JP4292992B2 - Composition for forming photocatalyst film and substrate with photocatalyst film - Google Patents
Composition for forming photocatalyst film and substrate with photocatalyst film Download PDFInfo
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- JP4292992B2 JP4292992B2 JP2003567988A JP2003567988A JP4292992B2 JP 4292992 B2 JP4292992 B2 JP 4292992B2 JP 2003567988 A JP2003567988 A JP 2003567988A JP 2003567988 A JP2003567988 A JP 2003567988A JP 4292992 B2 JP4292992 B2 JP 4292992B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 107
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000000758 substrate Substances 0.000 title claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 239000004115 Sodium Silicate Substances 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 14
- -1 Silicate compound Chemical class 0.000 claims description 13
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 13
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- 239000004065 semiconductor Substances 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
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- 239000004094 surface-active agent Substances 0.000 description 9
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002736 nonionic surfactant Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
Description
技術分野
本発明は、各種基材の表面に光触媒膜を形成できる光触媒膜形成用組成物、および該組成物から形成された光触媒膜および該光触媒膜を有する光触媒膜付き基材に関する。
背景技術
光触媒を光励起すると光触媒表面に付着した有機汚れなどが分解され、結果として親水性表面が実現することが知られている。光触媒膜を形成する方法として、乾式法の一種である熱分解法などが従来より知られている（例えば、特表平１１−５１２３３７号公報）。しかし、上記方法では、湿式法と比較して、親水持続性という点で劣っている問題があった。
また、光触媒とシリカとを含むコーティング組成物を用いて光触媒膜を形成する方法も知られている（例えば、特許２７５６４７４号公報）。しかし、上記方法のシリカを用いた膜は、親水持続性の点で劣り、かつ汚れ分解性が低い問題があった。
本発明は、上記の問題を解消するものであり、優れた親水性を基材の表面に付与でき、特に汚れ分解性に優れる光触媒膜を形成できる光触媒膜形成用組成物、該組成物から形成されてなる光触媒膜、および該光触媒膜付き基材の提供を目的とする。また、親水性の持続時間が長く、表面の耐摩耗性にも優れた光触媒膜を形成できる光触媒膜形成用組成物および該組成物から形成された光触媒膜および該光触媒膜付き基材の提供を目的とする。
発明の開示
本発明は、光触媒半導体微粒子、下記シリカ前駆体および媒体を必須とする光触媒膜形成用組成物を提供する。
シリカ前駆体：ケイ酸１００質量部に対してアルカリ金属イオンが０．００１〜１質量部含まれるケイ酸化合物。
また、本発明は、基材の表面に光触媒膜形成用組成物から形成されてなる光触媒膜、および該光触媒膜を有する光触媒膜付き基材を提供する。
発明を実施するための形態
本発明における光触媒半導体微粒子とは、該光触媒の価電子帯と伝導電子帯との間のエネルギー差よりも大きなエネルギーの光を照射したときに、価電子帯中の電子の励起によって伝導電子と正孔を生成しうる性質を有する材料をいう。このような光触媒半導体微粒子としては、アナターゼ型酸化チタン、ルチル型酸化チタン、酸化錫、酸化亜鉛、三酸化タングステン、酸化第二鉄、チタン酸ストロンチウムなどが好ましく挙げられる。
本発明における光触媒半導体微粒子の平均粒子径は、光散乱を利用して組成物中の微粒子の凝集粒子径をマイクロトラックＵＰＡ粒度分布計（ＨＯＮＥＹＷＥＬＬ社製）を用いて測定したものであり、好ましくは５〜９０ｎｍ、特に好ましくは４０〜７０である。平均粒子径があまりに小さいと、形成された光触媒膜の中に光触媒の微粒子が埋没してしまうため、光触媒の種々の効果が発現しにくい。また、平均粒子径があまりに大きいと、形成される光触媒膜の機械的強度が不足し、また、透明性が確保できないおそれがある。
本発明におけるシリカ前駆体とは、ケイ酸１００質量部に対してアルカリ金属イオンが０．００１〜１質量部含まれるケイ酸化合物であり、なかでも、０．００１〜０．２質量部含まれることが好ましく、０．００１〜０．１５質量部含まれることが特に好ましい。アルカリ金属イオン濃度は、セイコーインスツルメンツ社製ＳＰＳ４０００などを用いて、ＩＣＰ発光分析にて測定したものである。アルカリ金属イオンとしては、特に限定はなく、１種を用いてもよく、２種以上を用いてもよい。アルカリ金属イオンとしては、ナトリウムイオンまたはリチウムイオンが好ましい。また、ケイ酸化合物とは、後述するような後処理を施すことにより、シリカ膜を形成する化合物を意味する。
シリカ前駆体は、ケイ酸のアルカリ金属塩からアルカリ金属イオンの一部を除去して得られる生成物が好ましい。該生成物は、たとえば、陽イオン交換樹脂を用いて、ケイ酸のアルカリ金属塩からアルカリ金属イオンを減らす方法により得られる。使用する陽イオン交換樹脂の量、接触時間、接触方法等を制御することで、減らすアルカリ金属イオンの量を調節できる。
陽イオン交換樹脂としては、強酸性陽イオン交換樹脂（ＲＳＯ３Ｈ型）、弱酸性陽イオン交換樹脂（ＲＣＯＯＨ型）等が使用できるが、強酸性陽イオン交換樹脂を使用するのが反応速度の点で好ましい。
本発明の光触媒膜形成用組成物においては、アルカリ金属イオンの濃度は光触媒形成用組成物に対して質量換算で１〜８０ｐｐｍであるのが好ましく、特に１〜４０ｐｐｍ、さらには１〜２０ｐｐｍであるのが好ましい。アルカリ金属イオンの濃度が小さすぎると、該組成物の安定性および親水性が低下し、大きすぎると該組成物の安定性が著しく低下する。
ケイ酸のアルカリ金属塩としては、ケイ酸ナトリウム、ケイ酸リチウム、およびケイ酸カリウムなどの群から選ばれる１種以上が挙げられ、特にケイ酸ナトリウムおよび／またはケイ酸リチウムが好ましい。
ケイ酸ナトリウムとしては、ＳｉＯ２／Ｎａ２Ｏの組成比が異なる材料が知られており、特に限定されずに用いることができる。なかでも、Ｎａ２Ｏの含有比が小さい材料が好ましい。市販のケイ酸ナトリウムとしては、ケイ酸ソーダ１号（ＳｉＯ２／Ｎａ２Ｏのモル比：２．０〜２．３）（ケイ酸ソーダ１号とは日本化学工業社製の商品名である。以下、２〜４号についても同じ。）、ケイ酸ソーダ２号（同モル比：２．４〜２．７）、ケイ酸ソーダ３号（同モル比：３．０〜３．３）、ケイ酸ソーダ４号（同モル比：３．７〜３．９）がある。特に、Ｎａ２Ｏの含有比が小さいケイ酸ソーダ３号または４号が特に好ましい。
ケイ酸リチウムとしては、ＳｉＯ２／Ｌｉ２Ｏの組成比が異なる材料が知られており、特に限定されずに用いることができる。なかでも、Ｌｉ２Ｏの含有比が小さい材料が好ましい。市販のケイ酸リチウムとしては、ケイ酸リチウム３５（ＳｉＯ２／Ｌｉ２Ｏのモル比：３．５）（ケイ酸リチウム３５とは日本化学工業社製の商品名である。以下、４５、７５についても同じ。）、ケイ酸リチウム４５（同モル比：４．５）、ケイ酸リチウム７５（同モル比：７．５）がある。特に、Ｌｉ２Ｏの含有比が小さいケイ酸リチウム７５が特に好ましい。
本発明の光触媒膜形成用組成物には、界面活性剤が含まれるのが好ましい。該界面活性剤には主に２つの機能があり、第１は、組成物の基材に対する濡れ性を確保することであり、第２は、該組成物を用いて形成された光触媒膜の親水性をより高くすることである。界面活性剤の種類は特に限定されないが、非イオン系界面活性剤が液分散安定性の点で好ましく用いられる。特に、親水部がポリオキシアルキレンであり、疎水部が含フッ素有機基である化合物［たとえば、Ｃ８Ｆ１７ＣＨ２ＣＨ２ＣＨ（ＣＨ３）Ｏ（ＣＨ２ＣＨ２Ｏ）ｘ（ＣＨ２ＣＨ（ＣＨ３）Ｏ）ｙＨ［ｘ：ｙ＝７０：３０、ｘ＋ｙ＝５．７２、平均分子量８００］で表される化合物（以下、界面活性剤Ｑと記す。）等。］が好ましい。または、親水部がポリオキシアルキレンであり、疎水部がメチルポリシロキサンである化合物（たとえば、日本ユニカー社製、商品名「Ｌ−７７」等。）が好ましい。
本発明の光触媒膜形成用組成物において、シリカ前駆体は、光触媒半導体微粒子１００質量部に対して２５〜９００質量部含まれることが好ましく、特に５０〜４００質量部含まれることが好ましい。また、界面活性剤を含む場合は、界面活性剤は、光触媒半導体微粒子１００質量部に対して０．１〜１０質量部含まれることが好ましい。
シリカ前駆体の濃度が大きすぎると得られた光触媒膜の親水性の耐久性が低下し、小さすぎると得られた光触媒膜に親水性が付与されない。また、界面活性剤の割合が大きすぎると得られた光触媒膜の外観が損なわれ、親水性の耐久性が低下し、小さすぎると組成物の塗布性が優れず、光触媒膜の親水性が低下する。
本発明の光触媒膜形成用組成物は、媒体を含む。媒体としては、特に限定はなく、水を含む媒体が好ましく、溶剤が含まれていてもよい。溶剤は主に希釈のために用いられ、該組成物は溶液の形態であることが好ましい。該溶剤としては、低級アルコール、含窒素系溶剤、含イオウ系溶剤等の極性溶剤が好ましく、特に低級アルコールが好ましい。溶剤は２種類以上を用いてもよい。媒体としては、特に水が好ましい。
本発明の光触媒膜形成用組成物における光触媒半導体微粒子とシリカ前駆体との総量は、塗布する方法、目的とする光触媒膜の厚さにより決定すればよい。上記の総量は、該組成物の安定性、経済性等を考慮して、光触媒形成用組成物１００質量部に対して０．５〜５０質量部含まれることが好ましく、特に０．５〜１５質量部が好ましく、とりわけ０．５〜５質量部が好ましい。
本発明の光触媒膜形成用組成物には、機能性添加剤が含まれていてもよい。該機能性添加剤としては、着色用染料、顔料、紫外線吸収剤、酸化防止剤、本発明における光触媒半導体微粒子以外の酸化物微粒子（五酸化リン、酸化マグネシウム等。平均粒子径は２００ｎｍ以下が好ましい。）等が好ましく挙げられる。
本発明の光触媒膜形成用組成物を用いて、基材の表面に該組成物が塗布され、光触媒膜が形成され、光触媒膜付き基材が作られる。前記光触媒膜において、シリカ前駆体はシリカに変換されているが、部分的にシラノール基が残っていてもよい。
シリカ前駆体は、化合物中にシラノール基を有し、すなわちＳｉＯｓ（ＯＨ）ｔ（ｓ、ｔは０以上の整数であり、ｓ＋ｔ＝４。）で表される構造を有する（ただし、該構造において、水酸基でない酸素原子は、別のケイ素原子と化学結合している。）と考えられ、該シリカ前駆体から脱水縮合反応によりシリカが形成される。
本発明においては、公知の湿式法を用いて光触媒膜形成用組成物を基材の表面に塗布し、図１のとおり、基材２０上に光触媒膜３０が形成された光触媒膜付き基材１０を形成できる。湿式法としては、たとえば、スプレーコート法、はけ塗り、手塗り、回転塗布、浸漬塗布、各種印刷方式による塗布、カーテンフロー、ダイコート、フローコート等の塗布方法が好ましく挙げられる。
光触媒膜形成用組成物を塗布した後、媒体の除去や光触媒膜の硬度を高めることを目的として、後処理を施すことが好ましい。前記後処理としては、室温における乾燥や加熱や、紫外線、電子線等の電磁波の照射、加熱等が挙げられる。加熱は基材の耐熱性を考慮して、５０〜７００℃、特に１００〜３５０℃の範囲で５〜６０分間行うことが好ましい。特に基材が有機樹脂などの耐熱性が低い材料である場合や基材中の低分子化合物が加熱により基材外に拡散する場合には、前記後処理として、紫外線、電子線等の電磁波の照射を行うことが好ましい。
本発明においては、光触媒膜形成用組成物の濃度、溶剤の種類、塗布条件、後処理条件等を調節することにより、得られる光触媒膜の厚さを制御できる。光触媒膜の厚さは、厚すぎると膜にクラックが入ったり、干渉縞が生じたり、傷が発生した場合にその傷が目立つという欠点があり、薄すぎると所望の光触媒性能が発揮されないおそれがある。光触媒膜の厚さは、経済性も考慮して、１０〜３００ｎｍが好ましく、特に１０〜１５０ｎｍが好ましい。
本発明に用いられる基材は、特に限定されない。基材の形状は平板に限らず、全面に、または、一部に曲率を有していてもよい。本発明において用いられる基材は、ガラス、有機樹脂等の透明な基材が好ましい。前記ガラスとしては、例えば、板ガラスや自動車用ガラスに主として用いられるソーダライムガラスが挙げられ、前記有機樹脂としては、例えば、ポリカーボネート、アクリル、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレートなどの樹脂が挙げられる。また、前記有機樹脂の強度を上げるため、樹脂の表面にシリコーンハードコートを施してもよい。また、基材として、ガラス、有機樹脂等の透明な基材を用いる場合には、その視認性の観点から、光触媒膜付き基材の可視光透過率（ＪＩＳ Ｒ３１０６（１９９８年））が７０％以上であることが好ましい。
基材には前処理を施してもよい。前処理としては、プラズマ処理、コロナ放電、ＵＶ処理、オゾン処理等の放電処理、酸またはアルカリ等を用いた化学的処理、研磨材を用いた物理的処理等が挙げられる。前処理を行うことで、組成物の基材への濡れ性がよくなり、組成物が均一に塗布でき、形成された光触媒膜の基材への密着性を高めることができる。特に基材が有機樹脂の場合、前処理を行うことが好ましい。一般にプラスチックの改質に用いられる低圧水銀ランプ等による紫外線照射により行われる前処理は特に有効である。
また、これらの前処理および前述したような後処理は、得られる膜の性能を大きく左右することから、それぞれの処理条件を最適化する必要がある。例えば紫外線の照射による後処理により、脱水縮重合反応を進行させ膜の硬化を進めるとともに、基材表面と組成物との密着性をも向上させることができる。このように後処理により基材との密着性を向上させることができる場合には、前処理は必須ではない。必要以上に前処理をすることによりかえって基材を劣化させ性能低下をまねく場合もある。
本発明の光触媒膜付き基材は、その表面が親水性に優れ、かつ透明性に優れるため、輸送機器用物品、建築用物品等として好ましく用いられる。輸送機器用物品としては、電車、自動車、船舶、航空機等のボディー、窓ガラス、ミラー、各種表示素子用カバー板等が挙げられる。建築用物品としては、外壁、シーラント部分、窓ガラス、橋やトンネル等の構造物等が挙げられる。また他の用途として、照明用カバーガラス、遮音壁等が挙げられる。
本発明の光触媒膜付き基材は、その表面が親水性に優れるため、表面に付着した水滴が濡れ広がり、表面が曇らないという防曇性を有する。また、表面において有機汚れが分解される。さらに、表面への光照射によって、有機汚れの分解性能がさらに向上する。さらに、降雨により雨滴が表面を流れ落ちる際に汚れも同時に流れ落ちる（セルフクリーニング効果）。本発明の光触媒膜付き基材は、視界の確保、美観の保護またはメンテナンス費用の削減等の効果も期待できる。
本発明の光触媒膜形成用組成物から形成された光触媒膜は、従来のアルコキシシランであるＳｉ（ＯＲ）４（Ｒ：アルキル基）を加水分解して得られるＳｉＯｐ（ＯＨ）ｑ（ＯＲ）ｒ（ｐ、ｑは０以上の整数であり、ｒは１以上の整数であり、ｐ＋ｑ＋ｒ＝４。）で表される構造（ただし、該構造において、水酸基でない酸素原子は、別のケイ素原子と化学結合している。）を有する生成物を用いた組成物から形成された被膜よりも、親水持続性や汚れ分解性に優れる。
本発明の光触媒膜付き基材は、基材と光触媒膜との間に別の膜を設けてもよい。前記別の膜としては、例えば、アルカリバリア層（基材がアルカリ金属含有ガラスである場合、光触媒膜へのアルカリ金属の拡散を防止することを目的とした層）が挙げられる。
実施例
本発明を実施例（例１〜７、１０〜１２）、比較例（例８、９）により具体的に説明する。サンプルは、以下の方法を用いて評価した。評価結果を表１に示す。
［親水性］
サンプル作製直後の、光を照射していない初期の水の接触角を測定した。
［親水持続性］
サンプル作成直後からサンプルを光のあたらない環境に１週間保持した後、水の接触角を測定した。接触角は、２０°以下、さらには１０°以下であることが親水性維持の観点から好ましい。
［汚れ分解性］
作成直後のサンプルにオレイン酸を付着させ、水の接触角が７０°程度である汚れた表面を作り、その表面にブラックライト（中心波長３６５ｎｍ）を０．５ｍＷ／ｃｍ２の強度で６時間照射した後、水の接触角を測定した。接触角が１０°以下、さらには６°以下であることが防汚性の観点から好ましい。
［膜強度］
サンプルにテーバー磨耗試験（磨耗回数：１００回、荷重：４．９Ｎ。）を行い、磨耗試験前後におけるヘーズ値を測定（測定機器名：スガ試験機社製直読ヘーズコンピュータ）し、その変化量を求めた。変化量が３％以下であることが耐磨耗性の観点から好ましい。
［防汚性］
作成直後のサンプルを屋外に１ヶ月間曝露した後、汚れの程度（ほとんど汚れが目立たない：○、少し汚れが目立つ：△、かなり汚れが目立つ：×。）を肉眼で観察した。
［防曇性］
作成直後のサンプルに息を吹きかけ、曇りの有無（曇りなし：○、曇り発生：×。）を肉眼で観察した。
［例１］
ソーダライムガラス板（１００ｍｍ×１００ｍｍ、厚さ３．５ｍｍ）を用意し、その表面を酸化セリウムで研磨し、蒸留水で洗浄した後に乾燥させ、前処理済ガラス板とした。
水の３７．５ｇにケイ酸ソーダ４号（商品名：日本化学工業社製。ＳｉＯ２：２３．３５質量％、Ｎａ２Ｏ：６．２９質量％。ＳｉＯ２／Ｎａ２Ｏのモル比：３．８３。）の１２．５ｇを添加し、さらに強酸性陽イオン交換樹脂（三菱化学社製、商品名「ＳＫ１ＢＨ」。）の３０ｇを添加して、１０分間室温で撹拌して脱塩ケイ酸ソーダ液（ケイ酸の１００質量部に対してナトリウムイオンは０．１２質量部。）を調整した。
また、２−プロパノールの３２．１ｇに、アナターゼ型酸化チタン微粒子（平均粒子径：５６ｎｍ。以下、光触媒Ａと記す。）の水分散液（固形分濃度：１０質量％。）の９ｇおよび脱塩ケイ酸ソーダ液の８．９ｇを添加し、さらに界面活性剤「Ｌ−７７」（商品名：日本ユニカー社製）を液量に対して１００ｐｐｍとなるように添加して、コート液１（ナトリウムイオン濃度は１２ｐｐｍ。）を得た。
得られたコート液１の２ｍＬを前記処理済ガラス板の表面に滴下し、スピンコート法により塗布した後、大気雰囲気中２００℃にて６０分間焼成し、厚さ８０ｎｍの光触媒膜を有するサンプルを得た。
［例２］
水の３６．０７ｇにケイ酸リチウム７５（商品名：日本化学工業社製。ＳｉＯ２：２１．５４質量％、Ｌｉ２Ｏ：１．４３質量％。ＳｉＯ２／Ｌｉ２Ｏのモル比：７．４９。）の１３．９３ｇを添加し、さらに「ＳＫ１ＢＨ」の３０ｇを添加して、１０分間室温で撹拌して脱塩ケイ酸リチウム液（ケイ酸の１００質量部に対してリチウムイオンは０．１３質量部。）を調整した。
また、２−プロパノールの３２．１ｇに、光触媒Ａの９ｇおよび脱塩ケイ酸リチウム液の８．９ｇを添加し、さらに「Ｌ−７７」を液量に対して１００ｐｐｍとなるように添加して、コート液２（リチウムイオン濃度は１３ｐｐｍ。）を得た。得られたコート液２を用いて、例１と同様にして、厚さ８３ｎｍの光触媒膜を有するサンプルを得た。
［例３］
２−プロパノールの３２．１ｇに、光触媒Ａの１０．５ｇおよび例１における脱塩ケイ酸ソーダ液の６．６９ｇを添加し、さらに「Ｌ−７７」を液量に対して１００ｐｐｍとなるように添加して、コート液３（ナトリウムイオン濃度は７ｐｐｍ。）を得た。得られたコート液３を用いて、例１と同様にして、厚さ８２ｎｍの光触媒膜を有するサンプルを得た。
［例４］
２−プロパノールの３２．１ｇに、光触媒Ａの４．５ｇおよび例１における脱塩ケイ酸ソーダ液の１５．６ｇを添加し、さらに「Ｌ−７７」を液量に対して１００ｐｐｍとなるように添加して、コート液４（ナトリウムイオン濃度は２３ｐｐｍ。）を得た。得られたコート液４を用いて、例１と同様にして、厚さ８３ｎｍの光触媒膜を有するサンプルを得た。
［例５］
例１において、「Ｌ−７７」の代わりに界面活性剤Ｑを用いた以外は、例１と同様にしてサンプルを得た。
［例６］
例１において、大気雰囲気中２００℃にて６０分間焼成する代わりに、大気雰囲気中３００℃にて３０分間焼成してサンプルを得た。
［例７］
例１において、大気雰囲気中２００℃にて６０分間焼成する代わりに、大気雰囲気中６５０℃にて５分間焼成してサンプルを得た。
［例８］（比較例）
エタノールの９０ｇにテトラメトキシシランの５ｇを添加し、１０分間撹拌した後、硝酸水溶液（１質量％）の５ｇを徐々に添加し、テトラメトキシシランの加水分解生成物Ｂを得た。
２−プロパノールの３２．１ｇに、光触媒Ａの９ｇおよび前記加水分解生成物Ｂの８．９ｇを添加し、さらに「Ｌ−７７」を液量に対して１００ｐｐｍとなるように添加して、コート液８（ナトリウムイオン濃度は０ｐｐｍ。）を得た。
得られたコート液８を用いて、例１と同様にして、厚さ８０ｎｍの光触媒膜を有するサンプルを得た。
［例９］（比較例）
２−プロパノールの３２．１ｇに、光触媒Ａの９ｇおよびケイ酸ソーダ４号（ケイ酸の１００質量部に対してナトリウムイオンは２６．９質量部。）の８．９ｇを添加したところ、沈殿物が発生しコート液にできなかった。
［例１０］
シリコーンハードコート付きポリカーボネート樹脂板（１００ｍｍ×１００ｍｍ、厚さ５．０ｍｍ）を用意し、そのハードコート表面を蒸留水で洗浄した後に乾燥させ、前処理済ポリカーボネート板とした。
例１で得られたコート液１の２ｍＬを前記処理済ポリカーボネート板の表面に滴下し、スピンコート法により塗布した後、低圧ＵＶ照射装置（センエンジニアリング株式会社製ＰＬ７−２００）を用いランプと前記樹脂板との距離を２ｃｍとして、紫外線を５分間照射し、厚さ８０ｎｍの光触媒膜を有するサンプルを得た。ここでの紫外線とは、低圧水銀ランプによる２５３．７ｎｍと１８４．９ｎｍを主波長とする高エネルギーな紫外線（以降ＵＶ−Ｃと呼ぶ）を指す。
［例１１］
例１０において、シリコーンハードコート付きポリカーボネート樹脂板を洗浄、乾燥後、前述の低圧ＵＶ照射装置を用いてＵＶ−Ｃを２分間照射し、前処理済ポリカーボネート板とした以外は、例１０と同様にしてサンプルを得た。
［例１２］
例１０において、ＵＶ−Ｃを５分間照射する代わりに、メタルハライドランプ（アイグラフィックス株式会社製Ｍ０３−Ｌ３１）を用いランプと前記樹脂板との距離を１０ｃｍとして紫外線を５分間照射し、厚さ８０ｎｍの光触媒膜を有するサンプルを得た。ここでのメタルハライドランプとは、３００〜４５０ｎｍという、低圧水銀ランプより長波長の紫外線の出力が高いランプを指す。
本発明によれば、基材の表面に優れた親水性を付与できる光触媒膜形成用組成物が得られる。また、本発明の光触媒膜形成用組成物を用いて、親水性に優れる光触媒膜が低温で形成でき、該光触媒膜付き基材の表面は親水性に優れる。さらに、本発明の光触媒膜形成用組成物を用いて形成された光触媒膜は、特に汚れ分解性に優れ、また、親水性の持続時間が長い。このため、表面は常に清浄に保たれる。
本発明の光触媒膜形成用組成物を用いて形成された、優れた親水性が付与された基材の表面は、流滴性、防曇性、防汚性、耐磨耗性に優れる。すなわち、基材の表面に親水性が付与されることで、基材の表面に付着する水滴が濡れ広がり、表面が曇らない。また、太陽光等の光が照射されることよってさらに汚れの分解（特に有機物の汚れの分解）が促進される。さらに、降雨等により水が物品の表面を流れ落ちる際に無機物の汚れも流れ落ちる（セルフクリーニング効果）。
【図面の簡単な説明】
図１：本発明の光触媒膜付き基材の一実施例を示す概略断面図。
符号の説明
１０：光触媒膜付き基材
２０：基材
３０：光触媒膜TECHNICAL FIELD The present invention relates to a composition for forming a photocatalyst film that can form a photocatalyst film on the surface of various substrates, a photocatalyst film formed from the composition, and a substrate with a photocatalyst film having the photocatalyst film.
BACKGROUND ART It is known that when a photocatalyst is photoexcited, organic stains and the like attached to the surface of the photocatalyst are decomposed, and as a result, a hydrophilic surface is realized. As a method for forming a photocatalyst film, a thermal decomposition method, which is a kind of dry method, has been conventionally known (for example, JP-T-11-512337). However, the above method has a problem that it is inferior in hydrophilic sustainability as compared with the wet method.
A method of forming a photocatalyst film using a coating composition containing a photocatalyst and silica is also known (for example, Japanese Patent No. 2756474). However, the film using silica of the above method has a problem of poor hydrophilicity and low soil decomposability.
The present invention solves the above-described problems, and can be formed from a composition for forming a photocatalyst film that can form a photocatalyst film that can impart excellent hydrophilicity to the surface of a substrate and that is particularly excellent in soil degradability. An object of the present invention is to provide a photocatalyst film and a substrate with the photocatalyst film. Also provided are a composition for forming a photocatalyst film capable of forming a photocatalyst film having a long hydrophilic duration and excellent surface wear resistance, a photocatalyst film formed from the composition, and a substrate with the photocatalyst film. Objective.
DISCLOSURE OF THE INVENTION The present invention provides a composition for forming a photocatalyst film comprising the photocatalyst semiconductor fine particles, the following silica precursor and a medium as essential components.
Silica precursor: a silicic acid compound containing 0.001 to 1 part by mass of alkali metal ions with respect to 100 parts by mass of silicic acid.
Moreover, this invention provides the base material with a photocatalyst film which has a photocatalyst film formed from the composition for photocatalyst film formation on the surface of a base material, and this photocatalyst film.
BEST MODE FOR CARRYING OUT THE INVENTION The photocatalytic semiconductor fine particles in the present invention are the electrons in the valence band when irradiated with light having an energy larger than the energy difference between the valence band and the conduction electron band of the photocatalyst. A material having the property of generating conduction electrons and holes by excitation of. As such photocatalytic semiconductor fine particles, anatase type titanium oxide, rutile type titanium oxide, tin oxide, zinc oxide, tungsten trioxide, ferric oxide, strontium titanate and the like are preferably mentioned.
The average particle size of the photocatalytic semiconductor fine particles in the present invention is obtained by measuring the aggregate particle size of the fine particles in the composition using light scattering, using a Microtrac UPA particle size distribution meter (manufactured by HONEYWELL), preferably The thickness is 5 to 90 nm, particularly preferably 40 to 70. If the average particle diameter is too small, the photocatalyst fine particles are buried in the formed photocatalyst film, so that various effects of the photocatalyst are hardly exhibited. On the other hand, if the average particle size is too large, the formed photocatalytic film has insufficient mechanical strength, and transparency may not be ensured.
The silica precursor in the present invention is a silicic acid compound in which 0.001 to 1 part by mass of alkali metal ions is contained with respect to 100 parts by mass of silicic acid, and in particular, 0.001 to 0.2 parts by mass is contained. It is particularly preferable that 0.001 to 0.15 parts by mass is included. The alkali metal ion concentration is measured by ICP emission analysis using SPS4000 manufactured by Seiko Instruments Inc. There is no limitation in particular as an alkali metal ion, 1 type may be used and 2 or more types may be used. As the alkali metal ion, sodium ion or lithium ion is preferable. Moreover, a silicic acid compound means the compound which forms a silica film by performing post-processing as mentioned later.
The silica precursor is preferably a product obtained by removing a part of alkali metal ions from an alkali metal salt of silicic acid. The product is obtained, for example, by a method of reducing alkali metal ions from an alkali metal salt of silicic acid using a cation exchange resin. The amount of alkali metal ions to be reduced can be adjusted by controlling the amount of cation exchange resin used, the contact time, the contact method, and the like.
As the cation exchange resin, strong acid cation exchange resin (RSO 3 H type), weak acid cation exchange resin (RCOOH type), etc. can be used, but the reaction rate is to use strong acid cation exchange resin. This is preferable.
In the composition for forming a photocatalyst film of the present invention, the concentration of alkali metal ions is preferably 1 to 80 ppm in terms of mass relative to the composition for forming a photocatalyst, particularly 1 to 40 ppm, more preferably 1 to 20 ppm. Is preferred. When the concentration of alkali metal ions is too small, the stability and hydrophilicity of the composition are lowered, and when it is too large, the stability of the composition is significantly lowered.
Examples of the alkali metal salt of silicic acid include one or more selected from the group of sodium silicate, lithium silicate, and potassium silicate, and sodium silicate and / or lithium silicate are particularly preferable.
As sodium silicate, materials having different composition ratios of SiO 2 / Na 2 O are known, and can be used without any particular limitation. Among these, a material having a small content ratio of Na 2 O is preferable. As commercially available sodium silicate, sodium silicate No. 1 (SiO 2 / Na 2 O molar ratio: 2.0 to 2.3) (sodium silicate No. 1 is a trade name manufactured by Nippon Chemical Industry Co., Ltd.) Hereinafter, the same applies to Nos. 2 to 4, and sodium silicate 2 (same molar ratio: 2.4 to 2.7), sodium silicate 3 (same molar ratio: 3.0 to 3.3). , Sodium silicate No. 4 (same molar ratio: 3.7 to 3.9). In particular, sodium silicate No. 3 or No. 4 having a small content ratio of Na 2 O is particularly preferable.
As lithium silicate, materials having different composition ratios of SiO 2 / Li 2 O are known, and can be used without particular limitation. Among them, the material content ratio of Li 2 O is preferably small. As commercially available lithium silicate, lithium silicate 35 (SiO 2 / Li 2 O molar ratio: 3.5) (lithium silicate 35 is a trade name manufactured by Nippon Chemical Industry Co., Ltd., 45, 75 below. And lithium silicate 45 (same molar ratio: 4.5) and lithium silicate 75 (same molar ratio: 7.5). In particular, lithium silicate 75 having a small content ratio of Li 2 O is particularly preferable.
The composition for forming a photocatalyst film of the present invention preferably contains a surfactant. The surfactant mainly has two functions, the first is to ensure the wettability of the composition to the substrate, and the second is the hydrophilicity of the photocatalyst film formed using the composition. It is to make sex higher. The type of the surfactant is not particularly limited, but a nonionic surfactant is preferably used from the viewpoint of liquid dispersion stability. In particular, a compound in which the hydrophilic part is polyoxyalkylene and the hydrophobic part is a fluorine-containing organic group [for example, C 8 F 17 CH 2 CH 2 CH (CH 3 ) O (CH 2 CH 2 O) x (CH 2 CH (CH 3 ) O) A compound represented by y H [x: y = 70: 30, x + y = 5.72, average molecular weight 800] (hereinafter referred to as surfactant Q) and the like. ] Is preferable. Alternatively, a compound in which the hydrophilic part is polyoxyalkylene and the hydrophobic part is methylpolysiloxane (for example, trade name “L-77” manufactured by Nippon Unicar Co., Ltd.) is preferable.
In the composition for forming a photocatalyst film of the present invention, the silica precursor is preferably contained in an amount of 25 to 900 parts by mass, particularly preferably 50 to 400 parts by mass with respect to 100 parts by mass of the photocatalytic semiconductor fine particles. Moreover, when it contains surfactant, it is preferable that 0.1-10 mass parts of surfactant is contained with respect to 100 mass parts of photocatalyst semiconductor fine particles.
If the concentration of the silica precursor is too large, the durability of the hydrophilicity of the obtained photocatalyst film is lowered, and if it is too small, the obtained photocatalyst film is not hydrophilic. In addition, if the proportion of the surfactant is too large, the appearance of the obtained photocatalyst film is impaired, and the durability of the hydrophilicity is reduced. To do.
The composition for forming a photocatalytic film of the present invention contains a medium. There is no limitation in particular as a medium, The medium containing water is preferable and the solvent may be contained. The solvent is mainly used for dilution and the composition is preferably in the form of a solution. The solvent is preferably a polar solvent such as a lower alcohol, a nitrogen-containing solvent, or a sulfur-containing solvent, and particularly preferably a lower alcohol. Two or more kinds of solvents may be used. As the medium, water is particularly preferable.
The total amount of the photocatalyst semiconductor fine particles and the silica precursor in the composition for forming a photocatalyst film of the present invention may be determined according to the coating method and the desired thickness of the photocatalyst film. The total amount is preferably 0.5 to 50 parts by mass, particularly 0.5 to 15 parts per 100 parts by mass of the photocatalyst-forming composition in consideration of the stability and economics of the composition. Part by mass is preferable, and 0.5 to 5 parts by mass is particularly preferable.
The composition for forming a photocatalyst film of the present invention may contain a functional additive. Examples of the functional additive include coloring dyes, pigments, ultraviolet absorbers, antioxidants, and oxide fine particles (phosphorus pentoxide, magnesium oxide, etc.) other than the photocatalytic semiconductor fine particles in the present invention. The average particle size is preferably 200 nm or less. Etc.) are preferred.
Using the composition for forming a photocatalyst film of the present invention, the composition is applied to the surface of a substrate to form a photocatalyst film, and a substrate with a photocatalyst film is produced. In the photocatalyst film, the silica precursor is converted to silica, but silanol groups may partially remain.
The silica precursor has a silanol group in the compound, that is, a structure represented by SiO s (OH) t (s, t is an integer of 0 or more, and s + t = 4). In other words, oxygen atoms that are not hydroxyl groups are chemically bonded to other silicon atoms.), And silica is formed from the silica precursor by a dehydration condensation reaction.
In the present invention, a photocatalyst film-forming
After applying the composition for forming a photocatalyst film, it is preferable to perform a post-treatment for the purpose of removing the medium and increasing the hardness of the photocatalyst film. Examples of the post-treatment include drying and heating at room temperature, irradiation with electromagnetic waves such as ultraviolet rays and electron beams, and heating. In consideration of the heat resistance of the substrate, the heating is preferably performed at 50 to 700 ° C., particularly at 100 to 350 ° C. for 5 to 60 minutes. In particular, when the base material is a material having low heat resistance such as an organic resin, or when a low molecular compound in the base material diffuses out of the base material by heating, as the post-treatment, an electromagnetic wave such as an ultraviolet ray or an electron beam is used. Irradiation is preferably performed.
In the present invention, the thickness of the resulting photocatalyst film can be controlled by adjusting the concentration of the composition for forming a photocatalyst film, the type of solvent, coating conditions, post-treatment conditions, and the like. If the thickness of the photocatalyst film is too thick, the film has cracks, interference fringes, or scratches that may be noticeable. If it is too thin, the desired photocatalytic performance may not be exhibited. is there. The thickness of the photocatalyst film is preferably 10 to 300 nm, and particularly preferably 10 to 150 nm in consideration of economy.
The base material used for this invention is not specifically limited. The shape of the substrate is not limited to a flat plate, and may have a curvature on the entire surface or a part thereof. The substrate used in the present invention is preferably a transparent substrate such as glass or organic resin. Examples of the glass include soda lime glass mainly used for plate glass and automotive glass. Examples of the organic resin include resins such as polycarbonate, acrylic, polyethylene, polypropylene, and polyethylene terephthalate. In order to increase the strength of the organic resin, a silicone hard coat may be applied to the surface of the resin. When a transparent substrate such as glass or organic resin is used as the substrate, the visible light transmittance (JIS R3106 (1998)) of the substrate with a photocatalyst film is 70% from the viewpoint of visibility. The above is preferable.
The substrate may be pretreated. Examples of the pretreatment include plasma treatment, corona discharge, UV treatment, discharge treatment such as ozone treatment, chemical treatment using acid or alkali, physical treatment using an abrasive, and the like. By performing the pretreatment, the wettability of the composition to the substrate is improved, the composition can be uniformly applied, and the adhesion of the formed photocatalytic film to the substrate can be enhanced. In particular, when the substrate is an organic resin, pretreatment is preferably performed. In general, a pretreatment performed by ultraviolet irradiation by a low-pressure mercury lamp or the like generally used for plastic modification is particularly effective.
In addition, these pre-treatments and post-treatments as described above greatly affect the performance of the obtained film, and therefore it is necessary to optimize the respective treatment conditions. For example, by post-treatment by irradiation with ultraviolet rays, the dehydration condensation polymerization reaction can be advanced to promote the curing of the film, and the adhesion between the substrate surface and the composition can also be improved. Thus, when post-processing can improve adhesiveness with a base material, pre-processing is not essential. In some cases, pretreatment more than necessary may cause the base material to deteriorate and lower the performance.
The substrate with a photocatalyst film of the present invention is preferably used as an article for transportation equipment, an article for construction, and the like because its surface is excellent in hydrophilicity and excellent in transparency. Examples of articles for transportation equipment include bodies of trains, automobiles, ships, aircrafts, window glass, mirrors, various display element cover plates, and the like. Examples of building articles include outer walls, sealant portions, window glass, structures such as bridges and tunnels, and the like. Other applications include lighting cover glass and sound insulation walls.
The base material with a photocatalyst film of the present invention has an antifogging property that its surface is excellent in hydrophilicity, so that water droplets adhering to the surface spread out and the surface does not become cloudy. In addition, organic dirt is decomposed on the surface. Furthermore, the degradation performance of organic dirt is further improved by light irradiation on the surface. In addition, when rain drops fall on the surface due to rain, dirt also flows down simultaneously (self-cleaning effect). The base material with a photocatalyst film of the present invention can be expected to have effects such as ensuring visibility, protecting aesthetics, or reducing maintenance costs.
A photocatalyst film formed from the composition for forming a photocatalyst film of the present invention is obtained by hydrolyzing Si (OR) 4 (R: alkyl group), which is a conventional alkoxysilane, SiO p (OH) q (OR) r (p and q are integers greater than or equal to 0, r is an integer greater than or equal to 1 and p + q + r = 4) (However, in this structure, the oxygen atom which is not a hydroxyl group is another silicon atom. It is superior in hydrophilic sustainability and soil decomposability than a film formed from a composition using a product having a chemical bond.
In the base material with a photocatalyst film of the present invention, another film may be provided between the base material and the photocatalyst film. Examples of the another film include an alkali barrier layer (a layer intended to prevent diffusion of alkali metal into the photocatalytic film when the base material is alkali metal-containing glass).
Examples The present invention will be specifically described with reference to Examples (Examples 1 to 7, 10 to 12) and Comparative Examples (Examples 8 and 9). Samples were evaluated using the following method. The evaluation results are shown in Table 1.
[Hydrophilic]
Immediately after the preparation of the sample, the initial contact angle of water not irradiated with light was measured.
[Hydrophilic durability]
Immediately after the sample was prepared, the sample was kept in an environment free from light for 1 week, and then the contact angle of water was measured. The contact angle is preferably 20 ° or less, and more preferably 10 ° or less from the viewpoint of maintaining hydrophilicity.
[Soil degradability]
Oleic acid is attached to the sample immediately after preparation to create a dirty surface with a water contact angle of about 70 °, and the surface is irradiated with black light (center wavelength 365 nm) at an intensity of 0.5 mW / cm 2 for 6 hours. After that, the contact angle of water was measured. The contact angle is preferably 10 ° or less, and more preferably 6 ° or less from the viewpoint of antifouling properties.
[Membrane strength]
The sample is subjected to a Taber abrasion test (wear number: 100 times, load: 4.9 N), and the haze value before and after the abrasion test is measured (measuring instrument name: direct reading haze computer manufactured by Suga Test Instruments Co., Ltd.). Asked. The amount of change is preferably 3% or less from the viewpoint of wear resistance.
[Anti-fouling]
The sample immediately after preparation was exposed to the outdoors for 1 month, and then the degree of contamination (mostly less noticeable: ◯, slightly more noticeable: Δ, considerably more noticeable: ×) was observed with the naked eye.
[Anti-fogging property]
The sample immediately after preparation was blown, and the presence or absence of cloudiness (no cloudiness: ○, occurrence of cloudiness: x) was observed with the naked eye.
[Example 1]
A soda lime glass plate (100 mm × 100 mm, thickness 3.5 mm) was prepared, the surface was polished with cerium oxide, washed with distilled water and dried to obtain a pretreated glass plate.
Sodium silicate No. 4 (trade name: manufactured by Nippon Chemical Industry Co., Ltd., SiO 2 : 23.35% by mass, Na 2 O: 6.29% by mass. Molar ratio of SiO 2 / Na 2 O: 37.5 g of water 3.83.) Is added, and 30 g of a strongly acidic cation exchange resin (trade name “SK1BH”, manufactured by Mitsubishi Chemical Corporation) is added and stirred at room temperature for 10 minutes to remove demineralized silica. An acid soda solution (0.12 parts by mass of sodium ions with respect to 100 parts by mass of silicic acid) was prepared.
Further, 32.1 g of 2-propanol, 9 g of an aqueous dispersion (solid content concentration: 10% by mass) of anatase type titanium oxide fine particles (average particle size: 56 nm, hereinafter referred to as photocatalyst A) and desalting. 8.9 g of sodium silicate solution was added, and surfactant “L-77” (trade name: manufactured by Nihon Unicar Co., Ltd.) was added so as to be 100 ppm based on the liquid amount, and coating solution 1 (sodium The ion concentration was 12 ppm.).
2 mL of the obtained coating liquid 1 was dropped on the surface of the treated glass plate and applied by a spin coating method, and then baked at 200 ° C. for 60 minutes in an air atmosphere to prepare a sample having a photocatalytic film having a thickness of 80 nm. Obtained.
[Example 2]
Lithium silicate 75 (trade name: manufactured by Nippon Kagaku Kogyo Co., Ltd., SiO 2 : 21.54 mass%, Li 2 O: 1.43 mass%, molar ratio of SiO 2 / Li 2 O: 7 49.), and then 30 g of “SK1BH” was added and stirred for 10 minutes at room temperature to obtain a demineralized lithium silicate solution (the lithium ion was 0 with respect to 100 parts by mass of silicic acid). .13 parts by mass).
In addition, 9 g of photocatalyst A and 8.9 g of demineralized lithium silicate solution were added to 32.1 g of 2-propanol, and “L-77” was added to 100 ppm with respect to the liquid amount. Coating liquid 2 (lithium ion concentration was 13 ppm) was obtained. Using the obtained coating liquid 2, a sample having a photocatalytic film having a thickness of 83 nm was obtained in the same manner as in Example 1.
[Example 3]
To 32.1 g of 2-propanol, 10.5 g of photocatalyst A and 6.69 g of the desalted sodium silicate solution in Example 1 were added, and “L-77” was adjusted to 100 ppm based on the liquid amount. This was added to obtain coating solution 3 (sodium ion concentration was 7 ppm). Using the obtained coating solution 3, a sample having a photocatalytic film having a thickness of 82 nm was obtained in the same manner as in Example 1.
[Example 4]
To 32.1 g of 2-propanol, 4.5 g of photocatalyst A and 15.6 g of the desalted sodium silicate solution in Example 1 were added, and “L-77” was adjusted to 100 ppm with respect to the liquid amount. This was added to obtain coating solution 4 (sodium ion concentration was 23 ppm). A sample having a photocatalytic film having a thickness of 83 nm was obtained in the same manner as in Example 1 using the obtained coating liquid 4.
[Example 5]
A sample was obtained in the same manner as in Example 1 except that the surfactant Q was used instead of “L-77”.
[Example 6]
In Example 1, instead of baking at 200 ° C. for 60 minutes in the air atmosphere, a sample was obtained by baking at 300 ° C. for 30 minutes in the air atmosphere.
[Example 7]
In Example 1, instead of baking at 200 ° C. for 60 minutes in an air atmosphere, a sample was obtained by baking at 650 ° C. for 5 minutes in an air atmosphere.
[Example 8] (Comparative example)
After adding 5 g of tetramethoxysilane to 90 g of ethanol and stirring for 10 minutes, 5 g of an aqueous nitric acid solution (1% by mass) was gradually added to obtain a hydrolysis product B of tetramethoxysilane.
To 32.1 g of 2-propanol, 9 g of photocatalyst A and 8.9 g of the hydrolysis product B were added, and “L-77” was added so as to be 100 ppm with respect to the liquid amount. Liquid 8 (sodium ion concentration was 0 ppm) was obtained.
Using the obtained coating liquid 8, a sample having a photocatalytic film having a thickness of 80 nm was obtained in the same manner as in Example 1.
[Example 9] (Comparative Example)
When 9 g of photocatalyst A and 8.9 g of sodium silicate No. 4 (26.9 parts by mass of sodium ions with respect to 100 parts by mass of silicic acid) were added to 32.1 g of 2-propanol, a precipitate was formed. Occurred and could not be formed into a coating solution.
[Example 10]
A polycarbonate resin plate with a silicone hard coat (100 mm × 100 mm, thickness 5.0 mm) was prepared, and the hard coat surface was washed with distilled water and dried to obtain a pretreated polycarbonate plate.
After 2 mL of the coating liquid 1 obtained in Example 1 was dropped onto the surface of the treated polycarbonate plate and applied by spin coating, the lamp and the above were used using a low-pressure UV irradiation apparatus (PL7-200 manufactured by Sen Engineering Co., Ltd.). A sample having a photocatalyst film with a thickness of 80 nm was obtained by irradiating with ultraviolet rays for 5 minutes at a distance of 2 cm from the resin plate. The term “ultraviolet rays” as used herein refers to high-energy ultraviolet rays (hereinafter referred to as “UV-C”) having principal wavelengths of 253.7 nm and 184.9 nm by a low-pressure mercury lamp.
[Example 11]
In Example 10, the polycarbonate resin plate with a silicone hard coat was washed and dried, and then irradiated with UV-C for 2 minutes using the low-pressure UV irradiation apparatus described above to obtain a pretreated polycarbonate plate. Sample.
[Example 12]
In Example 10, instead of irradiating with UV-C for 5 minutes, a metal halide lamp (M03-L31 manufactured by Eye Graphics Co., Ltd.) was used, and the distance between the lamp and the resin plate was 10 cm. A sample having an 80 nm photocatalytic film was obtained. The metal halide lamp here refers to a lamp having a wavelength of 300 to 450 nm, which has a higher output of ultraviolet light having a longer wavelength than a low-pressure mercury lamp.
The surface of a base material imparted with excellent hydrophilicity, formed using the composition for forming a photocatalyst film of the present invention, is excellent in droplet property, antifogging property, antifouling property, and abrasion resistance. That is, by imparting hydrophilicity to the surface of the base material, water droplets adhering to the surface of the base material spread out and the surface does not become cloudy. In addition, irradiation with light such as sunlight further promotes decomposition of dirt (particularly, decomposition of organic dirt). Further, when water flows down on the surface of the article due to rain or the like, inorganic dirt also flows down (self-cleaning effect).
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a substrate with a photocatalyst film of the present invention.
Claims (15)
シリカ前駆体：ケイ酸１００質量部に対してアルカリ金属イオンが０．００１〜０．２質量部含まれるケイ酸化合物。A composition for forming a photocatalyst film comprising the photocatalyst semiconductor fine particles, the following silica precursor and a medium as essential.
Silica precursor: Silicate compound containing 0.001 to 0.2 parts by mass of alkali metal ions with respect to 100 parts by mass of silicic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002038409 | 2002-02-15 | ||
| JP2002038409 | 2002-02-15 | ||
| PCT/JP2003/001508 WO2003068871A1 (en) | 2002-02-15 | 2003-02-13 | Compositions for forming photocatalytic film and substrate provided with photocatalytic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2003068871A1 JPWO2003068871A1 (en) | 2005-06-02 |
| JP4292992B2 true JP4292992B2 (en) | 2009-07-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003567988A Expired - Fee Related JP4292992B2 (en) | 2002-02-15 | 2003-02-13 | Composition for forming photocatalyst film and substrate with photocatalyst film |
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| Country | Link |
|---|---|
| JP (1) | JP4292992B2 (en) |
| CN (1) | CN1315955C (en) |
| AU (1) | AU2003211967A1 (en) |
| WO (1) | WO2003068871A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006070141A (en) * | 2004-09-01 | 2006-03-16 | Asahi Glass Co Ltd | Composition for forming photocatalyst membrane and substrate with the photocatalyst membrane |
| US7863215B2 (en) | 2005-02-15 | 2011-01-04 | Mitsui Chemicals, Inc. | Photocatalyst, method for producing same, liquid dispersion containing photocatalyst and photocatalyst coating composition |
| CN100423832C (en) * | 2005-09-16 | 2008-10-08 | 长兴化学工业股份有限公司 | Compound photocatalyst and its production process and composition |
| CN101272858A (en) * | 2005-09-30 | 2008-09-24 | 三井化学株式会社 | Photocatalyst-containing organic material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56149465A (en) * | 1980-04-21 | 1981-11-19 | Mitsui Toatsu Chem Inc | Paint composition |
| JP3797037B2 (en) * | 1998-12-04 | 2006-07-12 | 東陶機器株式会社 | Photocatalytic hydrophilic coating composition |
| JP3684913B2 (en) * | 1999-04-22 | 2005-08-17 | 東陶機器株式会社 | Photocatalytic hydrophilic coating hydrophilic recovery agent |
-
2003
- 2003-02-13 WO PCT/JP2003/001508 patent/WO2003068871A1/en active Application Filing
- 2003-02-13 CN CNB038038226A patent/CN1315955C/en not_active Expired - Fee Related
- 2003-02-13 JP JP2003567988A patent/JP4292992B2/en not_active Expired - Fee Related
- 2003-02-13 AU AU2003211967A patent/AU2003211967A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CN1315955C (en) | 2007-05-16 |
| WO2003068871A1 (en) | 2003-08-21 |
| AU2003211967A1 (en) | 2003-09-04 |
| CN1633480A (en) | 2005-06-29 |
| JPWO2003068871A1 (en) | 2005-06-02 |
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