se and easily available.
水酸化第四アンモニウムの含有量についてはゾルを安定化させるため、酸化チタン（TiO2）１モルに対して0.01〜0.1モルの範囲で含有されることが望ましい。水酸化第四アンモニウムは下限以上であれば酸化チタンゾルを安定化させることができ、一方上限を超えて添加してもゾルの安定性が大幅に悪化することはないが、水酸化第四アンモニウムはわずかながら抗菌金属を溶解させるため、大量に用いることは好ましくない。
本発明において驚くべきことは、光触媒酸化チタンゾル中の銀の変色が上記水酸化第四アンモニウムに加えて、銅の存在下で更に抑えられることである。銅のゾル中の形態については不明であるが、添加する材料形態としては酸化物、水酸化物などがゾルを不安定化する硝酸イオンや塩素イオンを含まないため好ましい。本発明ゾル中の銅の含有量に関しては、銀に対する銅の割合がCuO／Ag2O（質量比）として1〜３０の範囲、好ましくは1〜１０の範囲で用いることが重要である。即ち、銅は少なくとも銀と同量以上用いる必要があり、下限を下廻ったときは銅の変色抑制効果は極度に低下する。また、上限を上廻って銅を添加してもそれに見合った変色抑制効果はない。
As for the content of quaternary ammonium hydroxide, in order to stabilize the sol, it is desirable that it is contained in the range of 0.01 to 0.1 mol with respect to 1 mol of titanium oxide (TiO 2 ). If the quaternary ammonium hydroxide is above the lower limit, the titanium oxide sol can be stabilized. On the other hand, addition of the quaternary ammonium hydroxide beyond the upper limit does not significantly deteriorate the stability of the sol. In order to dissolve the antibacterial metal slightly, it is not preferable to use a large amount.
What is surprising in the present invention is that the discoloration of silver in the photocatalytic titanium oxide sol is further suppressed in the presence of copper in addition to the quaternary ammonium hydroxide. The form in the copper sol is unknown, but as the material form to be added, oxides, hydroxides, and the like are preferable because they do not contain nitrate ions or chlorine ions that destabilize the sol. Regarding the copper content in the sol of the present invention, it is important that the ratio of copper to silver is in the range of 1 to 30, preferably 1 to 10, as CuO / Ag 2 O (mass ratio). That is, it is necessary to use at least the same amount of copper as silver, and when the lower limit is exceeded, the copper discoloration suppressing effect is extremely reduced. Moreover, even if copper is added exceeding the upper limit, there is no discoloration suppressing effect commensurate with it.
上述したように、本発明の光触媒酸化チタンゾルは銀および銅と水酸化第四アンモニウムとを含有する酸化チタンゾルであって、銀の変色を大幅に抑えることができ、その変色の目安として本発明では、３００〜４００ｎｍの波長閾の光照射による色質指数ΔL値が１０以下であることが特徴である。色質指数ΔL値に関しては後述するが、このΔL値が１０を超えると変色が大きく商品価値が著しく低下する。
次に本発明の酸化チタンゾルの製造方法について詳細に説明する。
本発明に用いるチタン塩としては、塩化チタン、硫酸チタン等を例示することができ、本発明のゾルはこれらチタン塩をアンモニア水で中和分解して得られるチタン酸のゲルを出発原料として用いることができる。これらのゲルを100℃以上の温度で水熱処理してアナターゼ型の結晶子を有する酸化チタンゾルが得られることは既に出願人らが開示しているが、本発明の光触媒酸化チタンゾルの製造方法に関しては、(1)チタン酸のゲルに銀および銅の酸化物または水酸化物を添加してから水熱処理した後、水酸化第四アンモニウムを添加する方法。(2)チタン酸のゲルに水酸化第四アンモニウムのみを添加してから水熱処理した後、銀および銅の酸化物または水酸化物を添加する方法。(3)チタン酸のゲルに銀および銅の酸化物または水酸化物並びに水酸化第四アンモニウムを同時に添加してから水熱処理する方法。(4)チタン酸のゲルを水熱処理した後に銀および銅の酸化物または水酸化物並びに水酸化第四アンモニウムを添加する方法。等を例示することができる。(1)および(3)の如く銀および銅の酸化物または水酸化物共存下で水熱処理した方が、銀の変色を抑えることができる。一般的に、これら添加物が多くなるに従い酸化チタンのアナターゼ型への結晶化を阻害する場合もあるのでこれら添加物の種類、量などを本発明の範囲内で適宜選択して製造することが好ましい。また、(4)の如く水熱処理後に銀と銅の酸化物または水酸化物および水酸化第四アンモニウムを添加した場合には、必要に応じて更に加熱することによってさらに安定化させることができる。加熱の時間は60〜100℃の温度で1〜3時間処理すればよい。
As described above, the photocatalytic titanium oxide sol of the present invention is a titanium oxide sol containing silver and copper and quaternary ammonium hydroxide, and can greatly suppress the discoloration of silver. The color quality index ΔL value by irradiation with light having a wavelength threshold of 300 to 400 nm is 10 or less. Although the color quality index ΔL value will be described later, when the ΔL value exceeds 10, the color change is large and the commercial value is remarkably lowered.
Next, the method for producing the titanium oxide sol of the present invention will be described in detail.
Examples of the titanium salt used in the present invention include titanium chloride and titanium sulfate. The sol of the present invention uses a titanic acid gel obtained by neutralizing and decomposing these titanium salts with ammonia water as a starting material. be able to. Although the applicants have already disclosed that these gels can be hydrothermally treated at a temperature of 100 ° C. or higher to obtain a titanium oxide sol having anatase type crystallites, regarding the method for producing the photocatalytic titanium oxide sol of the present invention, (1) A method of adding quaternary ammonium hydroxide after hydrothermal treatment after adding silver or copper oxide or hydroxide to the gel of titanic acid. (2) A method of adding silver or copper oxide or hydroxide after hydrothermal treatment after adding only quaternary ammonium hydroxide to titanic acid gel. (3) A method in which a silver and copper oxide or hydroxide and quaternary ammonium hydroxide are simultaneously added to a titanic acid gel and then hydrothermally treated. (4) A method of adding silver and copper oxides or hydroxides and quaternary ammonium hydroxide after hydrothermal treatment of the titanic acid gel. Etc. can be illustrated. As shown in (1) and (3), the discoloration of silver can be suppressed by hydrothermal treatment in the presence of an oxide or hydroxide of silver and copper. In general, as these additives increase, the crystallization of titanium oxide to anatase type may be inhibited. Therefore, the type and amount of these additives can be appropriately selected and manufactured within the scope of the present invention. preferable. Further, when silver and copper oxides or hydroxides and quaternary ammonium hydroxide are added after hydrothermal treatment as in (4), they can be further stabilized by heating as necessary. What is necessary is just to process for the time of a heating at the temperature of 60-100 degreeC for 1-3 hours.
本発明の光触媒酸化チタンゾルは、変色を大幅に低減化した酸化チタンからなるゾルであり、意匠性を重視した内装材用の薄膜形成材料として優れた効果を発揮するゾルであり、暗所のみならず光触媒効果を期待する各種用途に用いることができる。
本発明の光触媒酸化チタンゾルは、そのまま各種基材の表面に塗布することにより、光触媒性部材を製造することができる。また、必要に応じてバインダーを任意に添加して光触媒コーティング組成物とし、各種基材の表面に塗布することができる。
本発明の光触媒酸化チタンゾルに添加するバインダー材料については特に制限されるものではなく、有機系バインダーであっても無機系バインダーであっても良い。
The photocatalytic titanium oxide sol of the present invention is a sol composed of titanium oxide with greatly reduced discoloration, and is a sol that exhibits an excellent effect as a thin film forming material for interior materials with an emphasis on designability. It can be used for various applications where a photocatalytic effect is expected.
A photocatalytic member can be produced by applying the photocatalytic titanium oxide sol of the present invention to the surface of various substrates as it is. Further, if necessary, a binder can be optionally added to form a photocatalytic coating composition, which can be applied to the surface of various substrates.
The binder material added to the photocatalytic titanium oxide sol of the present invention is not particularly limited, and may be an organic binder or an inorganic binder.
有機系バインダーとしては、ポリエステル樹脂、ＰＶＡ樹脂、ポリエチレン−ＰＶＡ共重合樹脂、酢酸ビニル樹脂、ウレタン樹脂、アクリル樹脂、アクリルウレタン樹脂、アクリルスチレン樹脂、アクリルシリコーン樹脂、塩化ビニル樹脂等が挙げられる。
無機系バインダーとしてはジルコニウム化合物、ケイ素化合物、アルミニウム化合物等が挙げられる。具体的には、ジルコニウム化合物としては、四塩化ジルコニウム、オキシ塩化ジルコニウム、硝酸ジルコニウム、硫酸ジルコニウム、酢酸ジルコニウム、炭酸ジルコニウム等のジルコニウム塩、テトラエトキシジルコニウム、テトラ-i-プロポキシジルコニウム、テトラ-ｎ-ブトキシジルコニウム、テトラ-ｔ-ブトキシジルコニウム等のジルコニウムアルコキシド、等が挙げられる。ケイ素化合物としては、珪酸ナトリウム、珪酸カリウム、珪酸リチウム、珪酸セシウム、珪酸ルビジウム等のアルカリ珪酸塩、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロルシラン、メチルトリブロムシラン、メチルトリイソプロポキシシラン、メチルトリｔ−ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリクロルシラン、エチルトリブロムシラン、エチルトリイソプロポキシシラン等のアルコキシシラン、アルコキシシランの加水分解生成物であるシラノール、等が挙げられる。アルミニウム化合物としては、乳酸アルミニウム、リン酸アルミニウム、塩化アルミニウム等のアルミニウム塩、トリエトキシアルミニウム、トリ−ｉ−プロポキシアルミニウム、トリ−ｎ−ブトキシアルミニウム、トリ−ｔ−ブトキシアルミニウムアルミニウムアルコキシド等のアルミニウムアルコキシド、等が挙げられる。
また、コーティング組成物中にバインダー以外の添加物を添加することで、付加機能を持たせることも可能である。ここで、コーティング組成物中に添加できる添加物としては、例えば、コーティング組成物を着色するための顔料成分、塗膜に親水性能を付与するためのシリカ成分、コーティング組成物の保管安定性や作業性を良好に保つための増粘剤、消泡剤、分散剤等が挙げられる。
Examples of the organic binder include polyester resin, PVA resin, polyethylene-PVA copolymer resin, vinyl acetate resin, urethane resin, acrylic resin, acrylic urethane resin, acrylic styrene resin, acrylic silicone resin, and vinyl chloride resin.
Examples of the inorganic binder include a zirconium compound, a silicon compound, and an aluminum compound. Specifically, zirconium compounds include zirconium tetrachloride, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium acetate, zirconium carbonate and other zirconium salts, tetraethoxyzirconium, tetra-i-propoxyzirconium, tetra-n-butoxy. Zirconium alkoxides such as zirconium and tetra-t-butoxyzirconium, and the like can be mentioned. Examples of silicon compounds include alkali silicates such as sodium silicate, potassium silicate, lithium silicate, cesium silicate, and rubidium silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltribromosilane, methyltriisopropoxysilane, Examples thereof include alkoxysilanes such as methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltribromosilane and ethyltriisopropoxysilane, silanol which is a hydrolysis product of alkoxysilane, and the like. . Examples of the aluminum compound include aluminum salts such as aluminum lactate, aluminum phosphate, and aluminum chloride, aluminum alkoxides such as triethoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, and tri-t-butoxyaluminum alkoxide, Etc.
Moreover, it is also possible to give an additional function by adding additives other than a binder in a coating composition. Here, examples of the additive that can be added to the coating composition include a pigment component for coloring the coating composition, a silica component for imparting hydrophilic performance to the coating film, and storage stability and work of the coating composition. Examples thereof include a thickener, an antifoaming agent and a dispersing agent for maintaining good properties.
光触媒コーティング組成物を適用する基材は特に制限されるものではないが、基材が金属やセラミックス、例えばタイル等の耐熱性基材である場合は、光触媒コーティング組成物を表面に塗布した後に加熱乾燥することができ、基材表面に形成された光触媒含有膜は強く基材に密着する。また、基材が熱に弱い材質であったり、既存の壁面である場合には、常温で硬化可能なバインダーを含む光触媒コーティング組成物を表面に塗布することが好ましい。 The substrate to which the photocatalyst coating composition is applied is not particularly limited, but when the substrate is a heat-resistant substrate such as metal or ceramics, for example, tile, heating is performed after the photocatalyst coating composition is applied to the surface. The photocatalyst-containing film formed on the surface of the substrate can be strongly adhered to the substrate. Moreover, when the base material is a heat-sensitive material or an existing wall surface, it is preferable to apply a photocatalyst coating composition containing a binder curable at room temperature to the surface.
［実施例］
以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明は以下の実施例によってなんら制限を受けるものではない。なお、特に断らない限り％は質量％を示す。
本発明でいう色質指数ΔL値の測定方法および抗菌試験の方法については、以下に定義する。
[Example]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples. In addition, unless otherwise indicated,% shows the mass%.
The measurement method of the color quality index ΔL value and the antibacterial test method referred to in the present invention are defined below.
〈色質指数ΔLの測定方法〉
銀含有光触媒酸化チタンゾルをAg2O=0.05 %になるよう濃度調整した後、50mlのガラス製サンプル瓶に30g分注する。ブラックライト照射前のゾルの色質指数L１値を測定した後、サンプル瓶は震盪器に据え付け、20W型のブラックライト照射下で容器表面が1mW/cm2(365nm)になるようにセットし、30分間照射後のゾルの色質指数L２値を測定する。なお、色質指数L値の測定は日本電色工業(株)製Z-1001DPを用い、照射面積30mmφのセルに試料5gを入れて測定し、その差を色質指数ΔL値＝｜L１−L２｜とした。
<Measurement method of color quality index ΔL>
After the silver-containing photocatalytic titanium oxide sol in a concentration-adjusted to Ag 2 O = 0.05%, to 30g dispensing a glass sample bottle of 50 ml. After measuring the color quality index L1 value of the sol before black light irradiation, the sample bottle is set on a shaker and set so that the surface of the container is 1 mW / cm 2 (365 nm) under 20 W black light irradiation. The color quality index L2 value of the sol after irradiation for 30 minutes is measured. The color quality index L value was measured using a Z-1001DP manufactured by Nippon Denshoku Industries Co., Ltd., and a sample of 5 g was put in a cell with an irradiation area of 30 mmφ, and the difference was measured as the color quality index ΔL value = | L1− L2 |.
〈抗菌試験の方法〉
平成１７年度経済産業省委託事業成果「基準認証研究開発事業・光触媒試験方法の標準化」（平成１８年３月、社団法人日本ファインセラミック協会）記載の「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」に基づくフィルム密着法にて試験を行った。試験に用いた細菌は、大腸菌（Escherichia coli）NBRC3972である。また、試験に用いた培地などは、以下の通りである。
<Method of antibacterial test>
Results of FY 2005 commissioned by the Ministry of Economy, Trade and Industry, “Standard Certification R & D Project / Standardization of Photocatalyst Test Methods” (March 2006, Japan Fine Ceramics Association) “Fine Ceramics-Photocatalytic Antibacterial Processing Under Light Irradiation” The test was conducted by the film adhesion method based on the "antibacterial test method and antibacterial effect of products". The bacterium used for the test is Escherichia coli NBRC3972. Moreover, the culture medium etc. which were used for the test are as follows.
ａ）1/500濃度普通ブイヨン培地（以下、1/500ＮＢと言う。） 精製水1000mlに対して肉エキス3.0g、ペプトン10.0g、塩化ナトリウム5.0gを採り、フラスコに入れて混合し、内容物を十分に溶解した後、pH7.1±0.1（25℃）となるように水酸化ナトリウム溶液又は塩酸溶液で調整する。これを精製水で500倍に希釈し、pH6.7〜7.2（25℃）になるように水酸化ナトリウム溶液又は塩酸溶液で調整し、必要に応じて試験管又は三角フラスコに分注し、綿栓をして高圧蒸気殺菌する。 a) Normal bouillon medium with 1/500 concentration (hereinafter referred to as 1/500 NB) Take 3.0 g of meat extract, 10.0 g of peptone and 5.0 g of sodium chloride for 1000 ml of purified water, mix in a flask, and add the contents. Is sufficiently dissolved, and adjusted with sodium hydroxide solution or hydrochloric acid solution so that the pH becomes 7.1 ± 0.1 (25 ° C.). Dilute it 500 times with purified water, adjust with sodium hydroxide solution or hydrochloric acid solution to pH 6.7 to 7.2 (25 ° C), and dispense into test tubes or Erlenmeyer flasks as necessary. Cap and pasteurize with high pressure steam.
ｂ）ニュートリエント寒天培地 精製水1000mlに対して肉エキス3.0g、ペプトン5.0ｇ、寒天15.0gを採り、フラスコに入れて混合し、沸騰する水浴中で加熱して内容物を十分に溶解した後、pH6.8±0.2（25℃）になるように0.1mol/l水酸化ナトリウム溶液で調整し、綿栓をして高圧蒸気殺菌する。 b) Nutrient Agar Medium Take 1000g of purified water, 5.0g of peptone and 15.0g of agar for 1000ml of purified water, mix in a flask, and heat in a boiling water bath to fully dissolve the contents. Adjust to pH 6.8 ± 0.2 (25 ° C) with 0.1 mol / l sodium hydroxide solution, put on a cotton plug and pasteurize with high pressure steam.
ｃ）ＳＣＤＬＰ培地 精製水1000mlに対してガゼイン酸ペプトン17.0g、大豆製ペプトン3.0g、塩化ナトリウム5.0g、リン酸二水素カリウム2.5g、グルコース2.5g、レシチン1.0gを採り、フラスコに入れて混合し、内容物を十分に溶解し、更に非イオン界面活性剤7.0gを加えて溶解した後、pH7.0±0.2（25℃）になるように水酸化ナトリウム溶液又は塩酸溶液で調整し、必要に応じて試験管又は三角フラスコに分注し、綿栓をして高圧蒸気殺菌する。 c) SCDLP medium Take 17.0 g of peptone gazeinate, 3.0 g of soybean peptone, 5.0 g of sodium chloride, 2.5 g of potassium dihydrogen phosphate, 2.5 g of glucose, and 1.0 g of lecithin for 1000 ml of purified water, mix in a flask. Dissolve the contents sufficiently, and after adding 7.0 g of nonionic surfactant to dissolve, adjust with sodium hydroxide solution or hydrochloric acid solution so that the pH is 7.0 ± 0.2 (25 ° C). Dispense into test tubes or Erlenmeyer flasks according to, and sterilize with high-pressure steam using a cotton plug.
ｄ）生理食塩水 精製水1000mlに対して塩化ナトリウム8.5gを採り、フラスコに入れて十分に溶解した後、必要に応じて試験管又は三角フラスコに分注し、高圧蒸気殺菌する。 d) Physiological saline solution Take 8.5 g of sodium chloride with respect to 1000 ml of purified water, dissolve in a flask, and dispense into a test tube or an Erlenmeyer flask as necessary.
次に、試験における光の照射方法について以下に示す。紫外照射強度の測定は、光照射装置の床面に紫外線照度計の受光部を据え付け、受光部の上に試験に使用するフィルム及びガラス板を置き、指示値を読み取って行う。所定の紫外線照度が得られる位置を決め、試験片設置位置とする。試験菌液を接種した試験片への光照射は、試験菌液を接種した試験片の入った保存シャーレを保湿用ガラス又は保存シャーレの蓋で覆い、温度25±5℃に保った状態で光照射する。 Next, the light irradiation method in the test will be described below. The ultraviolet irradiation intensity is measured by installing a light receiving part of an ultraviolet illuminometer on the floor of the light irradiation apparatus, placing a film and a glass plate used for the test on the light receiving part, and reading the indicated value. A position where a predetermined ultraviolet illuminance can be obtained is determined and set as a test piece installation position. The test specimen inoculated with the test bacterial solution is irradiated with light in a state where the storage petri dish containing the test specimen inoculated with the test bacterial solution is covered with a moisturizing glass or storage petal lid and kept at a temperature of 25 ± 5 ° C. Irradiate.
試験菌液を接種した試験片の暗条件での保存は、試験菌液を接種した試験片の入った保存シャーレを保湿用ガラス又は保存シャーレの蓋で覆い、温度25±5℃に保った状態で光が当たらないように保存する。 Storage of the test specimen inoculated with the test bacterial solution in the dark condition is a state where the storage petri dish containing the test specimen inoculated with the test bacterial liquid is covered with a moisturizing glass or storage petri dish lid and kept at a temperature of 25 ± 5 ° C. Keep it away from light.
試験片には、平板状サンプルの平らな部分を50±2mm角（厚さ10mm以内）の正方形に切り取とったものを用いる。（光触媒抗菌加工していない試験片は9個、光触媒抗菌加工した試験片は6個準備する。）試験片の洗浄は、試験片の全面をエタノールを吸収させた局方ガーゼ又は脱脂綿で軽く2〜3回拭いた後、十分に乾燥させて行う。 As a test piece, a flat part of a flat sample is cut into a square of 50 ± 2 mm square (thickness within 10 mm). (Prepare 9 test specimens that have not been photocatalytically antibacterial and 6 specimens that have been photocatalyzed antibacterial.) Clean the specimens lightly with pharmacopeia or absorbent cotton that has absorbed ethanol over the entire surface of the specimens. After wiping 3 times, dry thoroughly.
試験菌の前培養は、菌を保存菌株からニュートリエント寒天培地に1白金耳移植し、温度37±1℃で16〜24時間培養する。さらに、この培養菌から新たなニュートリエント寒天培地に1白金耳移植し、温度37±1℃で16〜20時間培養する。 Pre-culture of the test bacteria is carried out by transferring 1 platinum ear from a stored strain to a nutrient agar medium and culturing at a temperature of 37 ± 1 ° C. for 16 to 24 hours. Furthermore, one platinum loop is transplanted from this culture to a new nutrient agar medium and cultured at a temperature of 37 ± 1 ° C. for 16 to 20 hours.
試験菌液の調製は、前培養した試験株の菌体1白金耳量を少量の1/500NBに均一に分散させ、顕微鏡による直接観察して菌数を測定する。この菌液を1/500NBを用いて適宜希釈し、菌数が約6.7×10 5〜約2.6×10 6個/mlとなるように調製し、これを試験菌液とする。 For the preparation of the test bacterial solution, the amount of 1 platinum loop of the pre-cultured test strain is uniformly dispersed in a small amount of 1 / 500NB, and the number of bacteria is measured by direct observation with a microscope. The bacterial suspension was diluted appropriately with 1 / 500NB, prepared as the number of bacteria is about 6.7 × 10 5 ~ about 2.6 × 10 6 cells / ml, to do this the test bacterial liquid.
試験菌液の接種は、試験菌液をピペットで正確に採取し、これを各試験片に滴下する。滴下した試験菌液の上に密着フィルムを被せ、菌液が密着フィルムの端からこぼれないように注意しながら試験菌液が密着フィルム全体に行きわたるように軽く押さえつけた後、保湿用ガラスを載せる。 Inoculation with the test bacterial solution is performed by accurately collecting the test bacterial solution with a pipette and dropping it on each test piece. Cover the dropped test bacteria solution with a sticky film, lightly press the test solution so that it does not spill from the edge of the sticky film, and then place the moisturizing glass. .
接種した試験菌液の洗い出しは、密着フィルムと試験片とを菌液がこぼれないように注意しながら滅菌したピンセットを用いて滅菌済みストマッカー袋内に入れ、これにピペットでSCDLP培地10mlを加え、手で試験片及び被覆フィルムを十分にもみ、試験菌を洗い出す。洗い出し液は速やかに、以下に示す菌数の測定に供する。 To wash out the inoculated test bacterial solution, put the adhesive film and the test piece in a sterilized stomacher bag using sterilized tweezers while being careful not to spill the bacterial solution, add 10 ml of SCDLP medium with a pipette, Examine test specimens and coated film by hand to wash out test bacteria. The washing solution is promptly used for the measurement of the number of bacteria shown below.
菌数の測定は、10倍希釈法による混釈平板培養法によって行う。洗い出し液を滅菌したピペットで1ml採り、生理食塩水9±0.1mlが入った試験管に加え、十分に攪拌する。さらに、この試験管から1mlを新しいピペットで採り、生理食塩水9±0.1mlが入った別の試験管に加え、十分に攪拌する。この操作を順次繰り返して、10倍希釈法による希釈系列を作製し、各希釈系列の試験管からそれぞれ別のシャーレ2枚に新しいピペットで1ml採り、45〜48℃に保温したニュートリエント寒天培地15〜20mlを入れ、蓋をして15分間室温で放置する。培地が凝固したら、シャーレを倒置し、37±1℃で40〜48時間培養する。培養後、30〜300個のコロニーが現れた希釈系列のシャーレのコロニー数を測定し、洗い出し液の菌濃度を式（数1）によって有効数字2桁まで求める。 The number of bacteria is measured by the pour plate culture method using a 10-fold dilution method. Take 1 ml of the washing solution with a sterilized pipette, add it to a test tube containing 9 ± 0.1 ml of physiological saline, and stir well. In addition, 1 ml from this tube is taken with a new pipette, added to another tube containing 9 ± 0.1 ml of physiological saline, and stirred well. Repeat this procedure in order to prepare a dilution series by the 10-fold dilution method. Take 1 ml of each dilution series from a test tube in two separate dishes with a new pipette and keep it at 45 to 48 ° C. Add ~ 20ml, cover and leave at room temperature for 15 minutes. When the medium has solidified, invert the petri dish and incubate at 37 ± 1 ° C. for 40-48 hours. After culturing, the number of colonies in the petri dish of the dilution series in which 30 to 300 colonies appeared is measured, and the bacterial concentration of the washing solution is obtained up to two significant figures by the formula (Equation 1).
生菌数は、式（数1）で求めた菌濃度から、式（数2）によって求めることができる。 The viable cell count can be obtained from the formula (Equation 2) from the bacterial concentration obtained from the equation (Equation 1).
コロニー数が“＜１”の場合の生菌数は“＜10”と表示し（Vが10mlの場合）、平均値を“10”として計算する。また、コロニー数が30個未満の場合は、測定したコロニー数を用いて生菌数を計算する。
抗菌活性値RL、RDと光照射による効果ΔRは、式（数２）で求めた生菌数をもとに、以下の式（数3）、式（数4）、式（数5）により算出することができる。
When the number of colonies is “<1”, the viable count is displayed as “<10” (when V is 10 ml), and the average value is calculated as “10”. When the number of colonies is less than 30, the number of viable bacteria is calculated using the measured number of colonies.
The antibacterial activity values R L and R D and the effect ΔR due to light irradiation are based on the number of viable bacteria determined by the equation (Equation 2), and the following equation (Equation 3), Equation (Equation 4), ).
四塩化チタン水溶液（TiO2＝0.5％）にアンモニア水（NH3=3.0％）を攪拌下で添加し、チタンゲルを生成させた。これをろ液中の塩素イオンがチタンゲル（TiO2）に対して100ppm以下になるまでろ過水洗し、TiO2=6.2％のチタンゲルからなるスラリーを得た。このスラリー200gにAg2O＋CuOが酸化チタン（TiO2）に対して５質量％、銀に対する銅の割合がCuO／Ag2O（質量比）＝５となる酸化銀(Ag2O、和光純薬工業(株)製)0.1 gと水酸化銅(Cu(OH)2、関東化学(株)製)0.6gを添加した。さらに、酸化チタン（TiO2）1モルに対して0.03モルとなる水酸化テトラメチルアンモニウム25%水溶液(多摩化学工業(株)製)1.7ｇを添加してよく攪拌した後、これをオートクレーブに入れ、130℃で10時間の水熱処理を行い、本発明のゾル（TiO2＝6.10％、Ag2O＝0.05％、CuO＝0.24％、水酸化テトラメチルアンモニウム＝0.2％）を得た。このゾルを100℃で乾燥させて得られる粉を粉末Ｘ線回折法により測定したところ、アナターゼ型の酸化チタンのピークが認められた。また、得られた本発明のゾルの変色の程度を評価するため、色質指数ΔＬ値を求めたところ、1.29であった。 Ammonia water (NH 3 = 3.0%) was added to a titanium tetrachloride aqueous solution (TiO 2 = 0.5%) with stirring to form a titanium gel. This was washed with filtered water until the chlorine ions in the filtrate were 100 ppm or less with respect to the titanium gel (TiO 2 ) to obtain a slurry made of titanium gel with TiO 2 = 6.2%. In 200 g of this slurry, Ag 2 O + CuO is 5% by mass with respect to titanium oxide (TiO 2 ), and the ratio of copper to silver is CuO / Ag 2 O (mass ratio) = 5. Silver oxide (Ag 2 O, Wako Pure Chemical Industries) Kogyo Co., Ltd. (0.1 g) and copper hydroxide (Cu (OH) 2 , Kanto Chemical Co., Ltd.) 0.6 g were added. Furthermore, after adding 1.7 g of tetramethylammonium hydroxide 25% aqueous solution (manufactured by Tama Chemical Industry Co., Ltd.) of 0.03 mol to 1 mol of titanium oxide (TiO 2 ) and stirring well, this was put in an autoclave. Then, hydrothermal treatment was performed at 130 ° C. for 10 hours to obtain a sol of the present invention (TiO 2 = 6.10%, Ag 2 O = 0.05%, CuO = 0.24%, tetramethylammonium hydroxide = 0.2%). When the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed. In addition, in order to evaluate the degree of discoloration of the obtained sol of the present invention, the color quality index ΔL value was 1.29.
［比較例1］
実施例1において、水酸化銅0.6ｇを添加しないことを除いてはまったく同一の条件で試験を行い、得られたゾルの色質指数ΔＬ値を求めたところ、12.33であった。
[Comparative Example 1]
In Example 1, the test was performed under exactly the same conditions except that 0.6 g of copper hydroxide was not added, and the color quality index ΔL value of the obtained sol was determined to be 12.33.
硫酸チタン水溶液（TiO2＝0.5％）にアンモニア水（NH3=3.0％）を攪拌下で添加し、チタンゲルを生成させた。これをろ液中の硫酸イオンがチタンゲル（TiO2）に対して100ppm以下になるまでろ過水洗し、TiO2=6.2%のチタンゲルからなるスラリーを得た。このスラリー200gにAg2O＋CuOが酸化チタン（TiO2）に対して５質量％、銀に対する銅の割合がCuO／Ag2O（質量比）＝５となる酸化銀0.1 gと水酸化銅0.6gおよび水酸化テトラメチルアンモニウム25%水溶液1.7ｇを添加してよく攪拌した後、これをオートクレーブに入れ、130℃で10時間の水熱処理を行ない、本発明のゾル（TiO2＝6.1％、Ag2O＝0.05％、CuO＝0.24％、水酸化テトラメチルアンモニウム＝0.2％）を得た。このゾルを100℃で乾燥させて得られる粉を粉末Ｘ線回折法により測定したところ、アナターゼ型の酸化チタンのピークが認められた。さらに、得られた本発明のゾルの変色の程度を評価するため、色質指数ΔＬ値を求めたところ、2.24であった。 Ammonia water (NH 3 = 3.0%) was added under stirring to the aqueous solution of titanium sulfate (TiO 2 = 0.5%), to produce a Chitangeru. This was washed with filtered water until sulfate ions in the filtrate became 100 ppm or less with respect to titanium gel (TiO 2 ), and a slurry made of titanium gel with TiO 2 = 6.2% was obtained. In 200 g of this slurry, Ag 2 O + CuO is 5% by mass with respect to titanium oxide (TiO 2 ), and the ratio of copper to silver is 0.1 g of silver oxide and 0.6 g of copper hydroxide with CuO / Ag 2 O (mass ratio) = 5. Then, 1.7 g of a 25% aqueous solution of tetramethylammonium hydroxide was added and stirred well, then this was placed in an autoclave and subjected to hydrothermal treatment at 130 ° C. for 10 hours to obtain the sol of the present invention (TiO 2 = 6.1%, Ag 2 O = 0.05%, CuO = 0.24%, tetramethylammonium hydroxide = 0.2%). When the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed. Furthermore, in order to evaluate the degree of discoloration of the obtained sol of the present invention, the color quality index ΔL value was 2.24.
四塩化チタン水溶液（TiO2＝0.5％）にアンモニア水（NH3=3.0％）を攪拌下で添加し、チタンゲルを生成させた。これをろ液中の塩素イオンがチタンゲル（TiO2）に対して100ppm以下になるまでろ過水洗した。このゲルをオートクレーブに入れ120℃で24時間の水熱処理を行い、TiO2=6.2%のチタンゾルを得た。このゾル200gに表１に示す割合になるように酸化銀と水酸化銅および水酸化テトラメチルアンモニウム25%水溶液1.7ｇを添加してよく攪拌し、本発明のゾルを得た。このゾルを100℃で乾燥させて得られる粉を粉末Ｘ線回折法により測定したところ、アナターゼ型の酸化チタンのピークが認められた。さらに、得られた本発明のゾルの変色の程度を評価するため、色質指数ΔＬ値を求めた。
また、本発明の各ゾルを室温で1ヶ月間放置した後観測したが、いずれも沈殿は見られず安定なゾルであった。
Ammonia water (NH 3 = 3.0%) was added to a titanium tetrachloride aqueous solution (TiO 2 = 0.5%) with stirring to form a titanium gel. This was washed with filtered water until the chlorine ions in the filtrate became 100 ppm or less with respect to titanium gel (TiO 2 ). This gel was put in an autoclave and hydrothermally treated at 120 ° C. for 24 hours to obtain a titanium sol having TiO 2 = 6.2%. Silver oxide, copper hydroxide, and 1.7 g of tetramethylammonium hydroxide 25% aqueous solution 1.7 g were added to 200 g of this sol so as to have the ratio shown in Table 1, and the sol of the present invention was obtained. When the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed. Further, in order to evaluate the degree of discoloration of the obtained sol of the present invention, a color quality index ΔL value was obtained.
In addition, each sol of the present invention was observed after being allowed to stand at room temperature for 1 month.
［比較例２］
四塩化チタン水溶液（TiO2＝0.5％）にアンモニア水（NH3=3.0％）を攪拌下で添加し、チタンゲルを生成させた。これをろ液中の塩素イオンがチタンゲル（TiO2）に対して100ppm以下になるまでろ過水洗し、TiO2=6.2％のチタンゲルからなるスラリーを得た。このスラリー200gに酸化銀0.1gと水酸化銅0.6gを添加してよく攪拌した後、これをオートクレーブに入れ、130℃で10時間の水熱処理を行なったところ、ゲル化してゾルは得られなかった。
[Comparative Example 2]
Ammonia water (NH 3 = 3.0%) was added to a titanium tetrachloride aqueous solution (TiO 2 = 0.5%) with stirring to form a titanium gel. This was washed with filtered water until the chlorine ions in the filtrate were 100 ppm or less with respect to the titanium gel (TiO 2 ) to obtain a slurry made of titanium gel with TiO 2 = 6.2%. After adding silver oxide 0.1g and copper hydroxide 0.6g to 200g of this slurry and stirring well, it was put in an autoclave and hydrothermally treated at 130 ° C for 10 hours. It was.
［比較例３］
四塩化チタン水溶液（TiO2＝0.5％）にアンモニア水（NH3=3.0％）を攪拌下で添加し、チタンゲルを生成させた。これをろ液中の塩素イオンがチタンゲル（TiO2）に対して100ppm以下になるまでろ過水洗し、TiO2=6.2％のチタンゲルからなるスラリーを得た。このスラリー200gに酸化銀0.1gと水酸化銅0.6gおよびモノエタノールアミン0.3ｇを添加してよく攪拌した後、これをオートクレーブに入れ、130℃で10時間の水熱処理を行ない、ゾルを得た。このゾルを100℃で乾燥させて得られる粉を粉末Ｘ線回折法により測定したところ、アナターゼ型の酸化チタンのピークが認められた。さらに、得られた本発明のゾルの変色の程度を評価するため、色質指数ΔＬ値を求めたところ、4.82であった。
しかしながら、得られたゾルは、室温で保存中７日後には粘度が上昇し、ゲル化した。
[Comparative Example 3]
Ammonia water (NH 3 = 3.0%) was added under stirring to the aqueous titanium tetrachloride solution (TiO 2 = 0.5%), to produce a Chitangeru. This was washed with filtered water until the chlorine ions in the filtrate were 100 ppm or less with respect to the titanium gel (TiO 2 ) to obtain a slurry made of titanium gel with TiO 2 = 6.2%. After adding 0.1 g of silver oxide, 0.6 g of copper hydroxide and 0.3 g of monoethanolamine to 200 g of this slurry and stirring well, this was put in an autoclave and hydrothermally treated at 130 ° C. for 10 hours to obtain a sol. . When the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed. Further, in order to evaluate the degree of discoloration of the obtained sol of the present invention, the color quality index ΔL value was calculated to be 4.82.
However, the obtained sol increased in viscosity and gelled after 7 days of storage at room temperature.
実施例１で得られた光触媒酸化チタンゾルに、アルカリ珪酸塩と水とを混合撹拌し、光触媒コーティング組成物を得た。光触媒コーティング組成物の組成は以下の通りである。 The photocatalytic titanium oxide sol obtained in Example 1 was mixed and stirred with an alkali silicate and water to obtain a photocatalytic coating composition. The composition of the photocatalytic coating composition is as follows.
光触媒酸化チタン（Ａｇ２Ｏ、ＣｕＯ含有） １３〜３０％
ＳｉＯ２ ４５〜７０％
Ｎａ２Ｏ ０〜２０％
Ｌｉ２Ｏ ０〜２０％
Ｋ２Ｏ ０〜２０％
コーティング組成物中のTiO2とSiO2との比率は1対3とし、コーティング組成物の固形分濃度は０.５%とした。本コーティング組成物を施釉タイルにスプレー塗布して８００℃で１分間加熱乾燥し、５０ｍｍ角に切り出したものを抗菌試験のサンプルとした。表２に示す条件で抗菌試験を行ったところ、抗菌活性値は、ＲＬが４.３、ＲＤが２.５であった。
Photocatalytic titanium oxide (containing Ag 2 O, CuO) 13-30%
SiO 2 45~70%
Na 2 O 0~20%
Li 2 O 0-20%
K 2 O 0~20%
The ratio of TiO 2 and SiO 2 in the coating composition was 1: 3, the solid content concentration of the coating composition was 0.5%. The coating composition was spray-applied to a glazed tile, heat-dried at 800 ° C. for 1 minute, and cut into 50 mm squares as antibacterial test samples. When the antibacterial test was conducted under the conditions shown in Table 2, the antibacterial activity values were 4.3 for RL and 2.5 for RD .
実施例１で得られた光触媒酸化チタンゾルに、アクリル樹脂エマルジョン、顔料酸化チタン、タルク、繊維顔料、コロイダルシリカ、水を加えて撹拌し、光触媒コーティング組成物を得た。光触媒コーティング組成物の組成は以下の通りである。 To the photocatalytic titanium oxide sol obtained in Example 1, an acrylic resin emulsion, pigment titanium oxide, talc, fiber pigment, colloidal silica, and water were added and stirred to obtain a photocatalytic coating composition. The composition of the photocatalytic coating composition is as follows.
光触媒酸化チタン（Ａｇ２Ｏ、ＣｕＯ含有） ０.０５〜５％
アクリル樹脂 ３０〜５０％
顔料（白） ３０〜４０％
タルク ５〜１０％
繊維顔料 ５〜１０％
ＳｉＯ２ ５〜２０％
コーティング組成物中のTiO2とアクリル樹脂との比率は1対２００とし、コーティング組成物の固形分濃度は５０%とした。本コーティング組成物をアルミニウム基材にローラー塗布して常温で７日間乾燥し、５０ｍｍ角に切り出したものを抗菌試験のサンプルとした。表２に示す条件で抗菌試験を行ったところ、抗菌活性値は、ＲＬが４.０、ＲＤが４.１であった。
Photocatalytic titanium oxide (containing Ag 2 O, CuO) 0.05 to 5%
Acrylic resin 30-50%
Pigment (white) 30-40%
Talc 5-10%
Fiber pigment 5-10%
SiO 2 5~20%
The ratio of TiO 2 and acrylic resin in the coating composition was 1: 200, and the solid content concentration of the coating composition was 50%. The coating composition was applied onto an aluminum base with a roller, dried at room temperature for 7 days, and cut into 50 mm squares as antibacterial test samples. When the antibacterial test was conducted under the conditions shown in Table 2, the antibacterial activity values were 4.0 for RL and 4.1 for RD .
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| KR20170010408A (en) | 2014-09-19 | 2017-01-31 | 쇼와 덴코 가부시키가이샤 | Antibacterial/antiviral composition, antibacterial/antiviral agent, photocatalyst, and bacteria/virus inactivation method |
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