JP2016168587A - Anatase type titanium oxide-containing composite film for interior use - Google Patents
Anatase type titanium oxide-containing composite film for interior use Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000011941 photocatalyst Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 150000003057 platinum Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 65
- 239000002253 acid Substances 0.000 abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 29
- 239000001301 oxygen Substances 0.000 abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 abstract description 29
- 238000001035 drying Methods 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
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- 238000002156 mixing Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 32
- 239000007864 aqueous solution Substances 0.000 description 26
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 230000000844 anti-bacterial effect Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000843 anti-fungal effect Effects 0.000 description 3
- 230000000840 anti-viral effect Effects 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009545 invasion Effects 0.000 description 3
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- -1 tetrafluoroborates Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000280258 Dyschoriste linearis Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
本発明は、アナターゼ型酸化チタンを含有する内装用複合膜に係り、より詳しくは、光触媒活性及び抗菌活性に優れ、膜形成能が高く、内装面との密着性が強く、塗装が容易で、且つ光化学反応によって生成する活性酸素による内壁面への侵襲が軽減された、アナターゼ型酸化チタンを含有する内装用複合膜に関する。 The present invention relates to an interior composite film containing anatase-type titanium oxide, more specifically, excellent photocatalytic activity and antibacterial activity, high film-forming ability, strong adhesion to the interior surface, easy to paint, The present invention also relates to an interior composite film containing anatase-type titanium oxide in which invasion to an inner wall surface by active oxygen generated by a photochemical reaction is reduced.
酸化チタンは、アナターゼ型とルチル型の結晶型を有する。この中、アナターゼ型酸化チタンは、光化学反応の触媒活性を有し、光の照射を受けて空気中の酸素を活性化して活性酸素を生成する。生成した活性酸素は、強力な酸化作用を示して種々の物体を酸化分解すると共に、強力な抗菌作用を有することが知られている（例えば、特許文献１、２を参照）。 Titanium oxide has anatase and rutile crystal forms. Among these, anatase-type titanium oxide has catalytic activity for photochemical reaction, and activates oxygen in the air upon irradiation with light to generate active oxygen. The generated active oxygen is known to have a strong antibacterial action as well as exhibiting a strong oxidizing action to oxidize and decompose various objects (see, for example, Patent Documents 1 and 2).
例えば、ガラスの表面に形成されたアナターゼ型酸化チタン膜は、光を受けると活性酸素を発生させてガラスの表面に付着した汚染物を分解除去する。汚染物が除去されたガラスは、本来の親水性をとり戻すので（親水化作用）、表面に付着した水が水玉にならずに広がって曇りを生じない（防曇効果）。アナターゼ型酸化チタン被膜は、この作用を利用して自動車ミラーや交通標識の表面に塗布されている。 For example, an anatase-type titanium oxide film formed on the glass surface generates active oxygen when receiving light, and decomposes and removes contaminants attached to the glass surface. Since the glass from which contaminants have been removed regains its original hydrophilicity (hydrophilization effect), the water adhering to the surface spreads without becoming polka dots and does not cause fogging (antifogging effect). Anatase-type titanium oxide coating is applied to the surface of automobile mirrors and traffic signs using this action.
また、アナターゼ型酸化チタン被膜は、付着した汚染物質を酸化分解すると共に、親水化作用によって雨水を付着面に浸みこませて汚染物質を洗い流すという自己洗浄作用を有する。
更に、光触媒皮膜から生成される活性酸素は、窒素酸化物（ＮＯＸ）や悪臭物質のような気体を酸化分解するので、アナターゼ型酸化チタン被膜が、高速道路の防音壁や家電製品などの空気清浄、脱臭作用等に用いられている。
The anatase-type titanium oxide film has a self-cleaning action of oxidatively decomposing adhering contaminants and washing away the contaminants by allowing rainwater to soak into the adhering surface by a hydrophilic action.
Furthermore, active oxygen generated from the photocatalytic coating oxidizes and decomposes gases such as nitrogen oxides (NOX) and malodorous substances, so the anatase-type titanium oxide coating is used to clean air barriers such as soundproof walls on highways and home appliances. It is used for deodorizing action.
このように、光触媒の有用性は広く認められており、平成２１年度の特許出願技術動向調査報告書によれば、当時の光触媒膜関連産業のグローバル市場規模は一千億円であって、将来的な潜在的な市場規模は、２兆８１千億円と見積もられていた（非特許文献１参照）が、市場規模は、まだここまで広がっていない。
このように巨大な潜在市場を開拓するための課題の一つとして、大量生産可能で、安価で、高熱処理を必要としないアナターゼ型酸化チタン被膜の製造方法の確立が要望されている。
In this way, the usefulness of photocatalysts is widely recognized. According to the patent application technology trend survey report in 2009, the global market scale of the photocatalyst film-related industry at that time was 100 billion yen, The potential market size was estimated to be 2,810.0 billion yen (see Non-Patent Document 1), but the market size has not yet expanded.
As one of the challenges for developing such a huge potential market, establishment of a method for producing an anatase-type titanium oxide coating that can be mass-produced, is inexpensive, and does not require high heat treatment is desired.
アナターゼ型酸化チタン被膜の形成方法は、酸化チタン粉体スラリーあるいは塩化チタンや硫酸チタンの水溶液を基体に塗布して焼成する塗布法、金属アルコキシドの加水分解で作製したゾルを基体に塗布して焼成するゾルゲル法、高真空中で酸化物のターゲットをスパッタリングし基体上に成膜するスパッタリング法、有機金属化合物やハロゲン化物を揮発させ加熱炉の中で分解して基体上に膜を作製するＣＶＤ法、固体粒子を大気中で発生させたプラズマ中で溶融し基体表面に照射するプラズマ溶射等がある。 The anatase-type titanium oxide coating is formed by applying a titanium oxide powder slurry or an aqueous solution of titanium chloride or titanium sulfate to the substrate and baking, or applying a sol produced by hydrolysis of metal alkoxide to the substrate and baking. Sol-gel method, sputtering method in which an oxide target is sputtered in a high vacuum to form a film on a substrate, and CVD method in which an organic metal compound or halide is volatilized and decomposed in a heating furnace to form a film on the substrate In addition, there is plasma spraying in which solid particles are melted in plasma generated in the atmosphere and irradiated on the surface of the substrate.
このうち、塗布法とゾルゲル法とが簡便で実用性が高いとされている。
しかし塗布法は、アナターゼ型酸化チタン膜の形成には数百度以上の温度を必要とするために、基体は高温に耐えるものに限られるという問題点があるし、ゾルゲル法も、原料ゾル中に酸や有機物質を焼成除去するのに４００℃以上の加熱が必要であるという同様の問題点を有する。
Among these, the coating method and the sol-gel method are simple and highly practical.
However, since the coating method requires a temperature of several hundred degrees or more to form the anatase-type titanium oxide film, there is a problem that the substrate is limited to one that can withstand high temperatures. There is a similar problem that heating at 400 ° C. or higher is necessary to remove the acid or organic substance by baking.
更に、光触媒から放出される活性酸素は、基体も侵襲してしまうという問題点がある。即ち、ガラス、金属、及びコンクリートのように、活性酸素に侵襲されない基体の上には光触媒膜を形成することができるが、例えばペイント塗装面のように、活性酸素に侵襲される基体の上に光触媒を塗布すると、汚染物と共に基体が侵襲され、基体の劣化が促進されてしまう。このために、活性酸素に分解される基体の表面にアナターゼ型酸化チタン膜を形成するためには、活性酸素を遮断するアンダーコートが必要である。しかし、そのようなアンダーコート材料は、種類が限定されているし、多くは形成するのに高温が必要である。
更に光触媒は、光のない、若しくは光の弱い場所では、十分な活性を発揮することができないが、抗菌活性に関しては、特に暗所には菌が繁殖しやすいという問題がある。
Furthermore, there is a problem that the active oxygen released from the photocatalyst also invades the substrate. That is, a photocatalytic film can be formed on a substrate that is not invaded by active oxygen, such as glass, metal, and concrete, but it can be formed on a substrate that is invaded by active oxygen, such as a painted surface. When the photocatalyst is applied, the substrate is invaded with contaminants, and the deterioration of the substrate is promoted. For this reason, in order to form an anatase-type titanium oxide film on the surface of a substrate that is decomposed into active oxygen, an undercoat that blocks active oxygen is required. However, such undercoat materials are limited in type and many require high temperatures to form.
Further, the photocatalyst cannot exhibit sufficient activity in a place where there is no light or light, but there is a problem that bacteria are likely to propagate particularly in a dark place with respect to the antibacterial activity.
近年、ペルオキソチタン酸水和物の水溶液を加熱することによってアナターゼ型酸化チタンが得られ、可視光に対しても光触媒活性を有する光触媒膜の形成が可能であることが開示されている（例えば、特許文献３、４を参照）。しかし、この方法で製造したアナターゼ型酸化チタン膜は、密着性が十分ではないという問題点を有する。また、光触媒によって生成される活性酸素の、基材に対する侵襲を防ぐためにはアンダーコートが必要であるという光触媒に共通の問題は解決されていない。 In recent years, it has been disclosed that anatase-type titanium oxide can be obtained by heating an aqueous solution of peroxotitanic acid hydrate, and that a photocatalytic film having photocatalytic activity even for visible light can be formed (for example, (See Patent Documents 3 and 4). However, the anatase-type titanium oxide film produced by this method has a problem that adhesion is not sufficient. Moreover, the common problem of the photocatalyst that an undercoat is necessary to prevent the active oxygen produced by the photocatalyst from invading the base material has not been solved.
本発明は、上記のような問題を解決するためになされたものであって、本発明の課題は、可視光や弱い光線であっても、光触媒活性を有して活性酸素を生成し、自己洗浄作用を有すると共に、内装面に対する活性酸素の侵襲を効果的に遮蔽するアナターゼ型酸化チタンを含有する内装用複合膜を提供することにある。 The present invention has been made to solve the above-described problems, and the object of the present invention is to generate active oxygen having photocatalytic activity even in the case of visible light or weak light, and An object of the present invention is to provide an interior composite film containing anatase-type titanium oxide which has a cleaning action and effectively shields active oxygen from invading the interior surface.
また本発明は、光照射時に光触媒によって生成された活性酸素による強い抗菌作用を示すと共に、暗所においても強い抗菌活性を有するナターゼ型酸化チタンを含有する内装用複合膜を提供することを課題とする。
更に本発明は、成膜性及び密着性が良く、触媒効率が高く、製造方法が容易であって安価なアナターゼ型酸化チタンを含有する内装用複合膜及びその製造方法を提供することを課題とする。
Another object of the present invention is to provide an interior composite film containing nathase-type titanium oxide that exhibits a strong antibacterial action due to active oxygen generated by a photocatalyst during light irradiation and has a strong antibacterial activity even in the dark. To do.
Furthermore, it is an object of the present invention to provide an interior composite film containing anatase-type titanium oxide, which has good film formability and adhesion, has high catalyst efficiency, is easy to manufacture and is inexpensive, and a method for manufacturing the same. To do.
かかる課題を解決するための本発明のアナターゼ型酸化チタンを含有する内装用複合膜は、建築物の内装面に形成非結晶性の酸化チタン層と、該非結晶性の酸化チタン層上に形成された貴金属の塩又はナノコロイドを含むアナターゼ型酸化チタン層と、を有し、貴金属の塩又はナノコロイドの含有量は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、アナターゼ型酸化チタンの重量を１００重量部とした場合に、１×１０−１乃至１×１０−８重量部の範囲内であることを特徴とする。 To solve this problem, an interior composite film containing anatase-type titanium oxide of the present invention is formed on a non-crystalline titanium oxide layer formed on an interior surface of a building, and on the non-crystalline titanium oxide layer. An anatase-type titanium oxide layer containing a noble metal salt or nanocolloid, and the content of the noble metal salt or nanocolloid is calculated by converting the weight of the noble metal salt or nanocolloid into the weight of the metal, and anatase type oxidation. When the weight of titanium is 100 parts by weight, it is in the range of 1 × 10 −1 to 1 × 10 −8 parts by weight.
本発明は、非結晶性の酸化チタン層の重量と、アナターゼ型酸化チタン層の重量と、の比が、１０：１乃至１：１０の範囲内であることが好ましい。
また本発明は、貴金属の塩又はナノコロイドが、銅、銀、金、及び白金の塩又はナノコロイドからなる群のうちの１以上であることを特徴とする。
In the present invention, the ratio of the weight of the amorphous titanium oxide layer to the weight of the anatase-type titanium oxide layer is preferably in the range of 10: 1 to 1:10.
Further, the present invention is characterized in that the noble metal salt or nanocolloid is one or more of the group consisting of a salt or nanocolloid of copper, silver, gold, and platinum.
更に本発明は、内装面が建造物内部の壁、天井、床、仕切部材、家具、及び照明器具を含むことができる。 In the present invention, the interior surface can include a wall, a ceiling, a floor, a partition member, furniture, and a lighting fixture inside the building.
本発明のアナターゼ型酸化チタンを含有する内装用複合膜は、チタン原料と過酸化水素水とからＡ液（ペルオキソチタン酸水溶液）を製造し、Ａ液を７０乃至２００℃で加熱して製造したアナターゼ型酸化チタン分散液に貴金属を加えてＢ液とし、内装面にＡ液を塗布し乾燥させた上に、Ｂ液を塗布し乾燥させて容易かつ安価に製造することができる。Ａ液を加熱してＢ液を製造する温度も、ゾル・ゲル法や酸化チタン塗布法よりはるかに低温で製造することができる。 The composite film for interior containing the anatase type titanium oxide of the present invention was produced by producing A liquid (peroxotitanic acid aqueous solution) from a titanium raw material and hydrogen peroxide solution, and heating the A liquid at 70 to 200 ° C. A noble metal is added to the anatase-type titanium oxide dispersion to obtain a B liquid. The A liquid is applied to the interior surface and dried, and then the B liquid is applied and dried to be easily and inexpensively manufactured. The temperature at which the A liquid is heated to produce the B liquid can also be produced at a much lower temperature than the sol-gel method or the titanium oxide coating method.
また本発明は、Ａ液を塗布し乾燥した上にＢ液を塗布し乾燥して形成することができ、Ｂ液から形成されたアナターゼ型酸化チタン層が、高い光触媒活性を有し、可視光や弱い光線であっても、光の照射を受けて光化学活性触媒機能を示し、活性酸素を生成して強い自己浄化作用及び強い抗菌、抗カビ、抗ウイルス活性を有すると共に、消臭作用、及びホルムアルデヒド分解作用を示した。
また、Ｂ液に含まれた貴金属が、暗所においても強い抗菌、抗カビ、抗ウィルス活性を示し、暗所では抗菌活性を示さない光触媒の弱点を補った。
In addition, the present invention can be formed by applying and drying the A liquid and then applying the B liquid and drying, and the anatase-type titanium oxide layer formed from the B liquid has a high photocatalytic activity and is visible light. Even with weak light, it exhibits photochemically active catalytic function upon irradiation with light, generates active oxygen and has strong self-purifying action and strong antibacterial, antifungal and antiviral activities, and deodorizing action, and It showed formaldehyde decomposition action.
Further, the noble metal contained in the liquid B compensated for the weak point of the photocatalyst that showed strong antibacterial, antifungal and antiviral activities even in the dark and did not show the antibacterial activity in the dark.
更に本発明のＡ液を塗布後乾燥することによって形成された非結晶性の酸化チタン層は、種々の基体と膜形成性及び接着性の良い高密度の膜を形成すると共に、アナターゼ型酸化チタン分散液（Ｂ液）から形成されたアナターゼ型酸化チタン層とも良好な接着性を有し、アナターゼ型酸化チタン層の接着性の不足を補うと共に、光触媒反応で生成された活性酸素に対する良好なアンダーコート層の作用を示した。 Further, the non-crystalline titanium oxide layer formed by applying and drying the liquid A of the present invention forms a high-density film having various film forming properties and good adhesiveness with anatase type titanium oxide. The anatase-type titanium oxide layer formed from the dispersion liquid (liquid B) also has good adhesiveness, compensates for the lack of adhesiveness of the anatase-type titanium oxide layer, and is excellent under active oxygen generated by the photocatalytic reaction The effect of the coating layer was shown.
以下に、本発明の実施形態に係るアナターゼ型酸化チタンを含有する内装用複合膜およびその製造方法を詳しく説明する。
本発明は、アナターゼ型酸化チタンを含有する内装用複合膜に関する。ここで、内装とは、建築物の内面に設けられた装備・部材であれば特に制限されないが、例えば壁、天井、床、扉、間仕切り、家具、照明器具、調理台、浴室、及び便所等を含むことができる。
Below, the composite film for interiors containing the anatase type titanium oxide which concerns on embodiment of this invention, and its manufacturing method are demonstrated in detail.
The present invention relates to an interior composite film containing anatase-type titanium oxide. Here, the interior is not particularly limited as long as it is equipment / members provided on the inner surface of the building. For example, walls, ceilings, floors, doors, partitions, furniture, lighting fixtures, cooking tables, bathrooms, toilets, etc. Can be included.
建築物の内装は、一般的に、外装のように厳しい外気条件には曝されることはなく、塗膜の強度はそれほど要求されないものの、より美麗さを要求され、また基材として活性酸素の侵襲を受けやすい材料が多く用いられるので、その対策が必要である。更に、建築物の内部は、受ける光の量が外装より少ないので、より高い光触媒活性を有する酸化チタン複合膜が要求される。内装で処理するべき汚染物としては、通常の汚染物のほかに、悪臭、ホルムアルデヒド、煙草の煙などがあり、また抗菌活性、特に暗所での強い抗菌活性が要求される。 The interior of a building is generally not exposed to harsh outside air conditions like the exterior, and the coating film strength is not so much required, but it is required to be more beautiful, and the active oxygen as a base material is not required. Since many materials that are susceptible to invasion are used, countermeasures are necessary. Furthermore, since the amount of light received inside the building is less than that of the exterior, a titanium oxide composite film having higher photocatalytic activity is required. Contaminants to be treated in the interior include normal odor, malodor, formaldehyde, cigarette smoke and the like, and antibacterial activity, particularly strong antibacterial activity in the dark, is required.
このため、本発明のアナターゼ型酸化チタンを含有する内装用複合膜は、ペルオキソチタン酸水溶液をＡ液とし、Ａ液を７０乃至２００℃で加熱して製造したアナターゼ型酸化チタン分散液に貴金属を加えてＢ液とし、内装面の基材にＡ液を塗布し乾燥させて膜性及び接着性の良いアンダーコート層を形成させて基材と光触媒層を接着させると共に、活性酸素から基材を保護し、その上にＢ液を塗布し乾燥させて、アナターゼ型酸化チタン及び貴金属を含有し光触媒作用及び殺菌作用を有する内装用複合膜を形成した。 For this reason, the composite film for interior containing the anatase-type titanium oxide of the present invention is prepared by adding a noble metal to an anatase-type titanium oxide dispersion prepared by heating an A-peroxide titanic acid aqueous solution A and heating the solution A at 70 to 200 ° C. In addition, as the B liquid, the A liquid is applied to the base material on the interior surface and dried to form an undercoat layer having good film properties and adhesiveness to adhere the base material and the photocatalyst layer, and the base material is removed from the active oxygen. It was protected, and the B liquid was applied thereon and dried to form an interior composite film containing anatase-type titanium oxide and a noble metal and having a photocatalytic action and a bactericidal action.
（ペルオキソチタン酸水溶液の製造）
本発明で、Ａ液として用いるペルオキソチタン酸水溶液は、本発明の実施に支障のないものであれば、何れの方法によって製造したものでも使用することができる。
特許文献５に記載されているように、チタン原料含有水溶液に、反応当量より過剰の水酸化水素水を加え、次いでアンモニア水を加えて中和し、得られた黄色溶液を放置してペルオキソチタン酸塩を沈殿させ、沈殿をろ取・洗浄し、水に懸濁させて過酸化水素水を加えると、黄色透明なペルオキソチタン酸水溶液（Ａ液）が得られる。塗布され、乾燥されたＡ液は、ペルオキソ基を有する非晶質の固体を形成する。
(Production of peroxotitanic acid aqueous solution)
In the present invention, the peroxotitanic acid aqueous solution used as the liquid A can be produced by any method as long as it does not hinder the practice of the present invention.
As described in Patent Document 5, an aqueous solution of titanium raw material containing hydrogen hydroxide water in excess of the reaction equivalent is added, and then neutralized by adding aqueous ammonia, and the resulting yellow solution is left to stand for peroxotitanium. The acid salt is precipitated, the precipitate is collected by filtration, washed, suspended in water and added with aqueous hydrogen peroxide to obtain a yellow transparent aqueous peroxotitanic acid solution (solution A). The applied and dried liquid A forms an amorphous solid having a peroxo group.
また、特許文献６に記載されているように、チタン原料含有水溶液にアルカリ成分を加えて生成させた水酸化チタンゲルを、沈殿形成に用いた物質が検出されなくなるまで十分に水洗して用いることができる。沈殿形成に用いた物質が残存していると、製造したペルオキソチタン酸水溶液（Ａ液）及び時段階のアナターゼ型酸化チタン分散液の凝集が起こり、生成したアナターゼ型酸化チタン分散液の酸化チタン粒子の大きさが大きくなって、塗布剤が不安定になり、密着性あるいは密度が劣る場合があった。得られた水酸化チタンゲルに、過酸化水素水を加えて一夜反応させると、黄色粘調液体のペルオキソチタン酸水溶液（Ａ液）が得られる。
このほか、種々のペルオキソチタン酸水溶液（Ａ液）の製造方法が特許文献７に記載されている。
Further, as described in Patent Document 6, the titanium hydroxide gel produced by adding an alkali component to a titanium raw material-containing aqueous solution should be sufficiently washed with water until the substance used for precipitation formation is no longer detected. it can. If the substance used for the formation of the precipitate remains, aggregation of the produced peroxotitanic acid aqueous solution (liquid A) and the anatase-type titanium oxide dispersion liquid occurs, and titanium oxide particles of the produced anatase-type titanium oxide dispersion liquid In some cases, the size of the coating becomes large, the coating agent becomes unstable, and the adhesion or density is inferior. When the resulting titanium hydroxide gel is added with a hydrogen peroxide solution and allowed to react overnight, a yellow viscous liquid peroxotitanic acid aqueous solution (A solution) is obtained.
In addition, Patent Document 7 describes a method for producing various peroxotitanic acid aqueous solutions (solution A).
ペルオキソチタン酸水溶液（Ａ液）の濃度は、Ａ液の重量を１００重量部とした場合に、ペルオキソチタン酸を酸化チタンに換算した重量が０．１乃至１０重量部であることが好ましい。ペルオキソチタン酸の酸化チタン重量に換算した含有量が０．１重量部以下では十分な厚さのアンダーコート層を形成することができないことがあり、１０重量部以上では、ペルオキソチタン酸水溶液の粘度が増加して取り扱いが困難になる場合がある。 The concentration of the aqueous solution of peroxotitanic acid (liquid A) is preferably 0.1 to 10 parts by weight when the weight of liquid A is 100 parts by weight and the weight of peroxotitanic acid converted to titanium oxide. If the content of peroxotitanic acid in terms of titanium oxide weight is 0.1 parts by weight or less, a sufficiently thick undercoat layer may not be formed. If it is 10 parts by weight or more, the viscosity of the peroxotitanic acid aqueous solution May be difficult to handle.
（アナターゼ型酸化チタン分散液の製造）
ペルオキソチタン酸水溶液（Ａ液）を７０℃乃至２００℃において、４０時間乃至２時間、好ましくは８０乃至１２０℃で３乃至３０時間、最も好ましい実例として９０℃乃至１００℃未満で５乃至２０時間の加熱処理をしてアナターゼ型酸化チタン分散液を製造することができる。加熱温度が７０℃以下では、反応に時間がかかりすぎて好ましくなく、２００℃以上に加熱しても、反応が速くなりすぎて制御が困難になると共に、装置が大掛かりになるだけでそれに見合う効果がない。
特許文献５、６に記載されているように、ペルオキソチタン酸水溶液を加熱処理した液を塗布し固化させて形成された膜のＸ線解析スペクトルは、アナターゼ型酸化チタンに基づくピークを有する。
(Manufacture of anatase-type titanium oxide dispersion)
A peroxotitanic acid aqueous solution (liquid A) at 70 ° C. to 200 ° C. for 40 hours to 2 hours, preferably 80 to 120 ° C. for 3 to 30 hours, most preferably 90 ° C. to less than 100 ° C. for 5 to 20 hours. An anatase-type titanium oxide dispersion can be produced by heat treatment. When the heating temperature is 70 ° C. or lower, the reaction takes too much time, which is not preferable. Even when heated to 200 ° C. or higher, the reaction becomes too fast and difficult to control, and the effect is commensurate with the large scale of the apparatus. There is no.
As described in Patent Documents 5 and 6, the X-ray analysis spectrum of a film formed by applying and solidifying a solution obtained by heating a peroxotitanic acid aqueous solution has a peak based on anatase-type titanium oxide.
（貴金属の塩又はナノコロイドの添加）
本発明は、アナターゼ型酸化チタン分散液に貴金属の塩又はナノコロイドを添加してＢ液とすることを特徴とする。使用する貴金属は、銅、銀、金、及び白金から選ばれる群のうちの１以上を含むことが好ましく、より好ましい例として、銀塩及び白金塩を挙げることができる。これらの貴金属は、強力な抗菌、抗カビ、及び抗ウィルス活性を示す。
(Addition of precious metal salt or nano colloid)
The present invention is characterized in that a noble metal salt or nanocolloid is added to an anatase-type titanium oxide dispersion to obtain a B solution. The precious metal used preferably contains one or more members selected from the group consisting of copper, silver, gold, and platinum, and more preferable examples include silver salts and platinum salts. These noble metals exhibit strong antibacterial, antifungal and antiviral activity.
貴金属を陽イオンとする貴金属塩の陰イオンは、強酸の塩として塩酸塩、硝酸塩、過塩素酸塩、硫酸塩、リン酸塩、テトラフロロホウ酸塩、及びヘキサフロロリン酸塩を例示することができ、また、弱酸の塩として酢酸塩、ギ酸塩、炭酸塩を例示することができるが、これらに限定されるものではない。また、白金塩としては、ヘキサクロロ白金酸及びテトラクロロ白金酸及びそれらの塩類を含むことができる。
貴金属ナノコロイドは、本発明の目的に可能物であれば、公知のものを使用することができる。
Anions of noble metal salts with noble metals as cations should be exemplified as hydrochlorides, nitrates, perchlorates, sulfates, phosphates, tetrafluoroborates, and hexafluorophosphates as strong acid salts. Examples of the weak acid salt include acetate, formate, and carbonate, but the salt is not limited thereto. Moreover, as a platinum salt, hexachloroplatinic acid, tetrachloroplatinic acid, and those salts can be included.
Any known noble metal nanocolloid can be used as long as it is possible for the purpose of the present invention.
Ｂ液中のアナターゼ型酸化チタンの濃度は、Ｂ液の重量を１００重量部とした場合に、酸化チタンの重量が０．１乃至１０重量部であることが好ましい。酸化チタンの重量が０．１重量部以下では、十分な厚さの光触媒層を形成することができにくくなり、１０重量部以上では、アナターゼ型酸化チタンの粘度が増加して取り扱いが困難になる場合がある。 The concentration of anatase-type titanium oxide in the B liquid is preferably 0.1 to 10 parts by weight of titanium oxide when the weight of the B liquid is 100 parts by weight. If the weight of titanium oxide is 0.1 parts by weight or less, it is difficult to form a photocatalyst layer having a sufficient thickness, and if it is 10 parts by weight or more, the viscosity of anatase-type titanium oxide increases and handling becomes difficult. There is a case.
Ｂ液中の貴金属の塩又はナノコロイドの濃度は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、Ｂ液の重量を１００重量部とした場合に、１×１０−４〜１×１０−９重量部の範囲内であることが好ましい。貴金属の量が１×１０−９重量部以下の濃度では、十分な抗菌活性を示すことができない可能性があり、また１×１０−４以上加えても、加えた量に比べて効果が増強されない。 The concentration of the salt or nanocolloid of the noble metal in the liquid B is 1 × 10 −4 to 1 when the weight of the salt or nanocolloid of the noble metal is converted to the weight of the metal and the weight of the liquid B is 100 parts by weight. It is preferable to be within the range of × 10 −9 parts by weight. If the amount of the precious metal is 1 × 10 −9 parts by weight or less, there is a possibility that sufficient antibacterial activity may not be exhibited, and the effect is enhanced compared to the amount added even if 1 × 10 −4 or more is added. Not.
（ペルオキソチタン酸水溶液（Ａ液）を塗布し乾燥する工程）
ペルオキソチタン酸水溶液（Ａ液）を塗布し乾燥する工程の塗布方法は、本発明の目的にかなうものであれば、何れの方法でもよい。塗布量は、特に制限されないが、１．０乃至１００ｍｌ／ｍ２であることができる。１．０ｍｌ／ｍ２以下では、ペルオキソチタン酸層の厚さが不十分になることがあり、１００ｍｌ／ｍ２以上厚く塗布しても効果が増加しないので不利である。塗布は１回で行うことも、複数回に分けて行うこともできる。また、乾燥温度が７０℃以上ではペルオキソチタン酸がアナターゼ型結晶に変化してしまうので、例えば４０℃以下で行うことが好ましい。
(Step of applying and drying a peroxotitanic acid aqueous solution (A solution))
The application method in the step of applying and drying the peroxotitanic acid aqueous solution (A solution) may be any method as long as it meets the object of the present invention. The coating amount is not particularly limited, but can be 1.0 to 100 ml / m 2 . If it is 1.0 ml / m 2 or less, the thickness of the peroxotitanic acid layer may be insufficient, and even if it is applied to a thickness of 100 ml / m 2 or more, the effect is not increased, which is disadvantageous. The application can be performed once or divided into a plurality of times. Further, when the drying temperature is 70 ° C. or higher, peroxotitanic acid is changed to anatase type crystals, and therefore, it is preferable to carry out at 40 ° C. or lower, for example.
Ｂ液を塗布し乾燥する工程の塗布方法は、本発明の目的にかなうものであれば、何れの方法でもよい。塗布量は、特に制限されないが、１．０乃至１００ｍｌ／ｍ２であることができる。１．０ｍｌ／ｍ２以下では、内壁としてアナターゼ型酸化チタン層の厚さが不十分なことがあり、１００ｍｌ／ｍ２以上厚く塗布しても効果が増加しないので不利である。塗布は１回で行うことも、複数回に分けて行うこともできる。乾燥は６０℃以下で行うことが好ましい。 The application method in the step of applying and drying the liquid B may be any method as long as it meets the object of the present invention. The coating amount is not particularly limited, but can be 1.0 to 100 ml / m 2 . If it is 1.0 ml / m 2 or less, the thickness of the anatase-type titanium oxide layer may be insufficient as the inner wall, and even if it is applied to a thickness of 100 ml / m 2 or more, the effect is not increased, which is disadvantageous. The application can be performed once or divided into a plurality of times. Drying is preferably performed at 60 ° C. or lower.
Ｂ液を塗布し乾燥する工程の塗布方法は、本発明の目的にかなうものであれば、何れの方法でもよい。塗布量は、特に制限されないが、１．０乃至１００ｍｌ／ｍ２であることができる。１．０ｍｌ／ｍ２以下では、内壁としてアナターゼ型酸化チタン層の厚さが不十分なことがあり、１００ｍｌ／ｍ２以上厚く塗布しても効果が増加しないので不利である。塗布は１回で行うことも、複数回に分けて行うこともできる。乾燥は６０℃以下で行うことが好ましい。 The application method in the step of applying and drying the liquid B may be any method as long as it meets the object of the present invention. The coating amount is not particularly limited, but can be 1.0 to 100 ml / m 2 . If it is 1.0 ml / m 2 or less, the thickness of the anatase-type titanium oxide layer may be insufficient as the inner wall, and even if it is applied to a thickness of 100 ml / m 2 or more, the effect is not increased, which is disadvantageous. The application can be performed once or divided into a plurality of times. Drying is preferably performed at 60 ° C. or lower.
Ａ液とＢ液の比は、Ａ液が含有するペルオキソチタン酸の重量を酸化チタンの重量に換算したチタン酸重量と、前記Ｂ液が含有するチタン酸重量と、の比が、１０：１乃至１：１０の範囲内であることが好ましく、４：１乃至１：４の範囲内であることがより好ましい。Ｂ液がＡ液の１／１０以下では、アナターゼ型酸化チタン層は光活性触媒として十分な活性を示すことができないことがあり、又Ａ液がＢ液の１／１０以下では、ペルオキソチタン酸層はアナターゼ型酸化チタン層が生成する活性酸素に対して十分なコーティング作用を示すことができないことがあり、複合膜としての特徴を示すことができないことがある。 The ratio of the A liquid and the B liquid is such that the ratio of the titanic acid weight obtained by converting the weight of peroxotitanic acid contained in the A liquid into the weight of titanium oxide and the titanic acid weight contained in the B liquid is 10: 1. To within a range of 1:10, more preferably within a range of 4: 1 to 1: 4. If the B liquid is 1/10 or less of the A liquid, the anatase-type titanium oxide layer may not exhibit sufficient activity as a photoactive catalyst, and if the A liquid is 1/10 or less of the B liquid, peroxotitanic acid The layer may not be able to exhibit a sufficient coating action on the active oxygen generated by the anatase-type titanium oxide layer, and may not be able to exhibit characteristics as a composite film.
以下に、実施例を示し、本発明を詳細に説明する。
（実施例１）
［第１工程］ペルオキソチタン酸水溶液（Ａ液）の製造
四塩化チタンの６０％（重量／容量）水溶液３９．６ｍｌを蒸留水で４０００ｍｌとした溶液に２．５％（重量／容量）アンモニア水、４４０ｍｌを滴下して水酸化チタンを沈殿させた。沈殿物をろ取し、蒸留水で洗浄後、蒸留水を加えて７２０ｍｌとした水酸化チタン懸濁液に、３０％（重量／容量）の過酸化水素水、８０ｍｌを加えて攪拌した。７℃において２４時間放置して余剰の過酸化水素水を分解させて、黄色粘性液体１０００ｍｌを得た。
Hereinafter, the present invention will be described in detail with reference to examples.
Example 1
[Step 1] Production of aqueous solution of peroxotitanic acid (liquid A) 2.5% (weight / volume) ammonia water in a solution of 39.6 ml of 60% (weight / volume) aqueous solution of titanium tetrachloride in 4000 ml of distilled water 440 ml was added dropwise to precipitate titanium hydroxide. The precipitate was collected by filtration and washed with distilled water. To the titanium hydroxide suspension made up to 720 ml by adding distilled water, 80 ml of 30% (weight / volume) hydrogen peroxide water was added and stirred. The mixture was allowed to stand at 7 ° C. for 24 hours to decompose excess hydrogen peroxide solution to obtain 1000 ml of a yellow viscous liquid.
［第２工程］Ｂ液の製造
第一工程で得られたペルオキソチタン酸水溶液を耐圧ガラス容器に密閉して水浴中で１２時間煮沸（９８〜１００℃）したところ、淡黄色半透明の１．００％（重量／容量）のアナターゼ型酸化チタン分散液が生成した。
１．００％（重量／容量）のアナターゼ型酸化チタン分散液１００ｍｌに対し、金属銀として０．１％（重量／容量）の銀を含む硝酸銀水溶液を０．１ｍｌ加え、１×１０−６％（重量／容量）を撹拌・混合しての銀を含むＢ液を作成した。
[Second Step] Production of Liquid B The peroxotitanic acid aqueous solution obtained in the first step was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.). A 00% (weight / volume) anatase-type titanium oxide dispersion was produced.
To 100 ml of an 1.00% (weight / volume) anatase-type titanium oxide dispersion, 0.1 ml of a silver nitrate aqueous solution containing 0.1% (weight / volume) of silver as metal silver was added. 1 × 10 −6 % Liquid B containing silver was prepared by stirring and mixing (weight / volume).
［第３工程］ペルオキソチタン酸水溶液（Ａ液）を内装面に塗布し乾燥する工程
第１工程で製造したペルオキソチタン酸水溶液（Ａ液）を、噴射スプレーを用いてスライドガラス上に１０ｍｌ／ｍ２の量で塗布して、２５℃で乾燥することによって、ペルオキソチタン酸層を製造した。
[Third Step] Step of Applying Peroxotitanic Acid Aqueous Solution (Liquid A) to the Interior Surface and Drying The Peroxotitanic Acid Aqueous Solution (Liquid A) produced in the first step is 10 ml / m on a slide glass using a spray spray. A peroxotitanic acid layer was prepared by coating in an amount of 2 and drying at 25 ° C.
［第４工程］Ｂ液を塗布し乾燥する工程
第３工程で製造したＡ液を塗布し乾燥したスライドガラス板の上に、第２工程で製造したＢ液を、１０ｍｌ／ｍ２の量で塗布して、４０℃で乾燥することによって、実施例１のアナターゼ型酸化チタンを含有する内装用複合膜を塗布した試料を得た。
[Fourth Step] Step of Applying and Drying Liquid B On the slide glass plate coated with and dried of Liquid A manufactured in Step 3, the amount of Liquid B manufactured in Step 2 is 10 ml / m 2 . The sample which apply | coated the composite film for interior containing the anatase type titanium oxide of Example 1 was obtained by apply | coating and drying at 40 degreeC.
（実施例２）
［第１工程］Ａ液の製造
６０％（重量／容量）四塩化チタン水溶液、５．００ｍｌを蒸留水で５００ｍｌに希釈した溶液に、３０％（重量／容量）過酸化水素水、２０ｍｌを加えて攪拌して褐色の透明液体を作製し、この溶液に１０％アンモニア水（濃アンモキア水１容量部：水９容量部）を滴下してｐＨを７とし、黄色透明の溶液を作製した。得られた溶液を２５℃で一昼夜放置し、黄色の析出沈殿物を生成させた。これを、ろ取し、洗浄後、蒸留水を加えて約１５０ｍｌとし、陽イオン交換樹脂（アンバーライトＩＲ−１２０Ｂ、Ｈ型）及び陰イオン交換樹脂（アンバーライトＩＲＡ−４１０、ＯＨ型）をそれぞれ２５ｇずつ投入して３０分間放置し、ろ過してイオン交換樹脂を取り除いた後、蒸留水で約１８０ｍｌとし、氷水で冷却し、３０％（重量／容量）過酸化水素水、２０ｍｌを加えて冷却することによって、１時間後に透明黄色液体のＡ液、２００ｍｌを得た。
第２工程〜第４工程は、実施例１と同様に行って実施例２のアナターゼ型酸化チタンを含有する内装用複合膜を塗布した試料を得た。
(Example 2)
[Step 1] Production of solution A 60% (weight / volume) titanium tetrachloride aqueous solution, 5.00 ml diluted with distilled water to 500 ml, 30% (weight / volume) hydrogen peroxide solution, 20 ml was added. The mixture was stirred to prepare a brown transparent liquid. To this solution, 10% aqueous ammonia (1 part by volume of concentrated ammonia water: 9 parts by volume of water) was added dropwise to adjust the pH to 7 to prepare a yellow transparent solution. The resulting solution was allowed to stand at 25 ° C. for a whole day and night to produce a yellow precipitate. This was filtered and washed, and then distilled water was added to make about 150 ml, and cation exchange resin (Amberlite IR-120B, H type) and anion exchange resin (Amberlite IRA-410, OH type) were respectively added. Add 25g each, leave it for 30 minutes, filter to remove the ion exchange resin, make about 180ml with distilled water, cool with ice water, cool by adding 20ml of 30% (weight / volume) hydrogen peroxide water As a result, 200 ml of a clear yellow liquid A was obtained after 1 hour.
The 2nd process-the 4th process were performed like Example 1, and the sample which applied the composite film for interiors containing the anatase type titanium oxide of Example 2 was obtained.
（実施例３）
［第１工程］Ａ液の製造
実施例１と同様にしてＡ液を得た。
［第２工程］Ｂ液の製造
第一工程で得られたペルオキソチタン酸水溶液を耐圧ガラス容器に封入して水浴中で１２時間煮沸（９８〜１００℃）したところ、淡黄色半透明の１．００％（重量／容量）のアナターゼ型酸化チタン分散液を得た。１．００％（重量／容量）のアナターゼ型酸化チタン分散液１００ｍｌに対し、金属白金として０．００１％（重量／容量）の白金ナノコロイド（特許文献８を参照）を含む水溶液を０．１ｍｌ加え、１×１０−８重量部（重量／容量）の白金ナノコロイドを含む１．００％（重量／容量）のＢ液を作成した。
第３工程及び第４工程は、実施例１と同様に行って実施例３のアナターゼ型酸化チタンを含有する内装用複合膜を塗布した試料を得た。
(Example 3)
[First Step] Production of Liquid A Liquid A was obtained in the same manner as in Example 1.
[Second Step] Production of Liquid B When the peroxotitanic acid aqueous solution obtained in the first step was sealed in a pressure-resistant glass container and boiled in a water bath for 12 hours (98 to 100 ° C.), a pale yellow translucent 1. A 00% (weight / volume) anatase-type titanium oxide dispersion was obtained. 0.1 ml of an aqueous solution containing 0.001% (weight / volume) platinum nanocolloid (see Patent Document 8) as metal platinum with respect to 100 ml of 1.00% (weight / volume) anatase type titanium oxide dispersion In addition, 1.00% (weight / volume) B liquid containing 1 × 10 −8 parts by weight (weight / volume) of platinum nanocolloid was prepared.
The 3rd process and the 4th process were performed like Example 1, and the sample which applied the composite film for interiors containing the anatase type titanium oxide of Example 3 was obtained.
（比較例１）
実施例１の第２工程で得たＢ液を、スライドガラス上に１０ｍｌ／ｍ２の量を塗布し、４０℃で乾燥、加熱処理することによって、比較例１のアナターゼ型酸化チタン層を塗布した試料を得た。
(Comparative Example 1)
The anatase-type titanium oxide layer of Comparative Example 1 was applied by applying the B liquid obtained in the second step of Example 1 on a slide glass in an amount of 10 ml / m 2 , drying at 40 ° C., and heat treatment. A sample was obtained.
（比較例２）
実施例１の第１工程で得たペルオキソチタン酸水溶液（Ａ液）を、スライドガラス上に１０ｍｌ／ｍ２の量を塗布して、４０℃で乾燥することによって、比較例２のアナターゼ型酸化チタン層を塗布した試料が得られた。
(Comparative Example 2)
The aqueous peroxotitanic acid solution (liquid A) obtained in the first step of Example 1 was applied to a slide glass in an amount of 10 ml / m 2 and dried at 40 ° C. A sample coated with a titanium layer was obtained.
（比較例３）
実施例１と同様に、但し第２工程で硝酸銀を加えずにアナターゼ型酸化チタン複合膜を塗布した試料を得た。
(Comparative Example 3)
As in Example 1, except that silver nitrate was not added in the second step, a sample coated with an anatase-type titanium oxide composite film was obtained.
（試験例１）酸化窒素除去試験
試料 ：実施例１〜３及び比較例１、２の試験片、及びガラス片
試験方法：ＪＩＳ Ｒ １７０１−１：２００４，ファインセラミックス−光触媒材料
の空気浄化性能試験方法−第１部：窒素酸化物の除去性能 ６．１，６．２
試験機関：株式会社 環境技術研究所
結果を表１に示す。
Air purification performance test method-Part 1: Nitrogen oxide removal performance 6.1, 6.2
Test organization: Environmental Technology Research Institute Co., Ltd. The results are shown in Table 1.
表２に示すように、アナターゼ型酸化チタン層及びペルオキシチタン酸層を有する実施例１〜３の複合膜は、優れた酸化窒素除去作用を有すること示された。比較例１は、アナターゼ型酸化チタンの光触媒層を有するが、成膜性が良くないために、酸化窒素除去作用が実施例１〜３より劣る。アナターゼ型酸化チタン層を有していない比較例２及びガラス片は、酸化窒素除去作用を有していない。 As shown in Table 2, it was shown that the composite films of Examples 1 to 3 having an anatase-type titanium oxide layer and a peroxytitanic acid layer have an excellent nitrogen oxide removing action. Although the comparative example 1 has a photocatalyst layer of anatase type titanium oxide, since the film formability is not good, the nitrogen oxide removing action is inferior to those of Examples 1 to 3. The comparative example 2 and glass piece which do not have an anatase type titanium oxide layer do not have a nitric oxide removal action.
（試験例２）活性酸素遮蔽試験
試料 ：１０ｃｍ×１０ｃｍの表面を磨いた木片に、０．１ｍｏｌメチレンブルーの
エタノール溶液を均等に噴霧して活性酸素遮蔽試験片を作成した。
実施例１〜３及び比較例１、２の方法に従って、但しガラス片の代わりに上
記の活性酸素遮蔽試験片を用いて活性酸素遮蔽試験用の試料を作成し、暗所
で２５℃で２日間乾燥した。
試験方法 １）０．１ｍｏｌメチレンブルー、及びそれ２倍及び４倍に希釈した溶液を
塗布した標準色調片を作成した。
２）ガラス片の代わりに上記の活性酸素遮蔽試験片を用いて試料から１０
ｃｍ離して、照度５０００ルックスの蛍光灯で照射して試験片の色相の変化
を観測し、下記の評価用語に従って評価した。
４：変化なし。
３：２倍に希釈した標準色調片と同等の色調になった。
２：４倍に希釈した標準色調片と同等の色調になった。
１：青色が殆ど消失した。
０：青色が完全に消失した。
結果 結果を表２に示す。
An active oxygen shielding test piece was prepared by spraying the ethanol solution uniformly.
According to the methods of Examples 1 to 3 and Comparative Examples 1 and 2, but instead of glass pieces
Prepare a sample for active oxygen shielding test using the active oxygen shielding test piece described above.
And dried at 25 ° C. for 2 days.
Test Method 1) 0.1 mol methylene blue and a solution diluted 2 and 4 times
An applied standard color piece was prepared.
2) 10% from the sample using the above active oxygen shielding test piece instead of the glass piece.
Change the hue of the test piece by illuminating with a fluorescent lamp with illuminance of 5000 lux at a distance of cm
Were observed and evaluated according to the following evaluation terms.
4: No change.
3: A color tone equivalent to that of a standard color piece diluted 2 times was obtained.
2: The color tone was equivalent to that of a standard color piece diluted 4-fold.
1: The blue color almost disappeared.
0: The blue color disappeared completely.
Results The results are shown in Table 2.
表２に示すように、アナターゼ型酸化チタン層及びペルオキシチタン酸層を有する実施例１〜３の複合膜は、チレンブルーの退色速度が遅く、アンダーコート層が活性酸素の侵襲を防いでいることが示された。触媒層を有し、アンダーコート層を有していない比較例１は、メチレンブルーが速かに退色し、活性酸素が基材に達していることが示された。 As shown in Table 2, the composite films of Examples 1 to 3 having an anatase-type titanium oxide layer and a peroxytitanic acid layer have a slow fading rate of Tylene Blue, and the undercoat layer prevents the invasion of active oxygen. Indicated. Comparative Example 1 having a catalyst layer and no undercoat layer showed that methylene blue faded quickly and active oxygen reached the substrate.
（試験例３）抗菌試験
試料 ：実施例１及び比較例３の試験片
試験機関：社団法人京都微生物研究所
試験方法：光照射フィルム密着法（明条件、暗条件）
「抗菌性技術協議会の光照射フィルム密着法」に従い、蛍光灯照射（５５０
０ｌｘ、１０ｃｍ）／非照射試験片上に滴下した菌液中の菌液について、
２４時間後に生菌数を測定した。
結果 結果を表３に示す。
Fluorescent lamp irradiation (550)
0 lx, 10 cm) / bacterial liquid in the bacterial liquid dropped on the non-irradiated test piece,
The number of viable bacteria was measured after 24 hours.
Results The results are shown in Table 3.
表３に示すように、アナターゼ型酸化チタン層及び銀を含む実施例１の複合膜は、明条件及び暗条件の何れにおいても抗菌活性を有すが、貴金属を含まない比較例３の試験片は、明条件下で抗菌活性を有するが、暗条件下では抗菌活性を有しないことが示された。 As shown in Table 3, the composite film of Example 1 containing an anatase-type titanium oxide layer and silver has antibacterial activity in both light and dark conditions, but the test piece of Comparative Example 3 containing no precious metal Has antibacterial activity under light conditions but no antibacterial activity under dark conditions.
以上、本発明に関する好ましい実施形態を説明したが、本発明は前記実施形態に限定されず、本発明の属する技術範囲を逸脱しない範囲での全ての変更が含まれる。 As mentioned above, although preferred embodiment regarding this invention was described, this invention is not limited to the said embodiment, All the changes in the range which does not deviate from the technical scope to which this invention belongs are included.
Claims (4)
前記貴金属の塩又はナノコロイドの含有量は、貴金属の塩又はナノコロイドの重量を金属の重量に換算し、前記アナターゼ型酸化チタンの重量を１００重量部とした場合に、１×１０−１乃至１×１０−８重量部の範囲内であることを特徴とするアナターゼ型酸化チタンを含有する内装用複合膜。 An undercoat layer made of amorphous titanium oxide formed on the interior surface of a building, a noble metal salt or nanocolloid formed on the undercoat layer, and a photocatalyst layer made of anatase titanium oxide. Have
The content of the noble metal salt or nanocolloid is 1 × 10 −1 to 1 × 10 −1 when the weight of the noble metal salt or nanocolloid is converted to the weight of the metal and the weight of the anatase titanium oxide is 100 parts by weight. An interior composite film containing anatase-type titanium oxide, characterized by being in the range of 1 × 10 −8 parts by weight.
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| JP6198921B1 (en) * | 2016-10-06 | 2017-09-20 | 株式会社バイオミミック | Photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays, and method for producing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09262481A (en) * | 1996-03-29 | 1997-10-07 | Tao:Kk | Photocatalyst and its production |
| JPH10235201A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Photocatalytic body and production thereof |
| JP2000135442A (en) * | 1998-08-28 | 2000-05-16 | Tao:Kk | Water-repellent substrate |
| JP2001191443A (en) * | 2000-01-11 | 2001-07-17 | Toyobo Co Ltd | Outdoor sheet |
| JP2003306992A (en) * | 2002-04-15 | 2003-10-31 | Bridgestone Corp | Antifouling panel building material |
| JP2007185616A (en) * | 2006-01-13 | 2007-07-26 | Sundecor:Kk | Photocatalyst layer and photocatalyst layer forming method |
-
2016
- 2016-02-24 JP JP2016032930A patent/JP6067899B2/en not_active Expired - Fee Related
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2017
- 2017-02-16 TW TW106105061A patent/TW201800238A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09262481A (en) * | 1996-03-29 | 1997-10-07 | Tao:Kk | Photocatalyst and its production |
| JPH10235201A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Photocatalytic body and production thereof |
| JP2000135442A (en) * | 1998-08-28 | 2000-05-16 | Tao:Kk | Water-repellent substrate |
| JP2001191443A (en) * | 2000-01-11 | 2001-07-17 | Toyobo Co Ltd | Outdoor sheet |
| JP2003306992A (en) * | 2002-04-15 | 2003-10-31 | Bridgestone Corp | Antifouling panel building material |
| JP2007185616A (en) * | 2006-01-13 | 2007-07-26 | Sundecor:Kk | Photocatalyst layer and photocatalyst layer forming method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6198921B1 (en) * | 2016-10-06 | 2017-09-20 | 株式会社バイオミミック | Photocatalyst composite coating film that transmits visible light and shields ultraviolet rays and infrared rays, and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6067899B2 (en) | 2017-01-25 |
| TW201800238A (en) | 2018-01-01 |
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