JP4125316B2 - Method for producing visible light transmitting photocatalyst coating solution and visible light transmitting photocatalyst coating solution - Google Patents
Method for producing visible light transmitting photocatalyst coating solution and visible light transmitting photocatalyst coating solution Download PDFInfo
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- JP4125316B2 JP4125316B2 JP2005306071A JP2005306071A JP4125316B2 JP 4125316 B2 JP4125316 B2 JP 4125316B2 JP 2005306071 A JP2005306071 A JP 2005306071A JP 2005306071 A JP2005306071 A JP 2005306071A JP 4125316 B2 JP4125316 B2 JP 4125316B2
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- 239000011248 coating agent Substances 0.000 title claims description 84
- 238000000576 coating method Methods 0.000 title claims description 84
- 239000011941 photocatalyst Substances 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000243 solution Substances 0.000 claims description 77
- 239000011240 wet gel Substances 0.000 claims description 52
- -1 silicon alkoxide Chemical class 0.000 claims description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 230000001699 photocatalysis Effects 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 239000003377 acid catalyst Substances 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000000499 gel Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- GEGLCBTXYBXOJA-UHFFFAOYSA-N 1-methoxyethanol Chemical compound COC(C)O GEGLCBTXYBXOJA-UHFFFAOYSA-N 0.000 claims description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 description 25
- 230000005540 biological transmission Effects 0.000 description 17
- 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 14
- 238000000034 method Methods 0.000 description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 11
- 229960000907 methylthioninium chloride Drugs 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 229920006298 saran Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 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
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Description
本発明は、基板材料の表面に塗膜処理を施して常温で乾燥させることにより可視光透過型光触媒被膜を形成する可視光透過型光触媒コーティング溶液の製造方法および可視光透過型光触媒コーティング溶液に関するものである。 The present invention relates to a method for producing a visible light transmissive photocatalyst coating solution that forms a visible light transmissive photocatalyst coating by applying a coating treatment to the surface of a substrate material and drying it at room temperature, and to a visible light transmissive photocatalyst coating solution. It is.
光触媒は、その表面に紫外線が照射されるとそれを吸収して自由電子と正孔が形成される。この電子や正孔が有機物に作用するとそれを最終的には水を二酸化炭素に分解する。このことから防汚、防臭、抗菌等の特性を発揮する。光触媒を有する代表的な物質には、二酸化チタン、酸化スズ、酸化亜鉛等の金属酸化物や硫化カドミウム、硫化銅等の硫化物がある。その中でもアナターゼ型二酸化チタンの光触媒能が極めて高いことが知られている。 When the surface of the photocatalyst is irradiated with ultraviolet rays, it absorbs it to form free electrons and holes. When these electrons and holes act on organic matter, it eventually decomposes water into carbon dioxide. For this reason, it exhibits properties such as antifouling, deodorization and antibacterial properties. Typical substances having a photocatalyst include metal oxides such as titanium dioxide, tin oxide, and zinc oxide, and sulfides such as cadmium sulfide and copper sulfide. Among them, it is known that the photocatalytic ability of anatase type titanium dioxide is extremely high.
そのため、二酸化チタン被膜を基材表面に形成して光触媒を持たせる種々の技術が提案されている。例えば、基材表面に二酸化チタン粒子を付着させた後焼結したり、二酸化チタン粒子を含むコーティング溶液を基材表面にコートした後焼成して光触媒被膜を形成する技術などが挙げられる。 Therefore, various techniques for forming a titanium dioxide film on the surface of a base material to have a photocatalyst have been proposed. For example, a technique in which titanium dioxide particles are attached to the surface of the substrate and then sintered, or a coating solution containing titanium dioxide particles is coated on the surface of the substrate and then fired to form a photocatalyst film.
しかしながら、従来の方法では基材表面に光触媒被膜を形成する際には数百℃もの高温での焼成過程が不可欠であり、基材に耐熱性が必要である。このため、光触媒をコーティングできる基材に制限があった。また、既に建てられている家の壁など既存の材料に新たに光触媒能を付与する場合は非常に困難であった。また、二酸化チタンを含む光触媒塗料では、バインダーとして種々の酸化物などが含まれており、それらが二酸化チタン粒子の表面を覆ってしまい、光吸収によって生成する電子や正孔と分解したい有機物との接触が阻害され十分な光触媒特性を得ることが困難となる。 However, in the conventional method, when the photocatalytic film is formed on the surface of the base material, a baking process at a high temperature of several hundred degrees Celsius is indispensable, and the base material needs heat resistance. For this reason, there is a limit to the base material on which the photocatalyst can be coated. Moreover, it has been very difficult to newly provide photocatalytic activity to existing materials such as walls of houses that have already been built. In addition, the photocatalyst paint containing titanium dioxide contains various oxides as a binder, which covers the surface of the titanium dioxide particles, and generates electrons and holes generated by light absorption between the organic substance to be decomposed. Contact is hindered, making it difficult to obtain sufficient photocatalytic properties.
最近、加熱処理を施さずに常温で光触媒被膜を作製する技術も提案されている。例えば、特開２００４−２５６７２７号公報では、有機溶媒にジメチルホルムアルデヒドとチタンアルコキシドと酸触媒を加えて撹拌して湿潤ゲルを作製後、乳酸を含む有機溶媒にその湿潤ゲルを加えて溶解したコーティング溶液が提案されている。 Recently, a technique for producing a photocatalytic film at room temperature without performing heat treatment has also been proposed. For example, JP-A-2004-256727 discloses a coating solution in which dimethylformaldehyde, titanium alkoxide and an acid catalyst are added to an organic solvent and stirred to prepare a wet gel, and then the wet gel is added and dissolved in an organic solvent containing lactic acid. Has been proposed.
また、チタンアルコキシドを加水分解して、非晶質チタニアゾルを形成したのち、水存在下に擬似水熱合成することで、結晶粒径２０ｎｍ以下のアナターゼを調製することが記載されている(特開２００１−２６２００７号公報(特許文献２)、特開２００１−２６２
００８号公報(特許文献３))。
Further, it is described that anatase having a crystal grain size of 20 nm or less is prepared by hydrolyzing titanium alkoxide to form an amorphous titania sol and then performing pseudohydrothermal synthesis in the presence of water (Japanese Patent Application Laid-Open No. 2005-318867). JP 2001-262007 A (Patent Document 2), JP 2001-262 A
No. 008 (Patent Document 3)).
しかしながら、特許文献２および３に記載された方法では、得られた分散液の安定性が低く、このため、長期安定性に優れた光触媒コーティングを得ることは困難であった。
一般に、光触媒能を持った粒子を含むコーティング液を用いて、加熱処理せずに常温で作製した光触媒被膜は基材に対する付着力は弱く、容易に剥離したり、粉落ちが起こった
りする。特にガラスなど透光性を有する基材上にこのようなコーティング液を塗布すると、透光性が損なわれる。そのため、応用が限られている。
In general, a photocatalyst film prepared at room temperature without using a coating solution containing particles having photocatalytic activity has low adhesion to the substrate, and is easily peeled off or powdered off. In particular, when such a coating liquid is applied onto a substrate having translucency such as glass, the translucency is impaired. Therefore, the application is limited.
本発明は、可視光の透光性を損なわずかつ基材との付着力の著しい改善を実現したものである。 比較的短時間で、可視光を８０％以上透過し、基材から容易に剥離しない光触
媒被膜を形成できる光触媒コーティング溶液の製造方法及び光触媒コーティング溶液を提供することを目的としている。
The present invention achieves a significant improvement in adhesion to a substrate without impairing the translucency of visible light. An object of the present invention is to provide a photocatalyst coating solution production method and a photocatalyst coating solution capable of forming a photocatalyst film that transmits 80% or more of visible light in a relatively short time and does not easily peel from a substrate.
本発明に係る可視光透過型光触媒コーティング溶液の製造方法の特徴は、Ｔｉ(ＯＲ)4
［Ｒは互いに独立で、炭素数１〜６の炭化水素基］で表される有機チタン化合物、およびホルムアルデヒドおよび／またはジメチルホルムアミドとを混合した混合溶液に、酸触媒を加えたのち、直ちに加圧下で１００〜２００℃の温度に加熱し、１分から４８時間反応させてアナターゼ型酸化チタンを含む湿潤ゲルを調製する工程(湿潤ゲル調製工程)、を含むことにある。
A feature of the method for producing a visible light transmissive photocatalyst coating solution according to the present invention is Ti (OR) 4
Immediately under pressure, an acid catalyst is added to a mixed solution in which an organic titanium compound represented by [R is independently of each other and a hydrocarbon group having 1 to 6 carbon atoms] and formaldehyde and / or dimethylformamide are added. And a step of preparing a wet gel containing anatase-type titanium oxide by heating to a temperature of 100 to 200 ° C. and reacting for 1 minute to 48 hours (wet gel preparation step).
前記湿潤ゲル調製工程の後、乳酸を０．５〜１０重量％の量で含む、2-エトキシエタノール、1-メトキシエタノール、2-プロパノールから選ばれる少なくとも１種の有機溶媒からなる溶液に、得られた湿潤ゲルを溶解する工程(湿潤ゲル溶解工程)を行う。
After the wet gel preparation step, a solution comprising at least one organic solvent selected from 2-ethoxyethanol, 1-methoxyethanol and 2-propanol containing lactic acid in an amount of 0.5 to 10% by weight is obtained. A step of dissolving the wet gel (wet gel dissolution step) is performed.
このような方法により、可視光に対して透明であり、かつ優れた光触媒特性を有するコーティング膜を形成できる。
また、前記湿潤ゲル調製工程において、
混合溶液に、あらかじめ、シリコンアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、チタンアルコキシド、ジルニアアルコキシドから選ばれる少なくとも１種のアルコキシドを０．１〜１．０重量％の量で添加しておいてもよく、
さらに、湿潤ゲル溶解工程において、さらにシリコンアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、チタンアルコキシド、ジルコニアアルコキシドからなる群から選ばれる少なくとも１種のアルコキシド、および／または、
酸化チタン、二酸化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウムからなる群から選ばれる少なくとも１種の無機酸化物を、
０．１〜１０重量％の量で添加してもよい。
By such a method, it is possible to form a coating film that is transparent to visible light and has excellent photocatalytic properties.
In the wet gel preparation step,
In the mixed solution, at least one alkoxide selected from silicon alkoxide, aluminum alkoxide, magnesium alkoxide, titanium alkoxide, and zirconia alkoxide may be added in an amount of 0.1 to 1.0% by weight in advance.
Further, in the wet gel dissolution step, at least one alkoxide selected from the group consisting of silicon alkoxide, aluminum alkoxide, magnesium alkoxide, titanium alkoxide, zirconia alkoxide, and / or
At least one inorganic oxide selected from the group consisting of titanium oxide, silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide,
You may add in the quantity of 0.1-10 weight%.
これによって、室温で塗布・乾燥すると基材に対するコーティング膜の付着力を著しく向上させることができる。
ゲル調製工程において、７０〜８５重量％の有機溶媒に、ホルムアルデヒドおよび／またはジメチルホルムアミドを１〜６重量％、酸触媒として０．１〜１．５モル／Ｌの硝酸水溶液を１〜３重量％加えた後、有機チタン化合物を５〜１５重量％の量で添加することがより望ましい態様である。
Thereby, when applied and dried at room temperature, the adhesion of the coating film to the substrate can be remarkably improved.
In the gel preparation step, 70 to 85% by weight of organic solvent is 1 to 6% by weight of formaldehyde and / or dimethylformamide, and 1 to 3% by weight of 0.1 to 1.5 mol / L nitric acid aqueous solution as an acid catalyst. It is a more desirable embodiment that the organic titanium compound is added in an amount of 5 to 15% by weight after the addition.
また、本発明に係る可視光透過型光触媒コーティング溶液は、前述したいずれのコーティング溶液の製造方法により得られる溶液であることを特徴としており、この溶液によれば、基材に塗布・乾燥後、可視光に対して透明であり、かつ剥離し難く光触媒特性に優れたコーティング膜を形成する。 Further, the visible light transmission type photocatalyst coating solution according to the present invention is characterized in that it is a solution obtained by any of the above-described methods for producing a coating solution, and according to this solution, after coating and drying on a substrate, A coating film which is transparent to visible light and hardly peels off and has excellent photocatalytic properties is formed.
以上の本発明によれば、短時間で常温乾燥により、基材に強固の付着し、耐水性に優れた可視光透過型光触媒コーティング膜を形成することができる。 According to the present invention described above, a visible light transmission photocatalyst coating film that adheres firmly to a substrate and is excellent in water resistance can be formed by drying at room temperature in a short time.
以下に、本発明に係る可視光透過型光触媒コーティング溶液の製造方法及び光触媒コーティング溶液の実施形態について説明する。
本実施形態の光触媒特性コーティング溶液の製造方法は、主として加圧加熱下で生成した超微粒子が二次元ネットワークを形成して湿潤ゲルを製造するステップと、必要に応じて湿潤ゲルを有機溶媒に溶解させるステップとを行っている。このような工程は概略図１に示される。
Below, the manufacturing method of the visible light transmission type photocatalyst coating solution which concerns on this invention, and embodiment of a photocatalyst coating solution are described.
The manufacturing method of the photocatalytic property coating solution of the present embodiment includes a step of producing a wet gel by forming a two-dimensional network mainly of ultrafine particles generated under pressure and heating, and if necessary, dissolving the wet gel in an organic solvent. Step to make. Such a process is shown schematically in FIG.
湿潤ゲルを製造するステップは、有機溶媒にホルムアルデヒドおよび／ジメチルホルムアミドと酸触媒を混合するステップと、それにチタンアルコキシドを加えて撹拌するステップと、さらに加圧加熱するステップを経て行われる。チタンアルコキシドを加えて撹拌するステップでは、徐々にチタンアルコキシドの加水分解が生じるが、その速度は極めて遅く、室温下では通常４８時間以上の時間がかかる。加えて、この条件では得られる湿潤ゲルは非晶質の微粒子から構成されており、顕著な光触媒特性を示さない。そこで、加圧加熱下で反応させると４８時間以内に加水分解反応が終了し、優れた光触媒特性を示す結晶を有する湿潤ゲルを得ることができる。また、反応時間の下限は１分間以上であればよい。より望ましい反応時間は２４〜４８時間である。 The step of producing the wet gel is performed through a step of mixing formaldehyde and / dimethylformamide and an acid catalyst in an organic solvent, a step of adding titanium alkoxide to the mixture, and a step of heating under pressure. In the step of adding and stirring the titanium alkoxide, the titanium alkoxide is gradually hydrolyzed, but the rate is extremely slow and usually takes 48 hours or more at room temperature. In addition, the wet gel obtained under these conditions is composed of amorphous fine particles and does not exhibit remarkable photocatalytic properties. Therefore, when the reaction is carried out under pressure and heating, the hydrolysis reaction is completed within 48 hours, and a wet gel having crystals exhibiting excellent photocatalytic properties can be obtained. Moreover, the minimum of reaction time should just be 1 minute or more. A more desirable reaction time is 24 to 48 hours.
本発明において、ホルムアルデヒドおよび／またはジメチルホルムアミドを添加する理由は、ゲルを乾燥させる際の亀裂の生成を抑制するためである。これを添加しない場合では、基材にコーティング溶液を塗布・乾燥すると、被膜に微細な亀裂が生成して、基材に対する固着力が悪く、指で膜を擦るだけで容易に剥離する。しかし、ジメチルホルムアルデヒドの添加により、被膜の表面と内部の収縮の違いによる毛細管力を緩和して、亀裂の生成を抑制する。本発明では、この効果を目的として添加している。 In the present invention, the reason for adding formaldehyde and / or dimethylformamide is to suppress the formation of cracks when the gel is dried. In the case where this is not added, when the coating solution is applied to the substrate and dried, fine cracks are generated in the coating, and the adhesion to the substrate is poor, and the film is easily peeled off simply by rubbing the film with a finger. However, the addition of dimethylformaldehyde relieves the capillary force due to the difference in shrinkage between the surface and the inside of the coating, and suppresses the formation of cracks. In the present invention, this effect is added for the purpose.
有機溶媒には、エチルアルコール、メチルアルコール、プロピルアルコール異性体、ブチルアルコール異性体、メチルセルソルブ、エチルセルソルブ、ブチルセルソルブ等が挙げられる。また、チタンアルコキシドには、テトラメチルチタネート、テトライソプロピルチタネート、テトラノルマルブチルチタネート、テトラエトキシチタネート、テトラ２−エチルヘキシルチタネートなどが挙げられる。また、酸触媒には硝酸、塩酸等が挙げられ、この中でも硝酸が好ましい。アルカリ触媒は本発明のゾルゲル反応には好ましくない。 Examples of the organic solvent include ethyl alcohol, methyl alcohol, propyl alcohol isomer, butyl alcohol isomer, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Examples of the titanium alkoxide include tetramethyl titanate, tetraisopropyl titanate, tetranormal butyl titanate, tetraethoxy titanate, and tetra 2-ethylhexyl titanate. Moreover, nitric acid, hydrochloric acid, etc. are mentioned as an acid catalyst, Among these, nitric acid is preferable. Alkaline catalysts are not preferred for the sol-gel reaction of the present invention.
本実施形態における有機チタン化合物、酸触媒、乳酸及び有機溶媒の好ましい含有量について説明する。
まず、有機チタン化合物(ＴｉＯＲ4)の含有量は、６〜１５重量％の範囲、好ましくは
９〜１３重量％とすることが好ましい。有機チタン化合物としては、チタンテトライソプロポキシドが望ましい。有機チタン化合物としては、チタンアルコキシド、チタンアセトナトキレートなどが挙げられる。このうち、チタンイソプロポキシド、チタンプロポキシド、チタンエトキシドなどが好ましい。
The preferred contents of the organic titanium compound, acid catalyst, lactic acid and organic solvent in the present embodiment will be described.
First, the content of the organic titanium compound (TiOR 4 ) is in the range of 6 to 15% by weight, preferably 9 to 13% by weight. As the organic titanium compound, titanium tetraisopropoxide is desirable. Examples of the organic titanium compound include titanium alkoxide and titanium acetonato chelate. Of these, titanium isopropoxide, titanium propoxide, titanium ethoxide and the like are preferable.
６重量％から１５重量％の範囲で、４８時間以内に湿潤ゲルが得られ、これは有機溶媒に均一に分散する。溶液の寿命は１年以上であり、しかも得られる被膜は無色透明であり、基材に対する付着力も強固となる。なお多すぎると、酸触媒の入っている溶液にチタンイソプロポキシドを添加した途端に加水分解反応が進行し、湿潤ゲルを調製できない。また少なすぎると基材に対する付着性が低くなる。 In the range of 6% to 15% by weight, a wet gel is obtained within 48 hours, which is uniformly dispersed in the organic solvent. The lifetime of the solution is one year or more, and the obtained film is colorless and transparent, and the adhesion to the substrate is strong. If the amount is too large, the hydrolysis reaction proceeds as soon as titanium isopropoxide is added to the solution containing the acid catalyst, and a wet gel cannot be prepared. On the other hand, if the amount is too small, the adhesion to the substrate is lowered.
次に、酸触媒の含有量は１〜７重量％、好ましくは２〜５重量％の範囲にある。この範囲にあれば、４８時間以内でゲル化が終了し、得られた湿潤ゲルを有機溶媒に均一に分散
し、溶液の寿命は１年以上であった。１重量％未満では溶液のゲル化が容易に進行しなかった。また７重量％以上を添加した場合では、急激な加水分解が進行し、均一に分散するような湿潤ゲルを調製できない。
Next, the content of the acid catalyst is in the range of 1 to 7% by weight, preferably 2 to 5% by weight. Within this range, gelation was completed within 48 hours, and the obtained wet gel was uniformly dispersed in an organic solvent, and the lifetime of the solution was 1 year or longer. If it was less than 1% by weight, gelation of the solution did not easily proceed. In addition, when 7% by weight or more is added, rapid hydrolysis proceeds and a wet gel that uniformly disperses cannot be prepared.
また、酸触媒の濃度は、０.１mol/Lより少ない場合では、得られる被膜の光触媒特性は低く、酸濃度が１.５mol/Lより多い場合では、ゲル調製時で急激な加水分解が進行し、均一に分散する湿潤ゲルを調製できないことがある。 In addition, when the concentration of the acid catalyst is less than 0.1 mol / L, the photocatalytic property of the resulting film is low, and when the acid concentration is more than 1.5 mol / L, rapid hydrolysis proceeds during gel preparation. However, a wet gel that uniformly disperses may not be prepared.
従って、酸触媒が硝酸の場合、濃度が０.１mol/Lから１.５mol/L、好ましくは０．８〜１．２mol/Lであり、ゲル調製溶液に対して１重量％から７重量％の範囲内で含有させ得
ることが好ましい。
Therefore, when the acid catalyst is nitric acid, the concentration is from 0.1 mol / L to 1.5 mol / L, preferably from 0.8 to 1.2 mol / L, and from 1% to 7% by weight based on the gel preparation solution. It is preferable that it can be contained within the range.
本発明では、前記湿潤ゲル調製工程の後、
乳酸を０．５〜１０重量％の量で含む、2-エトキシエタノール、1-メトキシエタノール、2-プロパノールから選ばれる少なくとも１種の有機溶媒からなる溶液に、
得られた湿潤ゲルを溶解する工程(湿潤ゲル溶解工程)を行ってもよい。
In the present invention, after the wet gel preparation step,
In a solution comprising at least one organic solvent selected from 2-ethoxyethanol, 1-methoxyethanol and 2-propanol, containing lactic acid in an amount of 0.5 to 10% by weight,
You may perform the process (wet gel melt | dissolution process) of melt | dissolving the obtained wet gel.
このような湿潤ゲル溶解工程によって、透明なコーティングを形成することが可能となる。
また、乳酸は可視光透過型光触媒コーティング溶液の全量に対して、より望ましくは０．８〜１０重量％の範囲内で含有させることが好ましい。低級カルボン酸の量が０.５重
量％より少ないと、湿潤ゲルの均一な分散が困難となるおそれがある。また、低級カルボン酸の量が１０重量％より多いと、被膜の乾燥時間が著しく長時間になったり、プラスチック基材上にコートする場合には基材を溶解するおそれがある。
Such a wet gel dissolution process makes it possible to form a transparent coating.
In addition, lactic acid is preferably contained within a range of 0.8 to 10% by weight with respect to the total amount of the visible light transmissive photocatalyst coating solution. When the amount of the lower carboxylic acid is less than 0.5% by weight, uniform dispersion of the wet gel may be difficult. On the other hand, if the amount of the lower carboxylic acid is more than 10% by weight, the drying time of the film may become extremely long, or the base material may be dissolved when it is coated on a plastic base material.
また、有機溶媒は可視光透過型光触媒コーティング溶液に対して、６０重量％から８０重量％の範囲内で含有させることが好ましい。６０重量％より少ないと溶液中の湿潤ゲルの濃度が濃くなりすぎて、基材上に被膜を形成した際に亀裂や剥離が生じるおそれがある。一方、８０重量％より多いと溶液中の湿潤ゲルの濃度が薄くなり、基材上に被膜を形成した際の被膜の付着力が低下して容易に剥離するおそれがある。 The organic solvent is preferably contained in the range of 60% by weight to 80% by weight with respect to the visible light transmissive photocatalyst coating solution. If it is less than 60% by weight, the concentration of the wet gel in the solution becomes too high, and there is a possibility that cracking or peeling occurs when a film is formed on the substrate. On the other hand, when the amount is more than 80% by weight, the concentration of the wet gel in the solution becomes thin, and there is a possibility that the adhesion force of the film when the film is formed on the substrate is lowered and the film is easily peeled off.
本発明では、ゲル調製工程で、酸触媒を加えたのち、直ちに加圧下で１００〜２００℃の温度に加熱する。なお、「直ちに」とは、酸触媒を添加終了後、保持することなく直ぐに加熱することである。 In this invention, after adding an acid catalyst at a gel preparation process, it heats to the temperature of 100-200 degreeC under pressure immediately. Note that “immediately” means heating immediately after the addition of the acid catalyst, without being held.
本実施形態における湿潤ゲルの調製時の好ましい温度と時間について説明する。
湿潤ゲルの調製時の温度が、１００℃以下では得られた湿潤ゲルは図２に示すように非晶質であり、光触媒特性は認められたものの、その性能は著しく低い。１１０℃以上で得られた湿潤ゲルは図３に示すようにアナターゼ相であり、高い光触媒特性を示す。２００℃以上の場合、アナターゼ相の湿潤ゲルが得られたが、それを有機溶媒に均一に分散するには困難になるおそれがある。
A preferable temperature and time during preparation of the wet gel in the present embodiment will be described.
When the temperature at the time of preparation of the wet gel is 100 ° C. or less, the obtained wet gel is amorphous as shown in FIG. 2, and although the photocatalytic property is recognized, its performance is remarkably low. The wet gel obtained at 110 ° C. or higher has an anatase phase as shown in FIG. 3, and exhibits high photocatalytic properties. When the temperature is 200 ° C. or higher, an anatase-phase wet gel is obtained, but it may be difficult to uniformly disperse it in an organic solvent.
このためゲル調製時の温度は１１０℃から２００℃の温度範囲内とすることが好ましい。
湿潤ゲルの調製時の反応時間は、４８時間以内とすることが好ましい。４８時間以上の時間とすると、得られた湿潤ゲルを有機溶媒に均一に分散することが困難になり、被膜を形成した際に亀裂や剥離を生じるおそれがある。
For this reason, it is preferable to make the temperature at the time of gel preparation into the temperature range of 110 degreeC to 200 degreeC.
The reaction time during preparation of the wet gel is preferably within 48 hours. When the time is 48 hours or longer, it is difficult to uniformly disperse the obtained wet gel in an organic solvent, and there is a risk of cracking or peeling when a film is formed.
このような湿潤ゲル調製時の反応は、通常、加圧下で行われる。加圧は、大気圧よりも高い圧力となれば特に制限されるものではない。通常、このような加圧下での加熱はオー
トクレーブなどの耐圧加熱容器が使用される。
The reaction at the time of preparing such a wet gel is usually performed under pressure. The pressurization is not particularly limited as long as the pressure is higher than the atmospheric pressure. Usually, a pressure-resistant heating container such as an autoclave is used for heating under such pressure.
また、前記湿潤ゲル調製工程において、混合溶液に、あらかじめ、シリコンアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、チタンアルコキシド、ジルコニアアルコキシドから選ばれる少なくとも１種のアルコキシドを０．１〜１．０重量％の量で添加しておいてもよく、
さらに、湿潤ゲル溶解工程において、さらにシリコンアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、チタンアルコキシド、ジルコニアアルコキシドからなる群から選ばれる少なくとも１種のアルコキシド、および／または、
酸化チタン、二酸化ケイ素、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウムからなる群から選ばれる少なくとも１種の無機酸化物を、
０．１〜１０重量％、好ましくは０．８〜１．２重量％の量で添加してもよい。
In the wet gel preparation step, at least one alkoxide selected from silicon alkoxide, aluminum alkoxide, magnesium alkoxide, titanium alkoxide, and zirconia alkoxide is previously added to the mixed solution in an amount of 0.1 to 1.0% by weight. You can add it,
Further, in the wet gel dissolution step, at least one alkoxide selected from the group consisting of silicon alkoxide, aluminum alkoxide, magnesium alkoxide, titanium alkoxide, zirconia alkoxide, and / or
At least one inorganic oxide selected from the group consisting of titanium oxide, silicon dioxide, aluminum oxide, magnesium oxide, zirconium oxide,
It may be added in an amount of 0.1 to 10% by weight, preferably 0.8 to 1.2% by weight.
これによって、室温で塗布・乾燥すると基材に対するコーティング膜の付着力を著しく向上させることができる。
本発明のより具体的な実施態様としては、ゲル調製工程において、７０〜８５重量％の有機溶媒に、ホルムアルデヒドおよび／またはジメチルホルムアミドを１〜６重量％、酸触媒として０．１〜１．５モル／Ｌの硝酸水溶液を１〜３重量％加えた後、有機チタン化合物を５〜１５重量％の量で添加することがより望ましい。このような実施態様によれば、所望とする可視光透過型光触媒コーティング溶液を効率的に製造することができる。
Thereby, when applied and dried at room temperature, the adhesion of the coating film to the substrate can be remarkably improved.
As a more specific embodiment of the present invention, in the gel preparation step, 1 to 6% by weight of formaldehyde and / or dimethylformamide is added to 70 to 85% by weight of an organic solvent, and 0.1 to 1.5% as an acid catalyst. More preferably, the organic titanium compound is added in an amount of 5 to 15 wt% after adding 1 to 3 wt% of the mol / L nitric acid aqueous solution. According to such an embodiment, a desired visible light transmission type photocatalyst coating solution can be efficiently produced.
本発明に係る可視光透過型光触媒コーティング溶液は、上記した方法で製造される。
かかるコーティング溶液は、ポットライフが長く長期安定性に優れるとともに、基材への付着性が高く、さらには、可視光透過性が高く、光触媒機能も高い。
The visible light transmission type photocatalyst coating solution according to the present invention is produced by the method described above.
Such a coating solution has a long pot life and excellent long-term stability, high adhesion to a substrate, high visible light permeability, and high photocatalytic function.
次に、本実施形態における湿潤ゲルの生成相及び可視光透過型光触媒コーティング溶液を常温塗布させた被膜の各種の性能試験を行った。なお、以下の各実施例により本発明をさらに詳細に説明するが、本発明はこれに限定されない。 Next, various performance tests were performed on the coating phase in which the wet gel formation phase and the visible light transmission type photocatalyst coating solution were applied at room temperature in this embodiment. In addition, although the following each Example demonstrates this invention further in detail, this invention is not limited to this.
［実施例１］
本発明の実施例１の可視光透過型光触媒コーティング溶液は、以下のようにして調製した。２−プロパノール８２.７重量％に対してジメチルホルムアミドを５.０重量％及び０.１mol/Lの硝酸を２.５重量％加えた後、これを撹拌しながらチタンテトライソプロポキ
シド９.８重量％を加えた。この溶液を耐圧容器内に入れ、１２０℃で４８時間加熱して
湿潤ゲルを調製した。メチルセルソルブ６０.０重量％に対して乳酸６.７重量％を加えた後湿潤ゲル３３.３重量％を加えて超音波分散して、可視光透過型光触媒コーティング溶
液を調製した。
[Example 1]
The visible light transmission photocatalyst coating solution of Example 1 of the present invention was prepared as follows. After adding 5.0% by weight of dimethylformamide and 2.5% by weight of 0.1 mol / L nitric acid to 82.7% by weight of 2-propanol, 9.8% of titanium tetraisopropoxide was stirred with stirring. Weight percent was added. This solution was put in a pressure vessel and heated at 120 ° C. for 48 hours to prepare a wet gel. After adding 6.7% by weight of lactic acid to 60.0% by weight of methyl cellosolve, 33.3% by weight of wet gel was added and ultrasonically dispersed to prepare a visible light transmission type photocatalyst coating solution.
［実施例２］
本発明の実施例２の可視光透過型光触媒コーティング溶液は、以下のようにして調製した。２−プロパノール８２.６重量％に対してジメチルホルムアミドを５.０重量％及び０.１mol/Lの硝酸を２.５重量％加えた後、これを撹拌しながら、テトラエトキシシラン０.１重量％を加えて撹拌し、その後チタンテトライソプロポキシド９.８重量％を加えた。
この溶液を耐圧容器内に入れ、１２０℃で４８時間加熱して湿潤ゲルを調製した。メチルセルソルブ６７.５重量％に対して乳酸７.５重量％を加えた後湿潤ゲル２５.０重量％を
加えて超音波分散して、可視光透過型光触媒コーティング溶液を調製した。
[Example 2]
The visible light transmission type photocatalyst coating solution of Example 2 of the present invention was prepared as follows. After adding 5.0% by weight of dimethylformamide and 2.5% by weight of nitric acid of 0.1 mol / L to 82.6% by weight of 2-propanol, 0.1 wt. % And stirred, and then 9.8% by weight of titanium tetraisopropoxide was added.
This solution was put in a pressure vessel and heated at 120 ° C. for 48 hours to prepare a wet gel. After adding 7.5% by weight of lactic acid to 67.5% by weight of methyl cellosolve, 25.0% by weight of wet gel was added and ultrasonically dispersed to prepare a visible light transmitting photocatalyst coating solution.
［実施例３］
本発明の実施例３の可視光透過型光触媒コーティング溶液は、以下のようにして調製した。２−プロパノール８２.７重量％に対してジメチルホルムアミドを５.０重量％及び０
.１mol/Lの硝酸を２.５重量％加えた後、これを撹拌しながらチタンテトライソプロポキ
シド９.８重量％を加えた。この溶液を耐圧容器内に入れ、１２０℃で４８時間加熱して
湿潤ゲルを調製した。メチルセルソルブ６０.０重量％に対して乳酸６.７重量％を加えた後湿潤ゲル３３.３重量％を加えて超音波分散した。その後この溶液に対してテトラエト
キシラン５重量％加えて撹拌し、可視光透過型光触媒コーティング溶液を調製した。
[Example 3]
The visible light transmission type photocatalyst coating solution of Example 3 of the present invention was prepared as follows. 5.0% by weight and 0% by weight of dimethylformamide with respect to 82.7% by weight of 2-propanol
After adding 2.5% by weight of 0.1 mol / L nitric acid, 9.8% by weight of titanium tetraisopropoxide was added with stirring. This solution was put in a pressure vessel and heated at 120 ° C. for 48 hours to prepare a wet gel. After 6.7% by weight of lactic acid was added to 60.0% by weight of methyl cellosolve, 33.3% by weight of wet gel was added and ultrasonically dispersed. Thereafter, 5% by weight of tetraethoxylane was added to this solution and stirred to prepare a visible light transmitting photocatalyst coating solution.
『試験１：紫外線照射下におけるコーティング膜の色素分解試験』
各実施例のコーティング膜の光触媒特性を調べるために、紫外線照射(約1000μW/cm2)
下における１０mg/Lのメチレンブルー溶液の分解試験を行った。試料は可視光透過型光触媒コーティング溶液をシャーレ内側にコーティングし、乾燥後、それにメチレンブルー溶液を２０ml入れて暗室内で紫外線を２日間照射した。なお、対象試料として可視光透過型光触媒コーティング溶液をコーティングしないでメチレンブルー溶液を入れた試料も作製し、同様の試験を行った。
[Test 1: Decomposition test of coating film under UV irradiation]
In order to investigate the photocatalytic properties of the coating film of each example, ultraviolet irradiation (about 1000 μW / cm 2 )
The degradation test of the 10 mg / L methylene blue solution below was performed. The sample was coated with a visible light transmissive photocatalyst coating solution on the inside of the petri dish, dried, and 20 ml of methylene blue solution was added thereto and irradiated with ultraviolet rays in a dark room for 2 days. In addition, the sample which put the methylene blue solution without coating visible light transmission type photocatalyst coating solution as an object sample was also produced, and the same test was done.
以上のような試験について、実施例１から実施例３で調製したコーティング溶液について評価し、その結果を表１に示す。 About the above tests, the coating solutions prepared in Example 1 to Example 3 were evaluated, and the results are shown in Table 1.
可視光透過型光触媒コーティング溶液をシャーレ内側にコーティングし、乾燥後、それにメチレンブルー溶液を２０ml入れて暗室内で紫外線を２日間照射した結果、表１に示すように実施例１〜３のいずれにおいてもメチレンブルーはほとんど分解された。これに対して、可視光透過型光触媒コーティング溶液をコーティングしていない試料では、メチレンブルーの分解は全く認められなかった。これより、本発明によって作製したコーティング膜は極めて優れた光触媒特性を示した。 A visible light transmission type photocatalyst coating solution was coated on the inside of the petri dish, and after drying, 20 ml of methylene blue solution was added thereto and irradiated with ultraviolet rays for 2 days in a dark room. Methylene blue was almost decomposed. On the other hand, no decomposition of methylene blue was observed in the sample not coated with the visible light transmission type photocatalyst coating solution. From this, the coating film produced by this invention showed the very outstanding photocatalytic characteristic.
また、実施例１の試料について、紫外線照射した場合の試験液の青色を、吸光度計を用いて測定した結果、図４に示すように照射時間の増加に伴って吸光度は急激に減少し、２日間の照射によりほとんどのメチレンブルーが分解された。 In addition, as a result of measuring the blue color of the test solution when irradiated with ultraviolet rays for the sample of Example 1 using an absorptiometer, the absorbance rapidly decreased as the irradiation time increased as shown in FIG. Most of the methylene blue was decomposed by daily irradiation.
『試験２：可視光透過型光触媒コーティング溶液から作製したコーティング膜の光透過
率の測定』
各実施例の可視光透過型光触媒コーティング溶液をコーティングした試料の光透過性を調べるために、近紫外〜近赤外領域おける光透過率を測定した。試料は、石英ガラス上に可視光透過型光触媒コーティング溶液をコーティングし、乾燥後、紫外・可視分光光度計を用いて、２００nm〜２０００nmの波長領域で光透過率を測定した。
“Test 2: Measurement of light transmittance of coating film prepared from visible light transmissive photocatalyst coating solution”
In order to examine the light transmittance of the sample coated with the visible light transmissive photocatalyst coating solution of each example, the light transmittance in the near ultraviolet to near infrared region was measured. The sample was coated with a visible light transmission photocatalyst coating solution on quartz glass, dried, and then measured for light transmittance in a wavelength region of 200 nm to 2000 nm using an ultraviolet / visible spectrophotometer.
以上のような試験の結果、いずれの実施例で作製したコーティング膜においても、図５に示すように可視光領域(４００nm〜８００nm)において、８０％以上の透過率を有しており、十分に透明であることが明らかとなった。 As a result of the test as described above, the coating film produced in any of the examples has a transmittance of 80% or more in the visible light region (400 nm to 800 nm) as shown in FIG. It became clear that it was transparent.
『試験３：可視光透過型光触媒コーティング溶液から作製したコーティング膜の基材に対する固着力の測定』
各実施例のコーティング膜の基材に対する固着力を調べるために、１０mg/Lのメチレンブルー溶液２０ml入れたシャーレ中に、可視光透過型光触媒コーティング溶液をコーティングして乾燥したスライドカラスを浸漬し、１週間ガラス紫外線照射(約1000μW/cm2)し
た。時間の経過に伴ってスライドガラスからコーティング膜が剥離しないかどうかを観察した。
"Test 3: Measurement of adhesion strength of coating film prepared from visible light transmissive photocatalyst coating solution to substrate"
In order to investigate the adhesion of the coating film of each example to the substrate, a slide crow coated with a visible light transmission type photocatalyst coating solution and immersed in a petri dish containing 20 ml of a 10 mg / L methylene blue solution was immersed in 1 Weekly glass UV irradiation (approximately 1000 μW / cm 2 ). It was observed whether or not the coating film was peeled off from the slide glass with time.
以上のような試験について、実施例１から実施例３の結果を表２に示す。 Table 2 shows the results of Examples 1 to 3 for the above tests.
実施例１においては、スライドカラスからコーティング膜の一部の剥離が認められたが、実施例２及び３においては１週間メチレンブルー中に浸漬してもコーティング膜の剥離は認められなかった。 In Example 1, peeling of a part of the coating film was observed from the slide crow, but in Examples 2 and 3, peeling of the coating film was not observed even when immersed in methylene blue for one week.
［比較例１］
特開２００１−２６２００８号公報実施例の記載に基づいて、テトライソプロポキシドを用い、チタンと水との比が1：４となるように調製し、１４０℃で１日間のゲル化条件
で湿潤ゲルを調製した。得られたアナターゼ型酸化チタンを２重量％となるように、2-メトキシエタノールに分散させ、２時間超音波照射して、コーティング溶液を調製した。
[Comparative Example 1]
JP-A-2001-262008 Based on the description in the examples, tetraisopropoxide was used so that the ratio of titanium to water was 1: 4, and it was wetted at 140 ° C. for 1 day under gel conditions. A gel was prepared. The obtained anatase-type titanium oxide was dispersed in 2-methoxyethanol so as to be 2% by weight, and subjected to ultrasonic irradiation for 2 hours to prepare a coating solution.
また対照として、前記実施例１のコーティング溶液と対比した。
溶液の分散状態を観察したところ、比較例のものは１週間で完全に沈降したが、実施例
１のものは高い分散状態を保っていた。
As a control, it was compared with the coating solution of Example 1.
When the dispersion state of the solution was observed, the comparative example completely settled in one week, but the example 1 maintained a high dispersion state.
また、上記コーティング溶液を、ガラス基板上に200ｎｍの厚さとなるように塗布した
後、乾燥したところ、比較例１のコーティング溶液を用いて形成したコーティングは、白濁しており、また厚さムラも大きかったが、実施例１のコーティング溶液を用いて形成したコーティングは透明性が高く、また厚さのムラもなかった。
In addition, when the coating solution was applied on a glass substrate so as to have a thickness of 200 nm and then dried, the coating formed using the coating solution of Comparative Example 1 was cloudy and had uneven thickness. Although it was large, the coating formed using the coating solution of Example 1 had high transparency and no uneven thickness.
さらに、得られたガラス基板上のコーティングを１０ｍｇ／ｌのメチレンブルー溶液２０ｍｌに浸漬し(試料の塗布面積は２．７×２．５ｃｍ)、表面をサランラップ(登録商標)で覆ったのち、ブラックライト下で、吸光度の変化を観察した。 Further, the obtained coating on the glass substrate was immersed in 20 ml of a 10 mg / l methylene blue solution (the coating area of the sample was 2.7 × 2.5 cm), and the surface was covered with Saran Wrap (registered trademark), and then the black light Below, the change in absorbance was observed.
結果を表３に示す。 The results are shown in Table 3.
表３より、実施例１のものは、比較例１とくらべて、吸光度の低下が大きく、光触媒機能が高いことが判明した。
以上のような各試験結果より、本発明により可視光透過型光触媒コーティング溶液を基材にコーティングすることで透明かつ光触媒特性を基材に容易に付与することができる。とくに、可視光透過型光触媒コーティング溶液を調製する際に、種々の金属アルコキシドやゾルを添加することで、その基材への固着力は向上する。
From Table 3, it was found that Example 1 had a greater decrease in absorbance and higher photocatalytic function than Comparative Example 1.
From the above test results, it is possible to easily impart transparent and photocatalytic properties to a substrate by coating the substrate with a visible light transmissive photocatalyst coating solution according to the present invention. In particular, when preparing a visible light transmissive photocatalyst coating solution, the adhesion to the substrate is improved by adding various metal alkoxides and sols.
なお、本発明に係る可視光透過型光触媒コーティング溶液を製造方法及びこれによる溶液は、前述した実施形態に限定されるものではなく、適宜変更することができる。 In addition, the manufacturing method of the visible light transmission type photocatalyst coating solution which concerns on this invention, and the solution by this are not limited to embodiment mentioned above, It can change suitably.
Claims (5)
化合物、およびホルムアルデヒドおよび／またはジメチルホルムアミドとを混合した混合溶液に、
酸触媒を加えたのち、直ちに加圧下で１００〜２００℃の温度に加熱し、１分から４８時間反応させてアナターゼ型酸化チタンを含む湿潤ゲルを調製する工程(湿潤ゲル調製工
程)、
前記湿潤ゲル調製工程の後、乳酸を０．５〜１０重量％の量で含む、2-エトキシエタノール、1-メトキシエタノール、2-プロパノールから選ばれる少なくとも１種の有機溶媒からなる溶液に、得られた湿潤ゲルを溶解する工程(湿潤ゲル溶解工程)
を含むことを特徴とする可視光透過型光触媒コーティング溶液の製造方法。 In a mixed solution in which an organotitanium compound represented by Ti (OR) 4 [R is independently of each other and a hydrocarbon group having 1 to 6 carbon atoms] and formaldehyde and / or dimethylformamide are mixed,
Immediately after adding the acid catalyst, heating to 100-200 ° C. under pressure and reacting for 1 minute to 48 hours to prepare a wet gel containing anatase-type titanium oxide (wet gel preparation step),
After the wet gel preparation step, a solution comprising at least one organic solvent selected from 2-ethoxyethanol, 1-methoxyethanol and 2-propanol containing lactic acid in an amount of 0.5 to 10% by weight is obtained. Step of dissolving the wet gel (wet gel dissolution step)
A method for producing a visible light transmissive photocatalyst coating solution, comprising:
混合溶液に、あらかじめ、シリコンアルコキシド、アルミニウムアルコキシド、マグネシウムアルコキシド、チタンアルコキシド、ジルコニアアルコキシドから選ばれる少なくとも１種のアルコキシドを０．１〜１．０重量％の量で添加する請求項１に記載の可視光透過型光触媒コーティング溶液の製造方法。 In the wet gel preparation step,
The visible solution according to claim 1, wherein at least one alkoxide selected from silicon alkoxide, aluminum alkoxide, magnesium alkoxide, titanium alkoxide, and zirconia alkoxide is added to the mixed solution in an amount of 0.1 to 1.0% by weight. A method for producing a light transmissive photocatalytic coating solution.
たはジメチルホルムアミドを１〜６重量％、酸触媒として０．１〜１．５モル／Ｌの硝酸水溶液を１〜３重量％加えた後、有機チタン化合物を５〜１５重量％の量で添加することを特徴とする請求項１〜３のいずれかに記載の可視光透過型光触媒コーティング溶液の製造方法。 In the gel preparation step, 70 to 85% by weight of organic solvent is 1 to 6% by weight of formaldehyde and / or dimethylformamide, and 1 to 3% by weight of 0.1 to 1.5 mol / L nitric acid aqueous solution as an acid catalyst. The method for producing a visible light transmissive photocatalyst coating solution according to any one of claims 1 to 3, wherein the organic titanium compound is added in an amount of 5 to 15 wt% after the addition.
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