JP4086055B2 - Antifogging and antifouling glass articles - Google Patents
Antifogging and antifouling glass articles Download PDFInfo
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- JP4086055B2 JP4086055B2 JP2005149198A JP2005149198A JP4086055B2 JP 4086055 B2 JP4086055 B2 JP 4086055B2 JP 2005149198 A JP2005149198 A JP 2005149198A JP 2005149198 A JP2005149198 A JP 2005149198A JP 4086055 B2 JP4086055 B2 JP 4086055B2
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- Prior art keywords
- film
- antifogging
- group
- glass article
- antifouling
- Prior art date
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- 239000011521 glass Substances 0.000 title claims description 69
- 230000003373 anti-fouling effect Effects 0.000 title claims description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 55
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 55
- 230000001699 photocatalysis Effects 0.000 claims description 37
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000003513 alkali Substances 0.000 claims description 33
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 33
- 239000011941 photocatalyst Substances 0.000 claims description 32
- 150000001282 organosilanes Chemical class 0.000 claims description 30
- 125000001153 fluoro group Chemical group F* 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 24
- 230000004888 barrier function Effects 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000000903 blocking effect Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 9
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
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- 150000001875 compounds Chemical class 0.000 description 15
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- 238000012423 maintenance Methods 0.000 description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
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- 239000002253 acid Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
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- 239000010936 titanium Substances 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 7
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- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 7
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- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 6
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 125000001309 chloro group Chemical class Cl* 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 238000011109 contamination Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000000460 chlorine Substances 0.000 description 2
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- FMLYSTGQBVZCGN-UHFFFAOYSA-N oxosilicon(2+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Si+2]=O.[O-2].[O-2] FMLYSTGQBVZCGN-UHFFFAOYSA-N 0.000 description 2
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- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
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- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
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- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
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Description
本発明は、防曇防汚ガラス物品、特に自動車、建築用の防曇防汚ガラス板およびメガネ、鏡、レンズ、ショーケースやその他の防曇防汚ガラス物品に関するものである。 The present invention relates to an antifogging and antifouling glass article, particularly to an antifogging and antifouling glass plate for automobiles and buildings, and glasses, a mirror, a lens, a showcase and other antifogging and antifouling glass articles.
主に自動車および建築の分野では、古くから防曇防汚ガラス板に対する強いニーズがある。特に自動車においては、安全走行の観点から窓ガラスへの防曇防汚性付与が重要な課題になりつつある。 Mainly in the field of automobiles and architecture, there is a strong need for anti-fogging and antifouling glass plates for a long time. Particularly in automobiles, imparting anti-fogging and antifouling properties to window glass is becoming an important issue from the viewpoint of safe driving.
従来から、ガラス物品への様々な防曇防汚コーティングが検討されてきた。例えば、界面活性剤を含有した有機及び／または無機薄膜のコーティング（以下「方法１」、例えば特許文献１）、親水性ポリマーのコーティング（以下「方法２」、例えば特許文献２）、親水性有機官能基を含有する有機無機複合膜のコーティング（以下「方法３」、例えば特許文献３）等である。 Conventionally, various anti-fogging and antifouling coatings on glass articles have been studied. For example, a coating of an organic and / or inorganic thin film containing a surfactant (hereinafter “Method 1”, for example, Patent Document 1), a hydrophilic polymer coating (hereinafter “Method 2”, for example, Patent Document 2), a hydrophilic organic It is a coating of an organic-inorganic composite film containing a functional group (hereinafter “Method 3”, for example, Patent Document 3).
また最近、光触媒として作用する酸化チタン薄膜をガラス表面に被覆した防曇防汚ガラスが提案された（以下「方法４」、例えば非特許文献１）。これは、ガラスの表面の酸化チタンが紫外光を吸収しそのエネルギーにより、ガラス表面に吸着した有機物が効率よく酸化分解される結果、著しい親水性を有する清浄な表面が得られることを利用したものである。また材料的に全て無機物で構成され機械的な強度にも優れている他、一旦汚れが付着しても光さえ当たれば、再び表面が清浄化され、親水性表面が復活する。表面が親水性を維持すれば、都会型汚れである親油性の黒い汚れが付き難く、また付いた汚れは降雨により除去され易く（例えば、非特許文献２、非特許文献３）、いわゆるセルフクリーニング性を持ち、防汚材料として使用できる。
前記方法１は、初期性能には優れているものの、徐々に界面活性剤が消費されることから、寿命が短いという欠点がある。 Although the method 1 is excellent in the initial performance, the surfactant is gradually consumed, so that the life is short.
前記方法２は、用途によっては有効な手段であるが、自動車、建築等の比較的大きな機械的強度が要求されるガラスに適用することはできない。 Although the method 2 is an effective means depending on the application, it cannot be applied to glass that requires a relatively large mechanical strength, such as an automobile or a building.
前記方法３は、防曇性能と機械的強度を両立させるために考案されたものであるが、いずれも性能面で限界がある。また、一旦汚れが付着した場合には防曇性能が著しく低下するという問題もある。 The method 3 has been devised in order to achieve both anti-fogging performance and mechanical strength, but all have limitations in terms of performance. There is also a problem that once the dirt is adhered, the anti-fogging performance is remarkably lowered.
前記方法４は原理的には他の方法では実現できない特徴を有しているものの、自動車および建物の内部における紫外光の強度は非常に弱いことから、実用に供する様な防曇防汚ガラス物品は今までのところ得られていない。 Although the method 4 has characteristics that cannot be realized by other methods in principle, the anti-fogging and antifouling glass article for practical use since the intensity of ultraviolet light in the interior of automobiles and buildings is very weak. Has not been obtained so far.
本発明は、自動車および建築物の窓ガラスならびにメガネ等に使用できる優れた長期防曇防汚性能を有する防曇防汚ガラス物品を提供することを目的としている。 An object of the present invention is to provide an anti-fogging and antifouling glass article having excellent long-term antifogging and antifouling performance that can be used for window glass and glasses for automobiles and buildings.
本発明は、ガラス基材の表面に、アルカリ遮断膜、光触媒膜、ならびに酸化珪素層またはポリアルキレンオキシド基、アルキル基、アルケニル基およびアリール基からなる群より選ばれる少なくとも一種の官能基を分子内に含むオルガノシランもしくはその加水分解物の層からなる有機物付着防止層をその順に積層してなる防曇防汚ガラス物品であって、前記光触媒膜が酸化チタンを１０重量％以上含みかつフッ素原子を含有してなる防曇防汚ガラス物品ある。
また本発明は、前記光触媒膜が酸化チタンからなりかつフッ素原子を含有してなる前記防曇防汚ガラス物品である。
また本発明は、前記光触媒膜が０．００２〜１重量％のフッ素原子を含有してなる前記防曇防汚ガラス物品である。
また本発明は、ガラス基材の表面に、アルカリ遮断膜、光触媒膜、ならびに酸化珪素層またはポリアルキレンオキシド基、アルキル基、アルケニル基およびアリール基からなる群より選ばれる少なくとも一種の官能基を分子内に含むオルガノシランもしくはその加水分解物の層からなる有機物付着防止層をその順に積層してなる防曇防汚ガラス物品であって、前記光触媒膜が酸化チタンを１０重量％以上含みかつ前記アルカリ遮断膜がフッ素原子を含有してなる防曇防汚ガラス物品である。
また本発明は、前記光触媒膜が酸化チタンからなる前記防曇防汚ガラス物品である。
また本発明は、前記アルカリ遮断膜が０．００２〜１０重量％のフッ素原子を含有してなる前記防曇防汚ガラス物品である。
また本発明は、前記光触媒膜がさらにフッ素原子を含む前記防曇防汚ガラス物品である。
また本発明は、前記有機物付着防止層が０．５〜５の厚み方向平均分子層数を有する前記防曇防汚ガラス物品である。
In the present invention, an alkali blocking film, a photocatalytic film, and a silicon oxide layer or at least one functional group selected from the group consisting of a polyalkylene oxide group, an alkyl group, an alkenyl group, and an aryl group are formed on the surface of a glass substrate. An antifogging and antifouling glass article comprising an organic substance adhesion preventing layer composed of an organosilane or a hydrolyzate layer thereof in that order, wherein the photocatalytic film contains 10% by weight or more of titanium oxide and contains fluorine atoms. There is an antifogging and antifouling glass article.
The present invention is also the antifogging and antifouling glass article, wherein the photocatalytic film is made of titanium oxide and contains fluorine atoms.
Moreover, this invention is the said anti-fogging antifouling glass article in which the said photocatalyst film | membrane contains 0.002-1 weight% fluorine atom.
Further, the present invention provides an alkali blocking film, a photocatalytic film, and a silicon oxide layer or at least one functional group selected from the group consisting of a polyalkylene oxide group, an alkyl group, an alkenyl group, and an aryl group on the surface of a glass substrate. An anti-fogging and antifouling glass article comprising an organic anti-adhesion layer composed of an organosilane or a hydrolyzate layer contained therein in that order, wherein the photocatalytic film contains 10% by weight or more of titanium oxide and the alkali This is an anti-fogging and antifouling glass article in which the barrier film contains fluorine atoms.
The present invention also provides the antifogging and antifouling glass article, wherein the photocatalytic film is made of titanium oxide.
Further, the present invention is the antifogging and antifouling glass article, wherein the alkali barrier film contains 0.002 to 10% by weight of fluorine atoms.
Moreover, this invention is the said anti-fogging antifouling glass article in which the said photocatalyst film | membrane contains a fluorine atom further.
Moreover, this invention is the said anti-fogging antifouling glass article in which the said organic substance adhesion prevention layer has the thickness direction average molecular layer number of 0.5-5.
ここで、Ｒａ値、Ｓｍ値はＪＩＳ Ｂ０６０１（１９９４）記載の方法により定義され、原子間力顕微鏡（例えば、セイコー電子株式会社製ＳＰＩ３７００）や電子顕微鏡（例えば、株式会社日立製作所製Ｈ−６００）を用いて観察、測定した断面曲線から計算できる。 Here, the Ra value and the Sm value are defined by the method described in JIS B0601 (1994), and an atomic force microscope (for example, SPI 3700 manufactured by Seiko Electronics Co., Ltd.) or an electron microscope (for example, H-600 manufactured by Hitachi, Ltd.). It can be calculated from the cross-sectional curve observed and measured using
光触媒を用いて優れた防曇防汚機能を得るためには三つの条件を同時に満足する必要がある。一つは、光触媒膜の表面に吸着した、曇りや汚れの原因となる有機物を効率よく酸化分解すること（高光触媒活性）である。二つ目は、有機物が表面に吸着しにくいこと（吸着防止性）である。三つ目は、特に、防曇性に必要なことであるが、水滴が付着したときの見かけの接触角を小さくすること（低接触角化）である。以上の三つが満足されて初めて、長期にわたる良好な防曇防汚性能が発現できることになる。 In order to obtain an excellent antifogging and antifouling function using a photocatalyst, it is necessary to satisfy three conditions simultaneously. One is to efficiently oxidize and decompose organic matter adsorbed on the surface of the photocatalyst film and causing fogging and dirt (high photocatalytic activity). The second is that organic substances are difficult to adsorb on the surface (anti-adsorption property). The third is particularly necessary for anti-fogging properties, but is to reduce the apparent contact angle when water droplets adhere (lower contact angle). Only when the above three conditions are satisfied, good antifogging and antifouling performance over a long period of time can be expressed.
本発明において、光触媒としては，ＴｉＯ２，ＺｎＯ，ＺｎＳ，ＷＯ３，Ｆｅ２Ｏ３，ＧａＡｓ，ＣｄＳｅ，ＧａＡｓＰ，ＣｄＳ，ＳｒＴｉＯ３，ＧａＰ，Ｉｎ２Ｏ３，ＭｏＯ３等が用いられるが、光触媒活性の高さと化学的な安定性から，現在最も広範に用いられている光触媒はＴｉＯ２であり，本発明にも特に好適に使用することができる。以下代表的に酸化チタンについて説明する。 In the present invention, TiO 2 , ZnO, ZnS, WO 3 , Fe 2 O 3 , GaAs, CdSe, GaAsP, CdS, SrTiO 3 , GaP, In 2 O 3 , MoO 3 and the like are used as the photocatalyst. Because of its high activity and chemical stability, the most widely used photocatalyst at present is TiO 2 and can be used particularly favorably in the present invention. Hereinafter, titanium oxide will be representatively described.
ガラス基材表面に直接に酸化チタン膜のような光触媒膜をコーティングしても、高い光触媒活性は得られない。これは、アルカリ金属を含有するガラス基材の中から熱処理の際に拡散して出てきたＮａイオンのようなアルカリ金属イオンが酸化チタン膜の結晶性を低下させるからである。この酸化チタン膜の結晶性の低下を防止するために、本発明において、ガラス基材に酸化珪素膜その他のアルカリ遮断膜を設け、その上に酸化チタンからなる光触媒膜または酸化チタンを含む光触媒膜をコーティングする。光触媒膜として酸化チタンを含む膜を用いる場合は、酸化チタンの含有率が、１０重量％以上であることが好ましい。酸化チタンが１０重量％より少ないと、表面の光触媒活性が低くなりすぎ実用的ではない。 Even if a photocatalytic film such as a titanium oxide film is directly coated on the surface of the glass substrate, high photocatalytic activity cannot be obtained. This is because alkali metal ions such as Na ions diffused out of the glass substrate containing alkali metal during the heat treatment lower the crystallinity of the titanium oxide film. In order to prevent the crystallinity of the titanium oxide film from being lowered, in the present invention, a glass substrate is provided with a silicon oxide film or other alkali blocking film, and a photocatalytic film made of titanium oxide or a photocatalytic film containing titanium oxide is provided thereon. Coating. When a film containing titanium oxide is used as the photocatalytic film, the content of titanium oxide is preferably 10% by weight or more. If the titanium oxide is less than 10% by weight, the surface photocatalytic activity becomes too low to be practical.
［アルカリ遮断膜］前記アルカリ遮断膜としては、酸化珪素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、および酸化セリウムからなる群より選ばれる単成分または多成分の組成からなるものが好適に使用される。これらの中で、酸化珪素（シリカ）単成分または主成分が酸化珪素である多成分のものが好ましく、酸化珪素と酸化ジルコニウムの２成分系金属酸化物であることがさらに好ましい。主成分が酸化珪素である金属酸化物は屈折率が低くガラス板の光学的特性を大きく損なうことなく成膜を行うことができ好ましく、酸化珪素と酸化ジルコニウムの２成分系金属酸化物では、アルカリ遮断性能が非常に高いのでさらに好ましく、酸化ジルコニウムの含有率は１重量％以上３０重量％以下のものが特に好ましい。含有率が１重量％より低いとアルカリ遮断性能向上効果は酸化珪素単体とあまり差がなく、３０重量％より高いとアルカリ遮断性能向上効果がもはや向上しないばかりか、屈折率増大による反射率向上が起こる傾向が強くなりガラス板の光学的特性を制御し難くなるので好ましくない。 [Alkali Barrier Film] As the alkali barrier film, a film composed of a single component or a multicomponent composition selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and cerium oxide is preferably used. Among these, a single component of silicon oxide (silica) or a multicomponent component whose main component is silicon oxide is preferable, and a two-component metal oxide of silicon oxide and zirconium oxide is more preferable. A metal oxide whose main component is silicon oxide has a low refractive index and can be formed without significantly degrading the optical characteristics of the glass plate. In the case of a two-component metal oxide of silicon oxide and zirconium oxide, The barrier performance is very high because it is very high, and the zirconium oxide content is particularly preferably not less than 1% by weight and not more than 30% by weight. When the content is lower than 1% by weight, the alkali barrier performance improvement effect is not much different from that of silicon oxide alone. When the content is higher than 30% by weight, the alkali barrier performance improvement effect is no longer improved, and the reflectance is improved by increasing the refractive index. Since the tendency to occur becomes strong and it becomes difficult to control the optical characteristics of the glass plate, it is not preferable.
前記アルカリ遮断膜の厚みは、１０ｎｍ以上３００ｎｍ以下であることが好ましい。厚みが１０ｎｍより薄いとアルカリ遮断効果が充分でなく、また３００ｎｍより厚いと膜による干渉色が顕著に認められるようになりガラス板の光学特性を制御し難くなるので好ましくない。 The thickness of the alkali blocking film is preferably 10 nm or more and 300 nm or less. If the thickness is less than 10 nm, the alkali blocking effect is not sufficient, and if it is more than 300 nm, the interference color due to the film becomes noticeable and it becomes difficult to control the optical characteristics of the glass plate, which is not preferable.
前記アルカリ遮断膜は公知の方法で形成できる。例えば、ゾルゲル法（例えば、山本雄二、神谷寛一、作花済夫、窯業協会誌、９０、３２８〜３３３（１９８２））、液相析出法（例えば特公平１−５９２１０、特公平４−１３３０１）、真空成膜法（真空蒸着、スパッタ）、焼付け法・スプレーコート（例えば特開昭５３−１２４５２３、特開昭５６−９６７４９）、ＣＶＤ法（例えば特開昭５５−９０４４１、特開平１−２０１０４６、特開平５−２０８８４９）などが例示できる。 The alkali barrier film can be formed by a known method. For example, the sol-gel method (for example, Yuji Yamamoto, Kouichi Kamiya, Sakuo Sakuhana, Journal of Ceramic Industry Association, 90, 328-333 (1982)), liquid phase precipitation method (for example, Japanese Patent Publication Nos. 1-59210 and 4-13301) , Vacuum film forming method (vacuum deposition, sputtering), baking method / spray coating (for example, JP-A-53-124523, JP-A-56-96749), CVD method (for example, JP-A-55-90441, JP-A-1-201046) JP-A-5-208849).
ゾルゲル法による、アルカリ遮断膜は、加水分解・縮重合可能な有機金属化合物またはクロロシリル基含有化合物またはそれらの加水分解物を含む塗布液をガラス基材上に塗布、乾燥、および必要に応じて熱処理することにより形成される。 The alkali barrier film by the sol-gel method is a coating solution containing an organometallic compound or a chlorosilyl group-containing compound or a hydrolyzate thereof that can be hydrolyzed / condensed on a glass substrate, dried, and optionally heat-treated. It is formed by doing.
前記微粒子の溶媒としては、水、メタノール、エタノール、プロパノール等の単体または混合体が好ましく、水がさらに好ましい。 The solvent for the fine particles is preferably a simple substance or a mixture of water, methanol, ethanol, propanol or the like, and more preferably water.
前記アルカリ遮断膜形成用塗布液中に含ませる加水分解・縮重合可能な有機金属化合物としては、金属アルコキシド、例えば、珪素、アルミニウム、ジルコニウム、チタン等のメトキシド、エトキシド、プロポキシド、ブトキシドなどが、単体あるいは混合体として好ましく用いられ、高分子量タイプのアルキルシリケート、例えばコルコート株式会社製「エチルシリケート４０」や三菱化学株式会社製「ＭＳ５６」なども用いることができる。前記有機金属化合物加水分解物として、市販のアルコキシシラン加水分解液、例えばコルコート株式会社製「ＨＡＳ−１０」、株式会社日板研究所製「セラミカＧ−９１」、「Ｇ−９２−６」、日本曹達株式会社製「アトロンＮＳＩ−５００」などを用いることができる。 Examples of the organometallic compound that can be hydrolyzed and polycondensed to be included in the coating solution for forming an alkali barrier film include metal alkoxides, for example, methoxide such as silicon, aluminum, zirconium, and titanium, ethoxide, propoxide, butoxide, High molecular weight type alkyl silicates such as “Ethyl silicate 40” manufactured by Colcoat Co., Ltd. and “MS56” manufactured by Mitsubishi Chemical Co., Ltd. can also be used. As the organometallic compound hydrolyzate, a commercially available alkoxysilane hydrolyzed solution, for example, “HAS-10” manufactured by Colcoat Co., Ltd., “Ceramica G-91”, “G-92-6” manufactured by Nihon Ita Laboratory, “Atron NSI-500” manufactured by Nippon Soda Co., Ltd. can be used.
前記アルカリ遮断膜形成用塗布液中に含ませるクロロシリル基含有化合物とは、クロロシリル基（−ＳｉＣｌｎＸ３−ｎ、ここでｎは１，２，または３であり、Ｘは水素、またはそれぞれ炭素数が１〜１０のアルキル基、アルコキシ基、またはアシロキシ基である）を分子内に少なくとも１個有する化合物であり、その中でも、少なくとも２個の塩素を有する化合物が好ましく、シランＳｉｎＨ２ｎ＋２（ここでｎは１〜５の整数）の中の少なくとも２個の水素を塩素で置換し、他の水素を必要に応じて前記アルキル基、アルコキシ基、またはアシロキシ基で置換したクロロシランおよびその縮重合物が好ましく、例えば、テトラクロロシラン（四塩化珪素、ＳiＣl４）、トリクロロシラン（ＳiＨＣl３）、トリクロロモノメチルシラン（ＳiＣＨ３Ｃl３）、ジクロロシラン（ＳiＨ２Ｃl２）、およびＣl−（ＳiＣl２Ｏ）ｎ−ＳiＣl３（ｎは１〜１０の整数）等を挙げることができる。前記クロロシリル基含有化合物の加水分解物も使用することができ、これらの中から、単独でまたは複数を組み合わせて使用することができるが、最も好ましいクロロシリル基含有化合物はテトラクロロシランである。クロロシリル基は反応性が非常に高く、自己縮合または基材表面と縮合反応をすることにより緻密な被膜を形成する。 The chlorosilyl group-containing compound contained in the coating solution for forming an alkali blocking film is a chlorosilyl group (—SiCl n X 3-n , where n is 1, 2, or 3 and X is hydrogen or carbon, respectively. A compound having at least one alkyl group, an alkoxy group, or an acyloxy group having a number of 1 to 10 in the molecule. Among them, a compound having at least two chlorines is preferable, and silane Si n H 2n + 2 ( Wherein n is an integer of 1 to 5, and at least two hydrogens are substituted with chlorine, and other hydrogens are optionally substituted with the alkyl group, alkoxy group, or acyloxy group, and polycondensation thereof. For example, tetrachlorosilane (silicon tetrachloride, SiCl 4 ), trichlorosilane (SiHCl 3 ), trichloromonomethylsila Down (SiCH 3 Cl 3), dichlorosilane (SiH 2 Cl 2), and Cl- (SiCl 2 O) n -SiCl 3 (n is an integer of from 1 to 10), and the like. A hydrolyzate of the chlorosilyl group-containing compound can also be used, and among these, a single chlorosilyl group-containing compound can be used alone or in combination, and the most preferable chlorosilyl group-containing compound is tetrachlorosilane. The chlorosilyl group has very high reactivity, and forms a dense film by self-condensation or condensation reaction with the substrate surface.
前記有機金属化合物またはクロロシリル基含有化合物またはそれらの加水分解物を含む溶液の溶媒は、実質的に前記有機金属化合物またはクロロシリル基含有化合物またはそれらの加水分解物を溶解すれば基本的に何でも良いが、メタノール、エタノール、プロパノール、ブタノール等のアルコール類が最も好ましく、前記有機金属化合物、クロロシリル基含有化合物、それらの加水分解物の合計を１〜３０重量％の濃度で含有させる。 The solvent of the solution containing the organometallic compound or the chlorosilyl group-containing compound or a hydrolyzate thereof may be basically anything as long as it substantially dissolves the organometallic compound, the chlorosilyl group-containing compound or the hydrolyzate thereof. Alcohols such as methanol, ethanol, propanol and butanol are most preferable, and the total of the organometallic compound, the chlorosilyl group-containing compound and the hydrolyzate thereof is contained at a concentration of 1 to 30% by weight.
前記有機金属化合物の加水分解には水が必要である。これは、酸性、中性の何れでも良いが、加水分解を促進するためには、触媒作用を有する塩酸、硝酸、硫酸、酢酸、クエン酸、スルホン酸等で酸性にした水を用いるのが好ましい。酸の添加量は特に限定されないが、有機金属化合物に対してモル比で０．００１〜５が良い。添加酸量が、モル比で０．００１より少ないと、有機金属化合物の加水分解の促進が充分でなく、またモル比で５より多くても、もはや加水分解促進の効果が向上せず、好ましくない。 Water is required for hydrolysis of the organometallic compound. This may be either acidic or neutral, but in order to promote hydrolysis, it is preferable to use water acidified with catalytic hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sulfonic acid or the like. . Although the addition amount of an acid is not specifically limited, 0.001-5 are good by molar ratio with respect to an organometallic compound. When the amount of the added acid is less than 0.001 in terms of molar ratio, the hydrolysis of the organometallic compound is not promoted sufficiently. Absent.
前記有機金属化合物の加水分解に必要な水の添加量は、有機金属化合物に対してモル比で０．１〜１００が良い。水添加量がモル比で０．１より少ないと、有機金属化合物の加水分解の促進が充分でなく、またモル比で１００より多いと、液の安定性が低下する傾向になり好ましくない。 The addition amount of water necessary for hydrolysis of the organometallic compound is preferably 0.1 to 100 in terms of molar ratio with respect to the organometallic compound. If the amount of water added is less than 0.1 in terms of molar ratio, the hydrolysis of the organometallic compound is not sufficiently promoted, and if it is more than 100 in terms of molar ratio, the stability of the liquid tends to decrease.
前記クロロシリル基含有化合物を用いる場合には、必ずしも水や酸の添加は必要ではない。付加的に全く水や酸を添加しなくても、溶媒中に含まれていた水分や雰囲気中の水分などにより加水分解が進行する。また、この加水分解に伴って液中に塩酸が遊離し、さらに加水分解が進行する。しかし、付加的に水や酸を加えても何ら差し支えない。 When the chlorosilyl group-containing compound is used, it is not always necessary to add water or acid. Even if no water or acid is added at all, hydrolysis proceeds due to moisture contained in the solvent or moisture in the atmosphere. Further, with this hydrolysis, hydrochloric acid is liberated in the liquid, and further hydrolysis proceeds. However, there is no problem even if water or acid is added additionally.
前記有機金属化合物やクロロシリル基含有化合物またはそれらの加水分解物を溶媒とともに混合し、必要に応じて水、酸触媒、および分散助剤を添加して、コーティング液を調製する。この時、有機金属化合物とクロロシリル基含有化合物は単独で用いても混合して用いてもどちらでも良い。 The organometallic compound, the chlorosilyl group-containing compound, or a hydrolyzate thereof is mixed with a solvent, and water, an acid catalyst, and a dispersion aid are added as necessary to prepare a coating solution. At this time, the organometallic compound and the chlorosilyl group-containing compound may be used alone or in combination.
前記有機金属化合物またはクロロシリル基含有化合物を溶媒に溶かし、触媒と水を加え、１０℃と溶液の沸点の間の所定の温度で５分間から２日間加水分解させ、アルカリ遮断膜形成用コーティング液を得る。なお、クロロシリル基含有化合物を用いる場合には触媒および水は特別に添加する必要はない。また、有機金属化合物の加水分解工程を省略するために、前記市販の有機金属化合物加水分解物溶液を用いても良い。得られたコーティング液は、その後コーティング方法に応じて適当な溶媒で希釈しても構わない。 The organometallic compound or chlorosilyl group-containing compound is dissolved in a solvent, a catalyst and water are added, and the mixture is hydrolyzed at a predetermined temperature between 10 ° C. and the boiling point of the solution for 5 minutes to 2 days. obtain. In addition, when using a chlorosilyl group containing compound, it is not necessary to add a catalyst and water specially. Further, in order to omit the hydrolysis step of the organometallic compound, the commercially available organometallic compound hydrolyzate solution may be used. The obtained coating solution may then be diluted with a suitable solvent according to the coating method.
次に、液相析出法によるアルカリ遮断膜は、例えば、１〜４ｍｏｌ／Ｌ濃度の珪フッ化水素酸のシリカ過飽和水溶液に珪酸塩ガラス基材を２５〜５０℃で１〜４時間浸漬することにより前記水溶液中から酸化珪素が基材の表面に析出し、アルカリ遮断酸化珪素膜が形成される。前記シリカ過飽和珪フッ化水素酸の水溶液は、１〜４ｍｏｌ／Ｌ濃度の珪フッ化水素酸水溶液に溶解させ、さらにホウ酸を１×１０−４〜１００×１０−４ｍｏｌ／Ｌの濃度になるように添加することにより得られる。 Next, the alkali barrier film by the liquid phase deposition method is, for example, immersing a silicate glass substrate in a silica supersaturated aqueous solution of hydrosilicofluoric acid having a concentration of 1 to 4 mol / L for 1 to 4 hours at 25 to 50 ° C. As a result, silicon oxide is deposited on the surface of the substrate from the aqueous solution, and an alkali-blocking silicon oxide film is formed. The aqueous solution of silica supersaturated hydrosilicofluoric acid is dissolved in an aqueous hydrosilicofluoric acid solution having a concentration of 1 to 4 mol / L, and boric acid is further adjusted to a concentration of 1 × 10 −4 to 100 × 10 −4 mol / L. It is obtained by adding so that it becomes.
［光触媒膜］前記アルカリ遮断膜の上にコーティングする光触媒膜の光触媒活性は膜厚に強く依存する。膜厚が薄すぎると光を充分に吸収できず、厚すぎると膜中で生じた光キャリヤーが膜の外側表面まで拡散できないために、ともに触媒活性が低下する。使用条件によっても最適な膜厚は異なるが、１０ｎｍ〜５００ｎｍの範囲、より好ましくは５０〜２００ｎｍの範囲で良好な光触媒活性を発現させることができる。 [Photocatalytic film] The photocatalytic activity of the photocatalytic film coated on the alkali blocking film strongly depends on the film thickness. If the film thickness is too thin, light cannot be absorbed sufficiently. If the film thickness is too thick, the photocarriers generated in the film cannot diffuse to the outer surface of the film, so that the catalytic activity decreases. Although the optimum film thickness varies depending on the use conditions, good photocatalytic activity can be exhibited in the range of 10 nm to 500 nm, more preferably in the range of 50 to 200 nm.
本発明における酸化チタンからなる光触媒膜または酸化チタンを含む光触媒膜は通常の薄膜製造方法を利用して作製されるが、中でもゾルゲル法が好ましく適用される。ゾルは、チタンアルコキシドまたはチタンアルコキシドと他の金属アルコキシドを同時に加水分解させて得られる。また酸化チタン微粒子を無機バインダー（チタン以外の金属のアルコキシドを含有する）中に分散させた市販の液を用いるのが簡単であり、好ましく用いられる。市販の液の例としては、「ＳＴ−Ｋ０３」（石原産業株式会社製、酸化チタン含有量５重量％、無機バインダー含有量５重量％）および「ＣＡ−６２」（多木化学株式会社製、酸化チタン含有量６重量％、バインダー量１．５重量％）等が挙げられる。 The photocatalyst film made of titanium oxide or the photocatalyst film containing titanium oxide in the present invention is produced by using an ordinary thin film production method, and among them, the sol-gel method is preferably applied. The sol is obtained by simultaneously hydrolyzing titanium alkoxide or titanium alkoxide and another metal alkoxide. Further, it is easy to use a commercially available liquid in which titanium oxide fine particles are dispersed in an inorganic binder (containing an alkoxide of a metal other than titanium), and is preferably used. Examples of commercially available liquids include “ST-K03” (Ishihara Sangyo Co., Ltd., titanium oxide content 5 wt%, inorganic binder content 5 wt%) and “CA-62” (Taki Chemical Co., Ltd., A titanium oxide content of 6% by weight, and a binder amount of 1.5% by weight).
これらアルカリ遮断膜の上に酸化チタン系薄膜を形成した後に、緻密化や酸化チタン結晶性の向上のために、好ましくは４５０〜６５０℃で１０分〜２時間の条件で加熱処理する。 After forming a titanium oxide-based thin film on these alkali blocking films, heat treatment is preferably performed at 450 to 650 ° C. for 10 minutes to 2 hours for densification and improvement of titanium oxide crystallinity.
［光触媒膜へのフッ素ドープ］さらに前記光触媒膜中に微量のフッ素原子をドーピングすることにより、さらに光触媒活性を増大させることが可能である。ドーパントとしてはトリフルオロ酢酸等が使用できる。これらトリフルオロ酢酸をはじめとするドーパントは、その後の熱処理によって分解し、原子状態のフッ素として酸化チタン結晶格子中にドーピングされる。フッ素原子の大きさは酸素原子の大きさとほぼ同じであるので、ドーピングされたフッ素原子は主に酸化チタンの酸素原子と置換された形で存在するものと考えられる。 [Fluorine doping of the photocatalytic film] Further, the photocatalytic activity can be further increased by doping a small amount of fluorine atoms into the photocatalytic film. A trifluoroacetic acid etc. can be used as a dopant. These dopants including trifluoroacetic acid are decomposed by a subsequent heat treatment, and are doped into the titanium oxide crystal lattice as fluorine in an atomic state. Since the size of the fluorine atom is almost the same as the size of the oxygen atom, it is considered that the doped fluorine atom exists mainly in a form substituted for the oxygen atom of titanium oxide.
ゾルゲル法で酸化チタン系光触媒膜を形成する場合、その原料であるチタンアルコキシドの溶液や酸化チタン微粒子分散液中に熱分解可能なフッ素化合物、例えばトリフルオロ酢酸（ＴＦＡ）を添加することにより、焼成等の熱処理後の膜中にはフッ素原子が０．００２〜１重量％ドープされ、さらに光触媒活性を増大させることができる。 When a titanium oxide photocatalyst film is formed by the sol-gel method, it is baked by adding a thermally decomposable fluorine compound such as trifluoroacetic acid (TFA) into the raw material titanium alkoxide solution or titanium oxide fine particle dispersion. The film after the heat treatment such as the above is doped with 0.002 to 1% by weight of fluorine atoms, and can further increase the photocatalytic activity.
また、真空蒸着法や化学気相蒸着（ＣＶＤ）法で酸化チタン光触媒膜を形成する場合も、原料中にフッ素化合物を添加することで同様のフッ素原子ドープが可能である。 Further, when a titanium oxide photocatalytic film is formed by a vacuum vapor deposition method or a chemical vapor deposition (CVD) method, the same fluorine atom doping can be performed by adding a fluorine compound to the raw material.
膜中のフッ素原子ドープ量が０．００２重量％より少ないと、光触媒活性の増大効果があまり顕著でなく、また１重量％より多くても光触媒活性がもはや増大しないので好ましくない。 When the fluorine atom doping amount in the film is less than 0.002% by weight, the effect of increasing the photocatalytic activity is not so remarkable, and when it is more than 1% by weight, the photocatalytic activity is no longer increased.
一方、アルカリ遮断膜中にフッ素原子をドープすることによっても、熱処理により酸化チタン系膜中にフッ素原子が拡散して、同様のドープ効果が得られる。アルカリ遮断膜中のフッ素原子ドープ量は０．００２重量％以上１０重量％以下が好ましい。アルカリ遮断膜中のフッ素原子ドープ量が０．００２重量％より少ないと、光触媒層の光触媒活性の増大効果があまり顕著でなく、また１０重量％より多くても光触媒層の光触媒活性がもはや増大しないので好ましくない。 On the other hand, also by doping fluorine atoms in the alkali blocking film, the fluorine atoms diffuse into the titanium oxide film by heat treatment, and the same doping effect is obtained. The fluorine atom doping amount in the alkali blocking film is preferably 0.002 wt% or more and 10 wt% or less. When the fluorine atom doping amount in the alkali blocking film is less than 0.002% by weight, the effect of increasing the photocatalytic activity of the photocatalyst layer is not so remarkable, and when it is more than 10% by weight, the photocatalytic activity of the photocatalyst layer no longer increases. Therefore, it is not preferable.
アルカリ遮断膜中へのフッ素原子ドープは、ゾルゲル法や真空蒸着法や焼付け法やスプレーコート法やＣＶＤ法等によりアルカリ遮断膜を作成する場合では、その原料中にフッ素化合物を添加する方法が通常用いられる。また、液相析出法により酸化珪素のアルカリ遮断膜を形成する場合には、原料溶液（珪フッ化水素酸のシリカ過飽和溶液）中にフッ素が０．１〜１０％含まれているので、この原料溶液に特別にフッ素化合物を添加する必要はなくそのまま使用できる。 Fluorine atom doping into the alkali barrier film is usually done by adding a fluorine compound to the raw material when the alkali barrier film is formed by a sol-gel method, vacuum deposition method, baking method, spray coating method, CVD method, etc. Used. Further, when an alkali barrier film of silicon oxide is formed by a liquid phase deposition method, 0.1 to 10% of fluorine is contained in the raw material solution (silica hydrosaturated solution of hydrofluoric acid). It is not necessary to add a fluorine compound to the raw material solution, and it can be used as it is.
［有機物付着防止層］前記の光触媒膜の上に下記のような有機物付着防止層を形成させることが好ましい。活性の高い酸化チタン膜のような光触媒膜は、紫外線照射直後には５度以下の小さな接触角を有していてかなり良好な初期防曇性能を有している。しかし、その表面に、有機物を吸着し易いため、吸着有機物量増加により経時的に防曇性能が劣化しやすい。本発明において、光触媒膜表面にＳｉＯｘ単分子相当層（ｘは１〜２）を形成することが好ましく、それにより、高い光触媒活性を維持しながら、かつ、有機物の吸着が効果的に抑制され、そして防曇性の劣化が防止される。有機物付着防止層である、ＳｉＯｘの単分子相当層の形成は、１，３，５，７−テトラメチルシクロテトラシロキサンのような珪素化合物の蒸気を光触媒表面に化学吸着させたり有機珪素化合物、例えばテトラアルコキシシランを含む液を光触媒膜表面に塗布したりした後に、酸素存在下で紫外光を照射したり加熱したりしてこれを分解することにより好適に行うことができ、その他に、真空蒸着法、ＬＢ法、液相析出法などの方法で直接に、ＳｉＯｘの単分子相当層を形成させてもよい。またＳｉＯｘ単分子相当層に代えて、ポリアルキレンオキシド基、アルキル基、アルケニル基およびアリール基からなる群より選ばれる少なくとも一種の官能基を分子内に含む有機金属化合物またはその加水分解物で光触媒膜表面を被覆することにより、防汚性能が顕著に向上する。これら有機金属化合物は紫外光の照射や温度上昇など外的要因により次第に分解され最終的にはＳｉＯｘ等の金属酸化物単分子相当層を形成し防汚性能は維持される。ここで、単分子相当層とは、実質的に単分子層であって、厚み方向に分子が平均して０．５〜５個配置された分子の層を指す。 [Organic substance adhesion prevention layer] It is preferable to form the following organic substance adhesion prevention layer on the photocatalyst film. A photocatalytic film such as a highly active titanium oxide film has a small contact angle of 5 degrees or less immediately after UV irradiation, and has a considerably good initial antifogging performance. However, since the organic matter is easily adsorbed on the surface, the antifogging performance is likely to deteriorate with time due to an increase in the amount of adsorbed organic matter. In the present invention, it is preferable to form a SiOx monomolecular equivalent layer (x is 1 to 2) on the surface of the photocatalyst film, thereby effectively suppressing the adsorption of organic matter while maintaining high photocatalytic activity, And anti-fogging deterioration is prevented. The formation of the SiOx monomolecular equivalent layer, which is an organic matter prevention layer, can be performed by chemically adsorbing a vapor of a silicon compound such as 1,3,5,7-tetramethylcyclotetrasiloxane on the surface of the photocatalyst or an organic silicon compound, for example, After applying a liquid containing tetraalkoxysilane to the surface of the photocatalyst film, it can be suitably performed by irradiating with ultraviolet light or heating in the presence of oxygen to decompose it. A single-molecule equivalent layer of SiOx may be directly formed by a method such as a method, an LB method, or a liquid phase precipitation method. Further, in place of the SiOx monomolecular equivalent layer, a photocatalytic film made of an organometallic compound containing at least one functional group selected from the group consisting of a polyalkylene oxide group, an alkyl group, an alkenyl group, and an aryl group in the molecule or a hydrolyzate thereof. By coating the surface, the antifouling performance is significantly improved. These organometallic compounds are gradually decomposed by external factors such as ultraviolet light irradiation and temperature rise, and finally form a metal oxide monomolecular equivalent layer such as SiOx to maintain the antifouling performance. Here, the monomolecular equivalent layer is substantially a monomolecular layer and refers to a molecular layer in which 0.5 to 5 molecules are arranged in the thickness direction on average.
前記有機金属化合物の分子内に含まれるポリアルキレンオキシド基としては、ポリエチレンオキシド基、ポリプロピレンオキシド基などが主に使用される。前記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基、ノニル基、デシル基などの炭素原子数が１〜１０の鎖状アルキル基、およびシクロペンチル基、シクロヘキシル基などの炭素原子数が３〜１０の環状アルキル基が主に使用される。前記アルケニル基としては、ビニル基、アリル基、ブテニル基、プロペニル基、ヘキセニル基、オクテニル基、シクロヘキセニル基などの炭素原子数が１〜１０の基が主に使用される。前記アリール基としては、フェニル基、トリル基、キシリル基などが主に使用される。これらの官能基、例えばポリエチレンオキシド基を分子内に含む有機金属化合物としては、［アルコキシ（ポリエチレンオキシ）アルキル］トリアルコキシシラン、［アルコキシ（ポリエチレンオキシ）アルキル］トリクロロシランのようなオルガノシラン、および［アルコキシ（ポリエチレンオキシ）アルキル］トリアルコキシチタンのような有機チタン化合物を挙げることができる。 As the polyalkylene oxide group contained in the molecule of the organometallic compound, a polyethylene oxide group, a polypropylene oxide group or the like is mainly used. Examples of the alkyl group include a chain alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group, and a cyclopentyl group. Cyclic alkyl groups having 3 to 10 carbon atoms such as cyclohexyl group are mainly used. As the alkenyl group, groups having 1 to 10 carbon atoms such as vinyl group, allyl group, butenyl group, propenyl group, hexenyl group, octenyl group, and cyclohexenyl group are mainly used. As the aryl group, a phenyl group, a tolyl group, a xylyl group and the like are mainly used. Organometallic compounds containing these functional groups, for example, polyethylene oxide groups in the molecule include organosilanes such as [alkoxy (polyethyleneoxy) alkyl] trialkoxysilane, [alkoxy (polyethyleneoxy) alkyl] trichlorosilane, and [ Mention may be made of organic titanium compounds such as alkoxy (polyethyleneoxy) alkyl] trialkoxytitanium.
これら官能基は無極性または低極性であるので、汚れ付着性が低く水滴に対する接触角の上昇が抑えられ、すなわち防曇持続性や親水維持性が良好となり好ましい。特にポリアルキレンオキシド基を含むオルガノシランを用いて作製した前記防曇防汚物品は、防曇特性が良好で防曇持続性や親水維持性（すなわち防汚性）が特に優れており、特に好ましい。前述したように、親水維持性が高いと、防汚性が良好である。 Since these functional groups are nonpolar or low in polarity, they are preferable because they have low adhesion to soils and can suppress an increase in contact angle with water droplets, that is, good antifogging sustainability and hydrophilicity sustainability. In particular, the antifogging and antifouling article prepared using an organosilane containing a polyalkylene oxide group has particularly good antifogging properties and is particularly excellent in antifogging durability and hydrophilicity maintenance (that is, antifouling property), which is particularly preferable. . As described above, when the hydrophilicity is high, the antifouling property is good.
また前記官能基は非反応性または低反応性であるので、汚れ成分と化学的結合を生じることもなく、汚れが表面に固定されることもなく、表面に付着した汚れが拭き取りなどにより簡単に除去できるので、たとえ汚れによって防曇性が消失しても簡単に防曇性を復活させることができる。 In addition, since the functional group is non-reactive or low-reactive, it does not cause chemical bonds with the dirt component, the dirt is not fixed to the surface, and the dirt attached to the surface can be easily removed by wiping. Since it can be removed, the antifogging property can be easily restored even if the antifogging property is lost due to dirt.
前記ポリアルキレンオキシド基を含むオルガノシランは、分子内にアルコキシル基やクロロ基を有するアルコキシシランやクロロシランであることが好ましい。アルコキシル基やクロロ基は容易に加水分解を受けて、オルガノシランが光触媒膜表面に強固に化学結合できる状態になるので、より防曇持続性の高い製品になる。前記オルガノシランの中で、ポリエチレンオキシド基を含有するアルコキシシラン、特に［アルコキシ（ポリエチレンオキシ）アルキル］トリアルコキシシラン、例えば［メトキシ（ポリエチレンオキシ）プロピル］トリメトキシシランが最も好適である。 The organosilane containing a polyalkylene oxide group is preferably an alkoxysilane or chlorosilane having an alkoxyl group or chloro group in the molecule. Alkoxyl groups and chloro groups are easily hydrolyzed, and organosilane can be firmly bonded to the surface of the photocatalyst film, resulting in a product with higher antifogging durability. Of the organosilanes, alkoxysilanes containing polyethylene oxide groups, particularly [alkoxy (polyethyleneoxy) alkyl] trialkoxysilanes such as [methoxy (polyethyleneoxy) propyl] trimethoxysilane are most preferred.
前記オルガノシランまたはその加水分解物を前記光触媒膜表面に結合または付着させる方法としては、前記オルガノシランまたはその加水分解物が前記光触媒膜表面に接触する方法なら何でも良い。例えば、前記オルガノシランまたはその加水分解物を含む液体を光触媒膜表面に塗布する方法（塗布法）、前記オルガノシランまたはその加水分解物を含む液体に光触媒膜形成物品を浸漬する方法（液相化学吸着法）、前記オルガノシランまたはその加水分解物の蒸気中に光触媒膜形成物品を置き吸着させる方法（気相化学吸着法）などが挙げられる。 As a method for bonding or adhering the organosilane or its hydrolyzate to the surface of the photocatalyst film, any method can be used as long as the organosilane or its hydrolyzate contacts the surface of the photocatalyst film. For example, a method of applying a liquid containing the organosilane or a hydrolyzate thereof onto a photocatalyst film surface (application method), a method of immersing a photocatalyst film-forming article in a liquid containing the organosilane or a hydrolyzate thereof (liquid phase chemistry) Adsorption method), a method of adsorbing a photocatalyst film-formed article in the vapor of the organosilane or its hydrolyzate (gas phase chemical adsorption method), and the like.
前記方法のうち塗布法が、最も簡単でコストも低く特に好ましい。前記塗布の方法は、公知の技術を用いれば良く、特に限定されないが、スピンコーター、ロールコーター、スプレーコーター、カーテンコーター等の装置を用いる方法や、浸漬引き上げ法（ディップコーティング法）、流し塗り法（フローコーティング法）などの方法や、塗布液を含ませた布や紙を光触媒膜表面に接触させ適当な力をかけて擦る方法（ラビング法）や、スクリーン印刷、グラビア印刷、曲面印刷などの各種印刷法が用いられる。 Of the above methods, the coating method is particularly preferred because it is the simplest and has low cost. The coating method may be any known technique, and is not particularly limited. A method using a spin coater, roll coater, spray coater, curtain coater, or the like, a dip pulling method (dip coating method), or a flow coating method. Such as (flow coating method), a method of rubbing a cloth or paper containing a coating solution in contact with the photocatalyst film surface and applying an appropriate force (rubbing method), screen printing, gravure printing, curved surface printing, etc. Various printing methods are used.
前記オルガノシランを溶かす溶媒は、特に限定されないが、安全性やコストや作業性の観点から水、アルコール類、ケトン類が単独または混合して、好ましく用いられる。アルコール類としては、メタノール、エタノール、プロパノール、ブタノールなどが挙げられ、ケトン類としては、アセトン、メチルエチルケトン、ジエチルケトンなどが挙げられる。 The solvent for dissolving the organosilane is not particularly limited, but water, alcohols and ketones are preferably used alone or in combination from the viewpoints of safety, cost and workability. Examples of alcohols include methanol, ethanol, propanol, butanol, and examples of ketones include acetone, methyl ethyl ketone, and diethyl ketone.
前記オルガノシランは必要に応じて加水分解させて用いる。オルガノシラン溶液に水と必要に応じて酸触媒を加え、一定温度下で一定時間加水分解を行い、必要に応じて希釈して塗布に用いる。 The organosilane is hydrolyzed if necessary. Water and an acid catalyst are added to the organosilane solution as necessary, hydrolysis is performed at a constant temperature for a certain period of time, and dilution is performed as necessary for use in coating.
加水分解の条件は特に限定されないが、２０〜６０℃の温度で３分間〜５０時間行うのが好ましい。温度が２０℃より低かったり時間が３分間より短い場合には加水分解の促進が充分でなく、また温度が６０℃より高かったり時間が５０時間より長くても、もはや加水分解促進の効果が向上せず、また塗布液寿命が短くなるので好ましくない。 The conditions for the hydrolysis are not particularly limited, but it is preferably performed at a temperature of 20 to 60 ° C. for 3 minutes to 50 hours. When the temperature is lower than 20 ° C or when the time is shorter than 3 minutes, the hydrolysis is not promoted sufficiently, and even when the temperature is higher than 60 ° C or longer than 50 hours, the effect of promoting the hydrolysis is no longer improved. And the life of the coating solution is shortened.
前記酸触媒としては、塩酸、硫酸、硝酸などの鉱酸の他、酢酸、ギ酸、クエン酸、ｐ−トルエンスルホン酸などの有機酸が用いられる。酸の添加量は特に限定されないが、オルガノシランに対してモル比で０．０００１〜５が良い。添加酸量が、モル比で０．０００１より少ないと、オルガノシランの加水分解の促進が充分でなく、またモル比で５より多くても、もはや加水分解促進の効果が向上せず、酸が過剰となり好ましくない。 As the acid catalyst, organic acids such as acetic acid, formic acid, citric acid and p-toluenesulfonic acid are used in addition to mineral acids such as hydrochloric acid, sulfuric acid and nitric acid. Although the addition amount of an acid is not specifically limited, 0.0001-5 are good by molar ratio with respect to organosilane. If the amount of added acid is less than 0.0001 in molar ratio, the hydrolysis of organosilane is not sufficiently promoted, and if it is more than 5 in molar ratio, the effect of promoting hydrolysis is no longer improved, It becomes excessive and is not preferable.
加水分解のため添加する水の量は特に限定されないが、オルガノシランに対してモル比で０．１以上が良い。添加水量が、モル比で０．１より少ないと、オルガノシランの加水分解の促進が充分でなく好ましくない。 The amount of water added for hydrolysis is not particularly limited, but is preferably 0.1 or more in terms of molar ratio with respect to the organosilane. If the amount of water added is less than 0.1 in terms of molar ratio, the hydrolysis of organosilane is not sufficiently promoted, which is not preferable.
一方、例えば［アルコキシ（ポリエチレンオキシ）アルキル］トリクロロシランのような加水分解速度が大きい、ポリアルキレンオキシド基含有オルガノシランでは、光触媒膜表面に吸着した水分のみで充分な加水分解が進行し脱水縮合反応により表面に固定できる場合がある。この場合には、溶存水分を充分に減じた非水系溶媒を用いて塗布液を調合した方が、得られる防曇物品の耐候性や防曇防汚性や防曇持続性や親水維持性の優れたものが得られるので好ましい。非水系溶媒としては、ｎ−ヘキサン、シクロヘキサン、キシレン、トルエンなどが例示できる。 On the other hand, polyalkylene oxide group-containing organosilanes such as [alkoxy (polyethyleneoxy) alkyl] trichlorosilane, which have a high hydrolysis rate, undergo sufficient hydrolysis only with water adsorbed on the surface of the photocatalyst film, and dehydration condensation reaction May be fixed to the surface. In this case, it is better to prepare the coating solution using a non-aqueous solvent in which dissolved water is sufficiently reduced, to improve the weather resistance, antifogging and antifouling properties, antifogging sustainability and hydrophilicity maintaining properties of the resulting antifogging article. It is preferable because an excellent product can be obtained. Examples of the non-aqueous solvent include n-hexane, cyclohexane, xylene, toluene and the like.
塗布に用いるオルガノシラン溶液の濃度は特に限定されないが、０．００１〜５重量％が好ましく用いられる。濃度が０．００１重量％より低いと得られる防曇防汚物品に充分な防曇持続性や親水維持性の向上が認め難くなり、また５重量％より高くても防曇性能や防汚性能がそれ以上良くならないので経済的でなく好ましくない。 Although the density | concentration of the organosilane solution used for application | coating is not specifically limited, 0.001 to 5 weight% is used preferably. If the concentration is lower than 0.001% by weight, it is difficult to recognize sufficient anti-fogging durability and hydrophilicity maintenance for the obtained anti-fogging and antifouling article. Is not preferable because it is not economical.
オルガノシラン溶液塗布後の光触媒膜は、２０〜１８０℃の温度で、３分間〜３時間乾燥または熱処理するのが好ましい。この処理により、オルガノシランの光触媒膜表面への結合が強くなり防曇防汚物品の耐久性、防曇持続性および親水維持性が向上する。温度が２０℃より低かったり時間が３分間より短い場合には前記効果が充分でなく好ましくない。温度が１８０℃より高いとオルガノシランが分解する場合があるので好ましくない。また、時間が３時間より長くても、もはや前記効果が向上しないので生産性の観点から好ましくない。 The photocatalyst film after application of the organosilane solution is preferably dried or heat-treated at a temperature of 20 to 180 ° C. for 3 minutes to 3 hours. By this treatment, the bonding of organosilane to the surface of the photocatalyst film is strengthened, and the durability, antifogging durability and hydrophilicity maintenance of the antifogging and antifouling article are improved. When the temperature is lower than 20 ° C. or the time is shorter than 3 minutes, the above effect is not sufficient and it is not preferable. When the temperature is higher than 180 ° C., the organosilane may be decomposed, which is not preferable. Further, even if the time is longer than 3 hours, the effect is no longer improved, which is not preferable from the viewpoint of productivity.
前記光触媒膜表面上にオルガノシラン単分子相当層を形成すれば、防曇持続性や防汚性が向上する。このオルガノシラン層は、紫外線照射や温度上昇等の外的要因により次第に分解され最終的にはＳｉＯｘの単分子相当層となり、防曇持続性や防汚性が維持される。 If an organosilane monomolecular equivalent layer is formed on the surface of the photocatalyst film, antifogging durability and antifouling properties are improved. This organosilane layer is gradually decomposed by external factors such as ultraviolet irradiation and temperature rise, and finally becomes a monomolecular equivalent layer of SiOx, and antifogging durability and antifouling properties are maintained.
本発明による防曇防汚ガラスは、優れた防曇防汚性能とその維持性を有していることが明らかであり、機械的耐久性も良好であることから、自動車、建築およびメガネ用のガラスとして好適に使用することが可能である。 The anti-fogging and antifouling glass according to the present invention clearly has excellent antifogging and antifouling performance and its maintainability, and has good mechanical durability. It can be suitably used as glass.
以下、実施例に基づいて本発明を詳細に説明するが、本発明はかかる実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited only to this Example.
ジルコニウムブトキシド５重量部をアセト酢酸エチル１重量部に加え、３０℃で２時間攪拌した（Ａ液）。一方別に、テトラエトキシシラン５０重量部、２−プロパノール１０００重量部、１Ｎの硝酸２．５重量部、および水５０重量部を加え、３０℃で２時間攪拌した（Ｂ液）。Ａ液とＢ液を混合し５０℃で３時間、さらに３０℃で１日間攪拌養生して、アルカリ遮断膜用ゾル液を得た。 5 parts by weight of zirconium butoxide was added to 1 part by weight of ethyl acetoacetate and stirred at 30 ° C. for 2 hours (solution A). Separately, 50 parts by weight of tetraethoxysilane, 1000 parts by weight of 2-propanol, 2.5 parts by weight of 1N nitric acid, and 50 parts by weight of water were added and stirred at 30 ° C. for 2 hours (Liquid B). Liquid A and liquid B were mixed and stirred and cured at 50 ° C. for 3 hours and further at 30 ° C. for 1 day to obtain an alkali-blocking film sol solution.
酸化セリウム系研磨剤で表面研磨・洗浄し、さらに純水中で超音波洗浄を行い乾燥したソーダライム珪酸塩ガラス板（６５ｍｍ×１５０ｍｍ×３ｍｍ）を、上記アルカリ遮断膜用ゾル液に浸漬し、ガラス板を１０ｃｍ／ｍｉｎの速度で引き上げてゾルを塗布した。その後、これを室温で数分間乾燥させ、さらに５００℃で３時間熱処理し、厚み約３０ｎｍの平坦で凹凸のないシリカ−ジルコニア薄膜（シリカ９２重量％、ジルコニア８重量％）が形成されたガラス板を得た。 A soda-lime silicate glass plate (65 mm × 150 mm × 3 mm), which has been surface-polished and washed with a cerium oxide-based abrasive and then ultrasonically washed in pure water and then dried, is immersed in the sol solution for alkali barrier film, The glass plate was pulled up at a speed of 10 cm / min to apply the sol. Then, this was dried at room temperature for several minutes, and further heat-treated at 500 ° C. for 3 hours to form a flat and uneven silica-zirconia thin film (92% by weight silica, 8% by weight zirconia) having a thickness of about 30 nm. Got.
次に、フッ素原子ドープ酸化チタン膜の作製方法について述べる。３５３ｍＬ（１．２ｍｏｌ）のチタンテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）に攪拌しながら２４８ｍＬ（２．４ｍｏｌ）のアセチルアセトン（ＡｃＡｃ）をビュレットを用いて徐々に滴下し、約１時間攪拌することにより安定なＴｉ（ＡｃＡｃ）２（ＯｉＰｒ）２錯体溶液を得た（母液）。一方、無水エタノール１３９８ｍＬにトリフルオロ酢酸（ＴＦＡ）０．７５ｇを溶解させた溶液を調製した。この溶液に先の母液を加えた後、充分に攪拌することにより、均一なフッ素原子ドープ酸化チタン膜用コーティング溶液を得た。前記平坦なシリカ−ジルコニア薄膜被覆ソーダライム珪酸塩ガラス基板を、このフッ素原子ドープ酸化チタン膜用コーティング液中に浸漬後、３２ｍｍ／ｍｉｎの速度で引き上げ、室温で３０分間乾燥後、さらに、５００℃で３０分間焼成することにより、フッ素原子が約０．３８重量％ドープされた厚み約６０ｎｍのアナタース型酸化チタン膜を成膜した。
このようにして、（ガラス基板／シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜）サンプルを作製した。
Next, a method for producing a fluorine atom-doped titanium oxide film will be described. To 353 mL (1.2 mol) of titanium tetraisopropoxide (Ti (OiPr) 4), 248 mL (2.4 mol) of acetylacetone (AcAc) is gradually added dropwise using a burette while stirring for about 1 hour. Thus, a stable Ti (AcAc) 2 (OiPr) 2 complex solution was obtained (mother liquor). On the other hand, a solution was prepared by dissolving 0.75 g of trifluoroacetic acid (TFA) in 1398 mL of absolute ethanol. After adding the previous mother liquor to this solution, the mixture was sufficiently stirred to obtain a uniform coating solution for a fluorine atom-doped titanium oxide film. The flat silica-zirconia thin film-coated soda lime silicate glass substrate is immersed in this fluorine atom-doped titanium oxide film coating solution, then pulled up at a rate of 32 mm / min, dried at room temperature for 30 minutes, and further heated to 500 ° C. Was baked for 30 minutes to form an anatase-type titanium oxide film having a thickness of about 60 nm doped with about 0.38 wt% of fluorine atoms.
In this way, a sample (glass substrate / silica-zirconia film / fluorine atom-doped titanium oxide film) was produced.
さらに以下に述べる方法により、前記フッ素原子ドープアナタース型酸化チタン膜の表面にＳｉＯｘ単分子層膜を形成させた。８０℃に保温された真空デシケータ中に前記（ガラス基板／シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜）サンプルをセットした後、２００μＬの１，３，５，７−テトラメチルシクロテトラシロクサン（ＴＭＣＴＳ）を注射器で注入した。その状態で３０分保持してから、１００℃に昇温し、デシケータ中を真空引きしながら３０分間加熱することにより未反応のＴＭＣＴＳを除去した。この方法により、酸化チタン膜上にＴＭＣＴＳの単分子膜を形成させた。さらに、５００Ｗ高圧水銀灯を用いて、８ｃｍの距離から１時間光照射することにより、ＴＭＣＴＳ膜を酸化して、ＳｉＯｘの単分子相当膜に変換した。このようにしてサンプルＧ（ガラス基板／シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜／ＳｉＯｘ単分子相当膜）を得た。酸化チタン膜中のフッ素原子ドープ量は０．３８重量％であり膜厚は約６０ｎｍであった。表面粗さを前記原子間力顕微鏡を用いて求めたところ、Ｒａが０．２ｎｍ未満、Ｓｍ＝４２０ｎｍであり、平滑であることがわかった。 Further, a SiOx monomolecular layer film was formed on the surface of the fluorine atom-doped anatase-type titanium oxide film by the method described below. After setting the (glass substrate / silica-zirconia film / fluorine atom-doped titanium oxide film) sample in a vacuum desiccator kept at 80 ° C., 200 μL of 1,3,5,7-tetramethylcyclotetrasiloxane ( TMCTS) was injected with a syringe. After maintaining for 30 minutes in this state, the temperature was raised to 100 ° C., and the unreacted TMCTS was removed by heating for 30 minutes while evacuating the desiccator. By this method, a TMCTS monomolecular film was formed on the titanium oxide film. Further, the TMCTS film was oxidized and converted into a single-molecule equivalent film of SiOx by irradiating light from a distance of 8 cm for 1 hour using a 500 W high-pressure mercury lamp. Thus, sample G (glass substrate / silica-zirconia film / fluorine atom-doped titanium oxide film / SiOx monomolecular equivalent film) was obtained. The fluorine atom doping amount in the titanium oxide film was 0.38% by weight, and the film thickness was about 60 nm. When the surface roughness was determined using the atomic force microscope, Ra was less than 0.2 nm and Sm = 420 nm, which was found to be smooth.
（比較例１）基板として１０ｃｍ角のソーダライム珪酸塩ガラス板（Ｎａ２Ｏ約１３％、Ｋ２Ｏ約０．８％含有）を用意した。このガラス板の表面は算術平均粗さ（Ｒａ）が０．２ｎｍ未満でありかつ凹凸の平均間隔（Ｓｍ）は４００ｎｍである平滑表面となっていた。 Was prepared (Comparative Example 1) 10 cm square soda-lime silicate glass plate as substrate (Na 2 O about 13%, K 2 O from about 0.8% containing). The surface of this glass plate was a smooth surface with an arithmetic average roughness (Ra) of less than 0.2 nm and an average interval of unevenness (Sm) of 400 nm.
次に、ディッピング（ゾルゲル）法による酸化チタン薄膜のコーティング法について説明する。８５．６ｇ（０．３ｍｏｌ）のチタンテトライソプロポキシド（Ｔｉ（ＯｉＰｒ）４）に攪拌しながら６０．３ｇ（０．６ｍｏｌ）のアセチルアセトン（ＡｃＡｃ）をビュレットを用いて徐々に滴下し、約１時間攪拌して安定なＴｉ（ＡｃＡｃ）２（ＯｉＰｒ）２錯体溶液を得た（母液）。この母液をエタノールで３．３倍に希釈してコーティング溶液とした。前記ソーダライム珪酸塩ガラス基板をコーティング液中に浸漬後、４．６ｃｍ／分の引き上げ速度で膜を形成させ、５００℃で３０分間焼成を行なった。得られたサンプルをサンプルＡ（ガラス基板／酸化チタン膜）とする。Ｘ線回折による分析の結果、サンプルＡの酸化チタン膜は非晶質であることが確認された。そしてサンプルＡの酸化チタン薄膜の厚みは約５０ｎｍであった。また原子間力顕微鏡による測定の結果、サンプルＡの酸化チタン膜の表面は算術平均粗さ（Ｒａ）が０．２ｎｍ未満でありかつ凹凸の平均間隔（Ｓｍ）は４００ｎｍである平滑表面となっていた。
このサンプルＡの表面に、実施例１と同様にしてＳｉＯｘ単分子相当膜を形成し、サンプルＡ’（ガラス基板／酸化チタン膜／ＳｉＯｘ単分子相当膜、比較例１）を得た。
Next, a method for coating a titanium oxide thin film by a dipping (sol-gel) method will be described. While stirring, 60.3 g (0.6 mol) of acetylacetone (AcAc) was gradually dropped into 85.6 g (0.3 mol) of titanium tetraisopropoxide (Ti (OiPr) 4 ) using a burette, and about 1 The mixture was stirred for a time to obtain a stable Ti (AcAc) 2 (OiPr) 2 complex solution (mother liquor). This mother liquor was diluted 3.3 times with ethanol to obtain a coating solution. The soda lime silicate glass substrate was immersed in a coating solution, a film was formed at a pulling rate of 4.6 cm / min, and baked at 500 ° C. for 30 minutes. Let the obtained sample be the sample A (glass substrate / titanium oxide film). As a result of analysis by X-ray diffraction, it was confirmed that the titanium oxide film of Sample A was amorphous. The thickness of the titanium oxide thin film of Sample A was about 50 nm. As a result of measurement by an atomic force microscope, the surface of the titanium oxide film of sample A is a smooth surface having an arithmetic average roughness (Ra) of less than 0.2 nm and an average interval of unevenness (Sm) of 400 nm. It was.
A SiOx monomolecular equivalent film was formed on the surface of Sample A in the same manner as in Example 1 to obtain Sample A ′ (glass substrate / titanium oxide film / SiOx monomolecular equivalent film, Comparative Example 1).
このサンプルＧおよびＡ’を、紫外線が当たらず、人が絶えず出入りする部屋の室内に放置し続け、その表面が汚れて防曇性が低下する程度を、呼気を吹きかけたときの曇り程度により評価した（呼気テスト）。すなわち表面を清浄にした直後のサンプルは呼気を吹きかけても曇りを生じないが、室内放置により大気中の汚れ成分がサンプル表面に吸着して呼気テストにより曇るようになる。室内放置を始めてから曇りが生じ始めるまでの時間（防曇維持時間）を防曇維持性の指標とした。この値が大きい程防曇維持性が高いといえる。さらに、室内放置により呼気テストで曇りが生じたサンプルに再度０．８ｍＷ／ｃｍ２の強度の紫外線（３６０〜３７０ｎｍ）を連続して照射し、呼気テストにより曇りが生じなくなるまでに要する紫外線照射時間（防曇回復時間）を防曇回復性の指標とした。なお、０．８ｍＷ／ｃｍ２の紫外線（３６０〜３７０ｎｍ）照射強度は、冬季、曇天、正午で北緯３５゜の戸外の地面での太陽光からの紫外線（３６０〜３７０ｎｍ）照射強度の２〜５倍に相当する。この防曇回復時間が小さい程防曇回復性が高いといえる。２４時間以上の防曇維持性と２時間以内の防曇回復性を満足することが多くの用途において要求される。さらに一般的には、防曇維持時間を防曇回復時間で除した値、すなわち、［防曇維持時間］／［防曇回復時間］の値が４０以上のものが防曇ガラス物品として好適に使用することができる。 Samples G and A ′ were evaluated by the degree of cloudiness when exhaled air was applied to the extent that the surface of the sample G and A ′ was left in a room where people were constantly coming and going without being exposed to ultraviolet rays, and the surface was soiled and the antifogging property was lowered. (Exhalation test). That is, the sample immediately after cleaning the surface does not become cloudy even when exhaled air is blown, but when left in the room, dirt components in the atmosphere are adsorbed on the sample surface and become cloudy by the breath test. The time from the start of standing indoors until the beginning of fogging (antifogging maintenance time) was used as an index of antifogging maintenance. It can be said that the larger this value is, the higher the antifogging maintenance property is. Furthermore, the ultraviolet irradiation time required until the sample that has become cloudy in the breath test by being left indoors is continuously irradiated again with ultraviolet light (360 to 370 nm) having an intensity of 0.8 mW / cm 2 , and clouding is not caused by the breath test. (Anti-fogging recovery time) was used as an index of anti-fogging recovery. The irradiation intensity of 0.8 mW / cm 2 of ultraviolet rays (360 to 370 nm) is 2 to 5 of the irradiation intensity of ultraviolet rays (360 to 370 nm) from sunlight on the outdoor ground at 35 ° north latitude at noon in the winter. It is equivalent to twice. It can be said that the smaller the antifogging recovery time, the higher the antifogging recovery property. Satisfying antifogging maintenance property of 24 hours or more and antifogging recovery property within 2 hours are required in many applications. More generally, a value obtained by dividing the antifogging maintenance time by the antifogging recovery time, that is, a value of [antifogging maintenance time] / [antifogging recovery time] of 40 or more is suitable as an antifogging glass article. Can be used.
また、防汚維持性を以下の屋外暴露試験によって行った。兵庫県伊丹市で屋外に試験ガラス板を垂直に設置して、雨水が試験ガラス板表面を流れ落ちる軒下垂直面を模した環境下で、６カ月間暴露試験を行い、試験後のガラス板の汚染状態評価を、下記表１の基準による目視評価にて行った。 Antifouling maintenance was performed by the following outdoor exposure test. A test glass plate is installed vertically in Itami, Hyogo Prefecture, and an exposure test is conducted for 6 months in an environment simulating the vertical surface of the eaves where rainwater flows down the surface of the test glass plate. The state evaluation was performed by visual evaluation according to the criteria shown in Table 1 below.
（表１）
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
評価 汚染状態
−−−−−−−−−−−−−−−−−−−−−−−−−
◎ ほとんど汚れが気にならない
○ 若干汚れており、薄く筋状汚れが見える
△ 汚れており、筋状汚れが目立つ
× 汚れが著しく、筋状汚れがかなり目立つ
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
(Table 1)
=========================
Evaluation Contamination status -------------------------
◎ Almost dirt is not worrisome ○ Slightly dirty and thin streaks appear △ Dirty and streaks are conspicuous × Dirt is remarkable and streaks are quite conspicuous ========= ===============
サンプルＧおよびＡ’の各種評価結果を表２に示す。サンプルＡ’（比較例１）は良好な防曇防汚維持性を有するものの、防曇回復性が劣っている。これに対して、サンプルＧ（実施例１）は良好な防曇維持性を有すると同時に防曇回復性が著しく改善されていることが明らかである。また、サンプルＡ’（比較例１）は防汚性が低いのに対して、サンプルＧ（実施例１）は良好な防汚性を有していることが明らかである。 Table 2 shows various evaluation results of samples G and A ′. Sample A ′ (Comparative Example 1) has good antifogging and antifouling maintenance properties, but has poor antifogging recovery properties. On the other hand, it is clear that sample G (Example 1) has a good anti-fogging maintenance property and at the same time, the anti-fogging recovery property is remarkably improved. Further, it is clear that sample A ′ (Comparative Example 1) has a low antifouling property, whereas Sample G (Example 1) has a good antifouling property.
実施例１で作製した、ＳｉＯｘ単分子相当膜形成前のサンプル（ガラス基板／平坦シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜）表面に、以下の方法で、ポリエチレンオキシド基を分子内に含むオルガノシラン層（厚み約４ｎｍ）を形成した。 Organo containing polyethylene oxide groups in the molecule by the following method on the surface of the sample (glass substrate / flat silica-zirconia film / fluorine atom-doped titanium oxide film) prepared in Example 1 before forming the SiOx monomolecular equivalent film A silane layer (thickness about 4 nm) was formed.
１Ｌのエタノールに０．１Ｎ酢酸を１ｍＬ添加し攪拌した。このエタノールを主体とする液７９８ｇに［メトキシ（ポリエチレンオキシ）プロピル］トリメトキシシラン（チッソ株式会社製「ＳＩＭ６４９２．７」、含有率９０％、分子量４６０〜５９０、エチレンオキサイド単位６〜９）を２ｇ添加し３０℃で１時間攪拌して塗布液を調製した。 1 mL of 0.1N acetic acid was added to 1 L of ethanol and stirred. 2 g of [methoxy (polyethyleneoxy) propyl] trimethoxysilane (“SIM6492.7” manufactured by Chisso Corporation, content 90%, molecular weight 460 to 590, ethylene oxide units 6 to 9) to 798 g of this ethanol-based liquid The mixture was added and stirred at 30 ° C. for 1 hour to prepare a coating solution.
実施例１のサンプル（ガラス基板／平坦シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜）を上記塗布液に浸漬し、５ｃｍ／ｍｉｎの速度で引き上げることにより、液を塗布した。これを１２０℃で３０分間乾燥、熱処理し、室温まで冷やした後に純水で軽く洗浄して、ポリエチレンオキシド基を分子内に含むオルガノシラン層（厚み約４ｎｍ）を形成させた。このサンプルに、５００Ｗ高圧水銀灯を用いて、８ｃｍの距離から２４時間光照射し、オルガノシラン層を酸化して、ＳｉＯｘの単分子相当膜に変換した。このサンプルをサンプルＪ（＝ガラス基板／平坦シリカ−ジルコニア膜／フッ素原子ドープ酸化チタン膜／ＳｉＯｘ単分子相当膜）とする。このサンプル表面の算術平均粗さ（Ｒａ）と凹凸の平均間隔（Ｓｍ）を、原子間力顕微鏡を用いて求めたところ、Ｒａが０．２ｎｍ未満でありかつＳｍが４３０ｎｍである平滑表面となっていた。 The sample of Example 1 (glass substrate / flat silica-zirconia film / fluorine atom-doped titanium oxide film) was immersed in the coating solution and pulled up at a rate of 5 cm / min to apply the solution. This was dried at 120 ° C. for 30 minutes, heat-treated, cooled to room temperature, and then lightly washed with pure water to form an organosilane layer (thickness: about 4 nm) containing polyethylene oxide groups in the molecule. This sample was irradiated with light from a distance of 8 cm for 24 hours using a 500 W high-pressure mercury lamp, and the organosilane layer was oxidized and converted into a single-molecule equivalent film of SiOx. This sample is designated as sample J (= glass substrate / flat silica-zirconia film / fluorine atom-doped titanium oxide film / SiOx monomolecular equivalent film). When the arithmetic average roughness (Ra) and the average interval (Sm) of the irregularities of the sample surface were determined using an atomic force microscope, a smooth surface having Ra of less than 0.2 nm and Sm of 430 nm was obtained. It was.
実施例１に述べたのと同じ方法で防曇防汚性能を評価した結果を表２に示す。これより、サンプルＪは優れた防曇防汚ガラスであることが明らかである。 Table 2 shows the results of evaluating the antifogging and antifouling performance by the same method as described in Example 1. From this, it is clear that Sample J is an excellent antifogging and antifouling glass.
基板としてゾルゲル法により約８０ｎｍ厚のフッ素原子ドープ平坦シリカ膜をコーティングした寸法６５ｍｍ×１５０ｍｍ×３ｍｍのソーダライム珪酸塩ガラス板を用意した。フッ素原子ドープ平坦シリカ膜は、以下の方法で成膜した。 A soda lime silicate glass plate having a size of 65 mm × 150 mm × 3 mm coated with a fluorine atom-doped flat silica film having a thickness of about 80 nm by a sol-gel method was prepared as a substrate. The fluorine atom-doped flat silica film was formed by the following method.
テトラメトキシシラン５０重量部、エタノール５３０重量部、２−プロパノール５３０重量部、１Ｎ硝酸２．５重量部、水３０重量部およびトリフルオロ酢酸（ＴＦＡ）１．４ｇを加え、５０℃で２時間攪拌し、さらに３０℃で１日間攪拌養生して、アルカリ遮断膜用ゾル液を得た。 Add 50 parts by weight of tetramethoxysilane, 530 parts by weight of ethanol, 530 parts by weight of 2-propanol, 2.5 parts by weight of 1N nitric acid, 30 parts by weight of water and 1.4 g of trifluoroacetic acid (TFA), and stir at 50 ° C. for 2 hours. Further, the mixture was stirred and cured at 30 ° C. for 1 day to obtain a sol solution for an alkali barrier film.
酸化セリウム系研磨剤で表面研磨・洗浄し、さらに純水中で超音波洗浄を行い乾燥したソーダライム珪酸塩ガラス板（１００ｍｍ×１００ｍｍ×３ｍｍ）を、上記アルカリ遮断膜用ゾル液に浸漬し、ガラス板を３０ｃｍ／ｍｉｎの速度で引き上げてゾルを塗布した。その後、これを室温で数分間乾燥させ、さらに２００℃で３時間熱処理し、厚み約９０ｎｍでフッ素が約３重量％ドープされたフッ素原子ドープ平坦シリカ膜が形成されたガラス板を得た。 A soda lime silicate glass plate (100 mm × 100 mm × 3 mm), which has been surface-polished and washed with a cerium oxide-based abrasive and then ultrasonically washed in pure water and then dried, is immersed in the sol solution for alkali barrier film, The glass plate was pulled up at a speed of 30 cm / min to apply the sol. Thereafter, this was dried at room temperature for several minutes and further heat treated at 200 ° C. for 3 hours to obtain a glass plate on which a fluorine atom-doped flat silica film having a thickness of about 90 nm and doped with about 3 wt% fluorine was formed.
このフッ素原子ドープ平坦シリカ膜形成ガラス板上に、以下の方法で厚み約５０ｎｍの光触媒膜（酸化チタン酸化珪素）を形成した。すなわち、市販の光触媒コーティング液ＳＴ−Ｋ０３（石原産業株式会社製、酸化チタン微粒子含有率５重量％、無機バインダー５重量％）を、エタノールを用いて４重量倍に希釈した。この液を前記フッ素原子ドープ平坦シリカ膜が形成されたガラス板上に、スピンコーティング法（１５００ｒｐｍ、１０秒、液量４ｍｌ）にて成膜し、５００℃で１時間熱処理して、光触媒薄膜を形成した。化学分析の結果、この光触媒薄膜は、酸化チタン約５０重量％と酸化珪素約５０重量％からなることを確認した。
この光触媒膜中には、フッ素原子ドープ平坦シリカ膜から拡散してきたと推定されるフッ素が約０．１重量％ドープされていることがラザフォード・バックスキャッタリング法により確認された。さらにこの光触媒膜の上に、実施例２記載の方法でＳｉＯｘ単分子相当層を形成した。
A photocatalytic film (titanium oxide silicon oxide) having a thickness of about 50 nm was formed on the fluorine atom-doped flat silica film-formed glass plate by the following method. That is, a commercially available photocatalyst coating liquid ST-K03 (manufactured by Ishihara Sangyo Co., Ltd., titanium oxide fine particle content 5% by weight, inorganic binder 5% by weight) was diluted 4 times by weight with ethanol. This liquid is formed on the glass plate on which the fluorine atom-doped flat silica film is formed by spin coating (1500 rpm, 10 seconds, liquid volume 4 ml), and heat-treated at 500 ° C. for 1 hour to form a photocatalytic thin film. Formed. As a result of chemical analysis, it was confirmed that this photocatalytic thin film was composed of about 50% by weight of titanium oxide and about 50% by weight of silicon oxide.
It was confirmed by the Rutherford backscattering method that this photocatalyst film was doped with about 0.1% by weight of fluorine presumed to diffuse from the fluorine atom-doped flat silica film. Further, a SiOx monomolecular equivalent layer was formed on the photocatalyst film by the method described in Example 2.
このサンプルをサンプルＮ（＝ガラス基板／平坦フッ素原子ドープシリカ膜／フッ素原子ドープ酸化チタン酸化珪素膜／ＳｉＯｘ単分子相当層）とする。このサンプル表面の算術平均粗さ（Ｒａ）と凹凸の平均間隔（Ｓｍ）を、原子間力顕微鏡を用いて求めたところ、Ｒａが１．２ｎｍでありかつＳｍが２０ｎｍであった。 This sample is designated as sample N (= glass substrate / flat fluorine atom-doped silica film / fluorine atom-doped titanium oxide silicon oxide film / SiOx monomolecular equivalent layer). When the arithmetic mean roughness (Ra) and the average interval (Sm) of the unevenness of the sample surface were determined using an atomic force microscope, Ra was 1.2 nm and Sm was 20 nm.
実施例１に述べたのと同じ方法で防曇防汚性能を評価した結果を表２に示す。これより、サンプルＮは優れた防曇防汚ガラスであることが明らかである。 Table 2 shows the results of evaluating the antifogging and antifouling performance by the same method as described in Example 1. From this, it is clear that Sample N is an excellent antifogging and antifouling glass.
［比較例２］実施例１で使用した１０ｃｍ角のソーダライム珪酸塩ガラス板を処理することなくそのままでサンプルＯとして各種防曇防汚性能を評価し、その結果を表２に示した。（比較例２） [Comparative Example 2] Various antifogging and antifouling performances were evaluated as Sample O without processing the 10 cm square soda lime silicate glass plate used in Example 1, and the results are shown in Table 2. (Comparative Example 2)
（表２）
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
サ
ン 防曇 防曇
プ 維持時間 回復時間 (イ)／(ロ) 曝露試験後
ル （時間） （時間） 防汚状態評価
（イ） （ロ）
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
実施例
１ Ｇ ４０ ０．２５ １６０ ◎
２ Ｊ ６０ ０．６ １００ ◎
３ Ｎ ４８ ０．３ １６０ ◎
比較例
１ Ａ’ １０ ５ ２ ×
２ Ｏ ２０ ０ − ×
＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝＝
(Table 2)
===============================
Sun Anti-fog Anti-fog Maintenance time Recovery time (b) / (b) After exposure test Le (time) (time) Antifouling condition evaluation
(B) (b)
-------------------------------
Example 1 G 40 0.25 160
2 J 60 0.6 100 ◎
3 N 48 0.3 160 ◎
Comparative Example 1 A ′ 10 5 2 ×
2 O 20 0-×
===============================
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