JP2005041771A - Titanium oxide, sol containing titanium oxide, thin film formed from said sol, and method for preparing said sol - Google Patents
Titanium oxide, sol containing titanium oxide, thin film formed from said sol, and method for preparing said sol Download PDFInfo
- Publication number
- JP2005041771A JP2005041771A JP2004196945A JP2004196945A JP2005041771A JP 2005041771 A JP2005041771 A JP 2005041771A JP 2004196945 A JP2004196945 A JP 2004196945A JP 2004196945 A JP2004196945 A JP 2004196945A JP 2005041771 A JP2005041771 A JP 2005041771A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- thin film
- brookite crystal
- brookite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 225
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000010409 thin film Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title abstract description 39
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
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- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 16
- 239000004033 plastic Substances 0.000 claims abstract description 11
- 229920003023 plastic Polymers 0.000 claims abstract description 10
- 239000000123 paper Substances 0.000 claims abstract description 9
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 33
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- 239000007864 aqueous solution Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 23
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 22
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- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 4
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- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
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Abstract
Description
本発明は、光触媒用酸化チタン、その原料となる酸化チタンゾル、該ゾルを用いてセラミックス、プラスチック等の基材上に形成した酸化チタンの薄膜と、それらの製造方法に関する。特に、波長４００ｎｍ以上の可視光に対して光触媒としての応答性が高い光触媒機能を有する物質、薄膜の製造方法に関する。 The present invention relates to a titanium oxide for photocatalyst, a titanium oxide sol as a raw material thereof, a titanium oxide thin film formed on a substrate such as ceramics or plastic using the sol, and a method for producing them. In particular, the present invention relates to a method for manufacturing a substance and a thin film having a photocatalytic function that is highly responsive as a photocatalyst to visible light having a wavelength of 400 nm or more.
従来、実用的に代表的な光触媒としては酸化チタンが幅広く使われている。酸化チタンには約４００ｎｍ以下の波長の紫外線を吸収して電子を励起させる性質がある。そこで、発生した電子とホールは粒子表面に到達すると、酸素や水と化合して様々なラジカル種を発生させる。このラジカル種が主として酸化作用を示し、表面に吸着した物質を酸化分解する。これが光触媒の基本原理である。こうした酸化チタンの光機能を利用して、抗菌、消臭、防汚、大気の浄化、水質の浄化等の環境浄化が検討されている。 Conventionally, titanium oxide has been widely used as a practically representative photocatalyst. Titanium oxide has the property of exciting electrons by absorbing ultraviolet light having a wavelength of about 400 nm or less. Therefore, when the generated electrons and holes reach the particle surface, they combine with oxygen and water to generate various radical species. This radical species mainly exhibits an oxidizing action, and oxidatively decomposes the substance adsorbed on the surface. This is the basic principle of the photocatalyst. Utilizing such a light function of titanium oxide, environmental purification such as antibacterial, deodorant, antifouling, air purification, water quality purification and the like has been studied.
近年、いわゆる可視光応答型光触媒の検討が種々なされている。例えば、四塩化チタンまたはチタンテトライソプロポキシドからアンモニア含有溶液により水酸化チタンを作成し、これを焼成することで、ＮＯｘを含む酸化チタンが得られ、その酸化チタンが可視光に対して活性があることが報告されている（非特許文献１）。 In recent years, various studies on so-called visible light responsive photocatalysts have been made. For example, titanium hydroxide is prepared from an aqueous solution containing titanium tetrachloride or titanium tetraisopropoxide and baked to obtain titanium oxide containing NOx. The titanium oxide is active against visible light. It has been reported (Non-Patent Document 1).
また、Ｘ線光電子分光法で結合エネルギー４５８ｅＶ〜４６０ｅＶの間にある酸化チタンのチタンのピークの半価幅を４回測定した時の１回目と２回目のチタンのピークの半価幅の平均値をＡとし、３回目と４回目のチタンのピークの半価幅の平均値をＢとしたときに指数Ｘ＝Ｂ／Ａが０．９７以下である酸化チタンが開示されている（特許文献３）。しかし、粉の活性が不満足であるばかりか、着色を示しているが故にその用途には制限がある。現実的には、透明性を要求されるような塗料には不適である、というような欠点を有している。 In addition, the average value of the half-value widths of the first and second titanium peaks when the half-value width of the titanium peak of titanium oxide having a binding energy between 458 eV and 460 eV is measured four times by X-ray photoelectron spectroscopy. Is a titanium oxide having an index X = B / A of 0.97 or less, where A is A and B is the average half-value width of the third and fourth titanium peaks (Patent Document 3). ). However, not only is the activity of the powder unsatisfactory, but the use is limited because it shows coloration. In reality, it has a drawback that it is unsuitable for a paint requiring transparency.
また、従来の多くの可視光応答型の光触媒は、その触媒能の十分な発現のためには、キセノンランプのような強力な光源を必要としている点においても現実性に乏しいと言わざるを得ない。既存の安価な光源、例えば、昼白色蛍光灯のような室内において常用される光源で十分な効果を発揮する光触媒があれば大きな実用上のメリットがある。 In addition, many of the conventional visible light responsive photocatalysts are not realistic in that they require a powerful light source such as a xenon lamp in order to fully exhibit their catalytic ability. Absent. If there is a photocatalyst that exhibits a sufficient effect with an existing inexpensive light source, for example, a light source commonly used indoors, such as a daylight fluorescent lamp, there is a great practical advantage.
さらに、光触媒能を種々の基材に付与するために、透明な酸化チタン薄膜が望まれており、その原料として分散性の良好なゾルが望まれている。しかしながら、従来の窒素原子を含有する酸化チタンを含むスラリーにおいては十分な分散性が得られにくく、透明かつ可視光応答性の高い酸化チタン薄膜を得ることが難しかった。
本発明の課題は、可視光に対する応答性が高いだけでなく、透明な薄膜が得られる酸化チタンゾルを製造することにある。 An object of the present invention is to produce a titanium oxide sol that not only has high responsiveness to visible light but also provides a transparent thin film.
また、セラミックス、金属、ガラス、プラスチック、紙、木材など、種々の基材に、簡易な手法で、可視光に対する応答性の高い光触媒薄膜を形成させること、さらにプラスチックなどの熱に弱い基材に対しても、意匠性を損なうことなく、可視光に対して応答性の高い光触媒薄膜を形成することにある。 In addition, a simple method can be used to form a photocatalytic thin film with high responsiveness to visible light on various substrates such as ceramics, metals, glass, plastics, paper, and wood. On the other hand, it is to form a photocatalytic thin film having high responsiveness to visible light without impairing the design.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、ブルッカイト結晶含有酸化チタンを合成する過程において、窒素含有化合物を接触させることによって、窒素原子を含有するブルッカイト結晶含有酸化チタンのゾルが得られることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have made a brookite crystal-containing titanium oxide containing a nitrogen atom by contacting a nitrogen-containing compound in the process of synthesizing a brookite crystal-containing titanium oxide. It was found that the sol was obtained.
また、該ゾルが安定であり、該ゾルからは透明な薄膜が得られることを見出した。 Moreover, it discovered that this sol was stable and a transparent thin film was obtained from this sol.
さらにこの薄膜は可視光に対しても高い応答性を有する光触媒膜となることを見出した。 Furthermore, it has been found that this thin film becomes a photocatalytic film having high responsiveness to visible light.
本発明は以下の発明からなる。
〔１〕０．００１〜１０質量％の窒素原子を含むブルッカイト結晶含有酸化チタン。
〔２〕ブルッカイト結晶含有酸化チタンが、Ｃｕ−Ｋα１線を用いる粉末Ｘ線回折で測定される面間隔ｄ（Å）において、ｄ＝２．９０（測定誤差範囲として±０．０２Å）にブルッカイト結晶由来のピークを有していることを特徴とする〔１〕に記載のブルッカイト結晶含有酸化チタン。
〔３〕ブルッカイト結晶含有酸化チタンが、Ｃｕ−Ｋα１線を用いる粉末Ｘ線回折で測定される面間隔ｄ（Å）において、少なくとも３．４６、２．９０、２．４８、２．１４、１．９１、１．７０、１．６７、１．５０、１．４７（測定誤差範囲として±０．０２Å）にブルッカイト結晶由来のピークを有していることを特徴とする〔２〕に記載のブルッカイト結晶含有酸化チタン。
〔４〕ブルッカイト結晶含有酸化チタンが、Ｃｕ−Ｋα１線を用いる粉末Ｘ線回折で測定される面間隔ｄ（Å）において、ｄ＝２．３８（測定誤差範囲として±０．０２Å）にアナターゼ結晶由来のピークを有していることを特徴とする〔１〕乃至〔３〕のいずれか１項に記載のブルッカイト結晶含有酸化チタン。
〔５〕ブルッカイト結晶含有酸化チタンが、Ｃｕ−Ｋα１線を用いる粉末Ｘ線回折で測定される面間隔ｄ（Å）において、ブルッカイト結晶由来のｄ＝２．９０近傍のピーク高さＡとアナターゼ結晶由来のｄ＝２．３８近傍のピーク高さＢとの比Ａ／Ｂが、０．５より大きいことを特徴とする、〔１〕乃至〔４〕いずれか１項に記載のブルッカイト結晶含有酸化チタン。
〔６〕ピーク高さ比Ａ／Ｂが、１から３０の範囲内であることを特徴とする〔５〕に記載のブルッカイト結晶含有酸化チタン。
〔７〕BET比表面積から算出される一次粒子径の平均値が０．０１〜０．１μｍであることを特徴とする〔１〕乃至〔６〕のいずれか1項に記載のブルッカイト結晶含有酸化チタン。
〔８〕〔１〕乃至〔７〕のいずれか１項に記載のブルッカイト結晶含有酸化チタンを含む光触媒機能を有する物質。
〔９〕〔１〕乃至〔７〕のいずれか１項に記載のブルッカイト結晶含有酸化チタンを含むゾル。
〔１０〕室温において密閉容器中で２４０時間静置後、液面から８０体積％の液をデカンテーションで分離し、残りを乾燥して得られる「下層固形分」が、ゾル全体の固形分量の３０質量％未満であることを特徴とする〔９〕に記載のゾル。
〔１１〕固形分が０．０１〜１０質量％の範囲内であることを特徴とする〔９〕または〔１０〕に記載のゾル。
〔１２〕窒素原子含有化合物を１質量％以上含む７５℃〜１００℃の熱水に四塩化チタン水溶液を加え、７５℃〜溶液の沸点の温度範囲で加水分解することを特徴とする、〔９〕乃至〔１１〕のいずれか１項に記載のゾルの製造方法。
〔１３〕窒素原子含有化合物が、水溶性であることを特徴とする、〔１２〕に記載のゾルの製造方法。
〔１４〕窒素原子含有化合物が、アンモニア、尿素、ヒドラジン、メチルアミン塩酸塩、ジメチルアミン塩酸塩、ジメチルアミン水溶液、トリメチルアミン塩酸塩、トリメチルアミン水溶液、エチルアミン塩酸塩、エチルアミン水溶液、ジエチルアミン塩酸塩、ジエチルアミン、トリエチルアミン塩酸塩、トリエチルアミンからなる群から選ばれた少なくとも１種類の化合物であることを特徴とする〔１２〕に記載ゾルの製造方法。
〔１５〕窒素原子含有化合物が、アンモニア、尿素、ヒドラジンからなる群から選ばれた少なくとも１種類の化合物であることを特徴とする〔１２〕に記載のゾルの製造方法。
〔１６〕窒素原子含有化合物が尿素であることを特徴とする〔１２〕に記載のゾルの製造方法。
〔１７〕還流冷却装置を備えた反応装置を使用し、加水分解中に系内の窒素含有化合物と塩化水素の逸出を抑制することを特徴とする〔１２〕乃至〔１６〕のいずれか１項に記載のゾルの製造方法。
〔１８〕ゾル中の塩素イオンを塩素元素として５０〜１０，０００質量ｐｐｍに調整することを特徴とする〔１２〕乃至〔１６〕のいずれか１項に記載のゾルの製造法。
〔１９〕ゾル中の塩素イオンを塩素元素として１００〜４，０００質量ｐｐｍに調整することを特徴とする〔１８〕に記載のゾルの製造法。
〔２０〕〔１〕乃至〔７〕のいずれか１項に記載のブルッカイト結晶含有酸化チタンを含む薄膜。
〔２１〕〔８〕に記載の光触媒機能を有する物質を含む薄膜。
〔２２〕〔９〕乃至〔１１〕のいずれか１項に記載のゾルを用いて形成された薄膜。
〔２３〕基材がセラミックス、金属、ガラス、プラスチック、紙、木材のいずれかである〔２０〕乃至〔２２〕のいずれか１項に記載の薄膜。
〔２４〕薄膜が焼成したものであることを特徴とする、〔２０〕乃至〔２３〕のいずれか１項に記載の薄膜。
〔２５〕８０℃以下の温度で乾燥するのみで光触媒能を発現することを特徴とする、〔２０〕乃至〔２３〕のいずれか１項に記載の薄膜。
The present invention comprises the following inventions.
[1] Brookite crystal-containing titanium oxide containing 0.001 to 10% by mass of nitrogen atoms.
[2] The brookite crystal-containing titanium oxide has a brookite crystal at d = 2.90 (measurement error range is ± 0.02 Å) at a surface interval d (Å) measured by powder X-ray diffraction using Cu—Kα1 ray. [1] The brookite crystal-containing titanium oxide according to [1], which has a peak derived from it.
[3] The brookite crystal-containing titanium oxide is at least 3.46, 2.90, 2.48, 2.14, 1. at an interplanar spacing d (Å) measured by powder X-ray diffraction using Cu—Kα1 rays. .91, 1.70, 1.67, 1.50, 1.47 (measurement error range is ± 0.02 mm), and has peaks derived from brookite crystals, according to [2] Brookite crystal-containing titanium oxide.
[4] Titanium oxide containing brookite crystal is anatase crystal at d = 2.38 (± 0.02 cm as a measurement error range) at an interplanar distance d (Å) measured by powder X-ray diffraction using Cu—Kα1 ray. The brookite crystal-containing titanium oxide according to any one of [1] to [3], wherein the titanium oxide has a peak derived from the above.
[5] The peak height A and the anatase crystal in the vicinity of d = 2.90 derived from a brookite crystal in the interplanar spacing d (Å) measured by powder X-ray diffraction using Cu—Kα1 ray for the titanium oxide containing brookite crystal [1] to [4] The brookite crystal-containing oxidation according to any one of [1] to [4], wherein a ratio A / B with a peak height B in the vicinity of d = 2.38 is greater than 0.5 titanium.
[6] The brookite crystal-containing titanium oxide according to [5], wherein the peak height ratio A / B is in the range of 1 to 30.
[7] The brookite crystal-containing oxidation according to any one of [1] to [6], wherein an average primary particle diameter calculated from a BET specific surface area is 0.01 to 0.1 μm. titanium.
[8] A substance having a photocatalytic function, comprising the brookite crystal-containing titanium oxide according to any one of [1] to [7].
[9] A sol containing the brookite crystal-containing titanium oxide according to any one of [1] to [7].
[10] After standing for 240 hours in a closed container at room temperature, 80% by volume of the liquid is separated from the liquid surface by decantation, and the rest is dried to obtain a “lower layer solid content” of the solid content of the entire sol. The sol according to [9], which is less than 30% by mass.
[11] The sol according to [9] or [10], wherein the solid content is in the range of 0.01 to 10% by mass.
[12] A titanium tetrachloride aqueous solution is added to 75 ° C. to 100 ° C. hot water containing 1% by mass or more of a nitrogen atom-containing compound, and hydrolyzed in a temperature range of 75 ° C. to the boiling point of the solution, [9 ] To [11] The sol production method according to any one of [11].
[13] The method for producing a sol according to [12], wherein the nitrogen atom-containing compound is water-soluble.
[14] The nitrogen atom-containing compound is ammonia, urea, hydrazine, methylamine hydrochloride, dimethylamine hydrochloride, dimethylamine aqueous solution, trimethylamine hydrochloride, trimethylamine aqueous solution, ethylamine hydrochloride, ethylamine aqueous solution, diethylamine hydrochloride, diethylamine, triethylamine [12] The method for producing a sol according to [12], wherein the sol is at least one compound selected from the group consisting of hydrochloride and triethylamine.
[15] The method for producing a sol according to [12], wherein the nitrogen atom-containing compound is at least one compound selected from the group consisting of ammonia, urea and hydrazine.
[16] The method for producing a sol as described in [12], wherein the nitrogen atom-containing compound is urea.
[17] Any one of [12] to [16], wherein a reactor equipped with a reflux cooling device is used to suppress escape of nitrogen-containing compounds and hydrogen chloride in the system during hydrolysis. The manufacturing method of sol as described in claim | item.
[18] The method for producing a sol according to any one of [12] to [16], wherein chlorine ions in the sol are adjusted to 50 to 10,000 mass ppm as chlorine element.
[19] The method for producing a sol according to [18], wherein chlorine ions in the sol are adjusted to 100 to 4,000 mass ppm as chlorine element.
[20] A thin film comprising brookite crystal-containing titanium oxide according to any one of [1] to [7].
[21] A thin film containing the substance having a photocatalytic function according to [8].
[22] A thin film formed using the sol according to any one of [9] to [11].
[23] The thin film according to any one of [20] to [22], wherein the base material is any one of ceramics, metal, glass, plastic, paper, and wood.
[24] The thin film according to any one of [20] to [23], wherein the thin film is fired.
[25] The thin film according to any one of [20] to [23], wherein the thin film exhibits photocatalytic activity only by drying at a temperature of 80 ° C. or lower.
本発明の窒素原子を含有するブルッカイト結晶含有酸化チタン、光触媒体、ゾルを使用することで、金属、ガラス、プラスチック、紙、木材などの種々の基材に、簡易な手法で、可視光に対して応答性の高い光触媒能を付与させることが可能となった。特に、該ゾルを用いて形成された薄膜は透明性が高いため、様々な基材や物品に対しても、意匠性を損なうことなく同様の光触媒能を付与することが可能である。 By using the brookite crystal-containing titanium oxide, photocatalyst, and sol of the present invention containing nitrogen atoms, various materials such as metal, glass, plastic, paper, and wood can be applied to visible light by a simple method. Thus, it has become possible to impart a highly responsive photocatalytic ability. In particular, since a thin film formed using the sol has high transparency, the same photocatalytic ability can be imparted to various substrates and articles without impairing the design.
本発明の窒素原子を含有するブルッカイト結晶含有酸化チタンのゾルは、安定したゾルでありながら、ゾル中の酸化チタン微粒子はある程度の結晶性を有している点も一つの特長であり、プラスチック、紙など、熱に弱い基材に対しても光触媒能を有する薄膜を形成しやすい。 The brookite crystal-containing titanium oxide sol containing nitrogen atoms of the present invention is a stable sol, and the titanium oxide fine particles in the sol also have a certain degree of crystallinity, which is a feature of plastic, It is easy to form a thin film having a photocatalytic activity even on a heat-sensitive substrate such as paper.
本発明による酸化チタンゾルを用いて製造される酸化チタン薄膜は、不純物が非常に少なく、酸化チタン微粒子が非常に微細な粒子であり、さらにこの酸化チタン微粒子が１次粒子に限りなく近い状態にまで分散しているという顕著な特徴を有している。また、結晶性が高いことから光触媒能力が高く、可視光に対する応答性も高い。 The titanium oxide thin film produced by using the titanium oxide sol according to the present invention has very few impurities, the titanium oxide fine particles are very fine particles, and the titanium oxide fine particles are almost as close to primary particles as possible. It has the remarkable feature of being dispersed. In addition, since the crystallinity is high, the photocatalytic ability is high and the response to visible light is also high.
さらに、本発明の薄膜は、膜強度および剥離強度が強いという特徴を有しているだけでなく、成膜後に紫外線を照射することで光触媒能を高めることも可能である。 Furthermore, the thin film of the present invention has not only the characteristics of high film strength and peel strength, but also can enhance the photocatalytic ability by irradiating ultraviolet rays after film formation.
本発明におけるブルッカイト結晶含有酸化チタンとは、例えば、非特許文献８に記載されているようなブルッカイト型酸化チタンの特徴を有する結晶相を含んでいることを言う。ブルッカイト型の結晶相のみからなるものに限定されるものではなく、ルチル型の結晶相、アナターゼ型の結晶相を含んでいても良い。また、非晶質な部分を含んでいても良い。少なくとも、明らかにブルッカイト型の特徴を有する結晶相の存在が確認できることが必要である。ブルッカイト結晶相の存在を確認する方法として、最も簡便で汎用的に用いられる方法は、粉末Ｘ線回析法である。酸化チタンにブルッカイト結晶相が存在する場合、Cu-Kα１線の回折角から算出される面間隔ｄ（Å）について、３．４６、２．９０、２．４８、２．１４、１．９１、１．７０、１．６７、１．５０、１．４７などにピークの存在が確認できる。ピーク値には測定誤差として０．０２Å程度の誤差が許容される。 The brookite crystal-containing titanium oxide in the present invention means that it contains a crystal phase having the characteristics of brookite-type titanium oxide as described in Non-Patent Document 8, for example. It is not limited to a brookite-type crystal phase alone, and may include a rutile-type crystal phase and an anatase-type crystal phase. Moreover, an amorphous part may be included. At least, it is necessary to be able to confirm the presence of a crystal phase clearly having a brookite-type characteristic. As a method for confirming the presence of the brookite crystal phase, the most convenient and widely used method is a powder X-ray diffraction method. When a brookite crystal phase is present in titanium oxide, the interplanar spacing d (Å) calculated from the diffraction angle of the Cu—Kα1 line is 3.46, 2.90, 2.48, 2.14, 1.91, Presence of peaks can be confirmed at 1.70, 1.67, 1.50, 1.47 and the like. An error of about 0.02 mm is allowed for the peak value as a measurement error.
粉末X線回折法で算出される、ｄ＝２．９０Å近傍のピークは、ブルッカイト結晶相固有の典型ピーク、ｄ＝２．３８Å近傍のピークはアナターゼ結晶相固有の典型ピーク、ｄ＝３．２５Å近傍のピークはルチル結晶相固有の典型ピークであることが知られている。 Calculated by powder X-ray diffraction method, a peak near d = 2.90Å is a typical peak specific to brookite crystal phase, a peak near d = 2.38Å is a typical peak unique to anatase crystal phase, d = 3.25Å It is known that the nearby peak is a typical peak unique to the rutile crystal phase.
したがって、これらのピーク高さを比較すれば、酸化チタンにおけるブルッカイト、アナターゼ、ルチルの各結晶相の存在比率が概算できる。 Therefore, by comparing these peak heights, the abundance ratios of brookite, anatase, and rutile crystal phases in titanium oxide can be estimated.
本発明の酸化チタンの合成方法では、高温での処理を行わないため、ルチルの存在比率は小さくなる。従って、ブルッカイトとアナターゼの存在比率、つまり、ｄ＝２．９０近傍のピーク高さＡと、ｄ＝２．３８近傍のピーク高さＢによって、酸化チタンの結晶相を特徴付けることができる。 In the method for synthesizing titanium oxide according to the present invention, since the treatment at high temperature is not performed, the abundance ratio of rutile becomes small. Therefore, the crystal phase of titanium oxide can be characterized by the abundance ratio of brookite and anatase, that is, the peak height A in the vicinity of d = 2.90 and the peak height B in the vicinity of d = 2.38.
本発明では、ブルッカイト結晶相が含まれている。つまり、ブルッカイト結晶相固有の典型ピークであるｄ＝２．９０Å近傍のピークが検出されれば良いが、ブルッカイト結晶相とアナターゼ結晶相との存在比であるピーク高さ比Ａ／Ｂの値が、０．５より大きいことが好ましい。Ａ／Ｂの値が１より大きいとさらに好ましく、より好ましくは１から３０の範囲であり、さらに好ましくは１から１０である。
Ａ／Ｂの値が０．５より小さいと、ゾルの安定性が良くない場合がある。一方、Ａ／Ｂの値が３０より大きいと、合成が難しく実用的でない場合がある。本発明のブルッカイト結晶含有酸化チタンは、可視光に対する応答性を高めるために、窒素原子が含まれている。窒素原子の含有量は、０．００１〜１０質量％であり、好ましくは０．０１〜５質量％であり、より好ましくは０．１〜２質量％である。０．００１質量％未満では、可視光に対する応答性が低下する。また、１０質量％を超える場合、酸化チタン本来の特徴が失われてしまい、光触媒能が低下してしまう。
In the present invention, a brookite crystal phase is included. That is, it is only necessary to detect a peak in the vicinity of d = 2.90Å which is a typical peak unique to the brookite crystal phase, but the value of the peak height ratio A / B which is the abundance ratio between the brookite crystal phase and the anatase crystal phase is , Preferably greater than 0.5. The value of A / B is more preferably greater than 1, more preferably 1 to 30, and even more preferably 1 to 10.
If the A / B value is less than 0.5, the sol stability may not be good. On the other hand, if the value of A / B is greater than 30, synthesis may be difficult and impractical. The brookite crystal-containing titanium oxide of the present invention contains nitrogen atoms in order to enhance the response to visible light. Content of a nitrogen atom is 0.001-10 mass%, Preferably it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%. If it is less than 0.001% by mass, the response to visible light is lowered. Moreover, when it exceeds 10 mass%, the original characteristic of titanium oxide will be lost and photocatalytic capability will fall.
酸化チタン中の窒素原子の定量法に関しては公知の方法を用いればよく、特に制限はないが、例えば日本工業規格（ＪＩＳ）Ｈ１６１２「チタン及びチタン合金中の窒素定量方法」に準ずる方法を用いれば良い。 A known method may be used for the determination method of nitrogen atoms in titanium oxide, and there is no particular limitation. For example, if a method according to Japanese Industrial Standard (JIS) H1612 “Method for determining nitrogen in titanium and titanium alloys” is used. good.
窒素原子の存在は、酸化チタン粒子の粒子内であっても、表面であってもよい。粒子内であれば、酸素原子を置換した位置であってもいいし、結晶格子間に存在していてもいい。表面に存在する場合には、その存在形態は特に限定されず、全体的でも部分的でも構わないが、部分的な被覆としての存在が好ましい。部分的に存在する形態としては、島状であっても、群島状であっても、マスクメロン状であってもかまわない。 The presence of nitrogen atoms may be in the titanium oxide particles or on the surface. As long as it is inside the particle, it may be at a position where an oxygen atom is substituted, or may exist between crystal lattices. When present on the surface, the form of existence is not particularly limited, and may be whole or partial, but the presence as a partial coating is preferred. The form that exists partially may be an island shape, an archipelago shape, or a mask melon shape.
窒素原子を導入する方法に特に制限はない。例えば、酸化チタンをターゲットとして、窒素を含む雰囲気中でスパッタする方法が挙げられる。また、酸化チタンまたはその薄膜を、アンモニアを含む雰囲気に接触させる方法が挙げられる。その際の温度は特に制限されないが、ブルッカイト型の結晶構造をルチル型の結晶構造に転移させない場合には、０〜４００℃の範囲内で実施するのが好適である。 There is no restriction | limiting in particular in the method of introduce | transducing a nitrogen atom. For example, there is a method of sputtering in an atmosphere containing nitrogen using titanium oxide as a target. Moreover, the method of making titanium oxide or its thin film contact the atmosphere containing ammonia is mentioned. The temperature at that time is not particularly limited, but when the brookite-type crystal structure is not transferred to the rutile-type crystal structure, the temperature is preferably within a range of 0 to 400 ° C.
本発明のブルッカイト結晶含有酸化チタンは、他の粒子、粉末、焼結物、液状物などに混合したり付着させたりして使用することも可能である。本発明において、光触媒機能を有する物質とは、粒子、粉末、焼結物、成形体、樹脂などの固体、ゾル、スラリー、ペースト、コーティング組成物などの液状物であって、酸化チタンを光触媒成分として含有する物質を意味する。 The brookite crystal-containing titanium oxide of the present invention can also be used by mixing or adhering to other particles, powders, sintered products, liquid materials and the like. In the present invention, the substance having a photocatalytic function is a solid such as particles, powder, a sintered product, a molded product, a resin, or a liquid such as sol, slurry, paste, coating composition, and titanium oxide is a photocatalytic component. Means the substance contained as
本発明におけるゾルについて説明する。 The sol in the present invention will be described.
ゾル中の固形分は、該ゾル１００ｇをビーカーに秤取り、１２０℃の恒温乾燥器に３０時間以上入れておき、残った固形分の質量を秤量することで測定できる。 The solid content in the sol can be measured by weighing 100 g of the sol in a beaker, placing it in a constant temperature dryer at 120 ° C. for 30 hours or more, and weighing the mass of the remaining solid content.
さらに、本発明におけるゾルは、安定なゾル状態を維持していることが特徴であり、長時間静置しても固形分が沈降しない。そのことを定義するため、以下のような測定法を定めた。密閉容器に入れて、室温にて２４０時間静置後、液面から８０体積％相当分をデカンテーションで分離し、残りを１２０℃の恒温乾燥器に３０時間以上入れておき、水分を蒸発させる。残った固形分の質量を測定することで、「下層固形分量」とした。この下層固形分が、ゾル全体の固形分量の３０質量％未満であることが好ましい。 Furthermore, the sol in the present invention is characterized by maintaining a stable sol state, and the solid content does not settle even when left for a long time. In order to define this, the following measurement methods were established. Place in an airtight container and let stand at room temperature for 240 hours. Then, 80 volume% equivalent is separated from the liquid surface by decantation, and the rest is placed in a constant temperature dryer at 120 ° C. for 30 hours or more to evaporate water. . By measuring the mass of the remaining solid content, it was set as “lower solid content”. It is preferable that this lower layer solid content is less than 30 mass% of the solid content of the whole sol.
ゾルを塗膜して光触媒薄膜を作成することを考慮した場合、ゾル中の固形分は、特に限定されず、用途において最適な濃度を採用すればよいが、０．０１〜１０質量％であることが好ましい。固形分が０．０１質量％より少ない場合は、塗膜した際に光触媒能を有する薄膜を得ることができない可能性がある。また、固形分が１０質量％より多い場合は、ゾルとしての安定性が悪くなったり、塗膜して得られる薄膜の透明性が悪くなる可能性がある。 In consideration of creating a photocatalyst thin film by coating a sol, the solid content in the sol is not particularly limited, and an optimal concentration may be employed in the application, but is 0.01 to 10% by mass. It is preferable. When the solid content is less than 0.01% by mass, there is a possibility that a thin film having a photocatalytic ability cannot be obtained when it is coated. Moreover, when there is more solid content than 10 mass%, the stability as a sol may worsen or the transparency of the thin film obtained by coating may worsen.
本発明のゾルは、これを濾過、水洗、乾燥することにより酸化チタン粒子を得ることもできる。ゾル中の酸化チタン粒子は細かい方が酸化チタン薄膜の光触媒作用が高まり、また透明性もよくなる。また触媒作用の点から酸化チタン粒子が結晶質であることが好ましい。但し、細かすぎる酸化チタン粒子を得ることは製造上の困難を伴うので、ゾル中の酸化チタン粒子の一次粒子径は平均で０．０１〜０．１μｍであることが望ましく、好ましくは０．０２〜０．０８μｍであり、より好ましくは０．０３〜０．０６μｍである。 Titanium oxide particles can also be obtained by filtering, washing and drying the sol of the present invention. The finer the titanium oxide particles in the sol, the higher the photocatalytic action of the titanium oxide thin film and the better the transparency. From the viewpoint of catalytic action, the titanium oxide particles are preferably crystalline. However, since it is difficult to obtain titanium oxide particles that are too fine, the primary particle diameter of the titanium oxide particles in the sol is desirably 0.01 to 0.1 μm on average, preferably 0.02 It is -0.08 micrometer, More preferably, it is 0.03-0.06 micrometer.
本発明のゾルの製造方法について、特に制限はないが、以下に記載した方法を例示することができる。
ブルッカイト結晶含有酸化チタンゾルは、特許文献１の方法により製造することができる。ブルッカイト結晶含有酸化チタンのゾルを得るには、酸化チタンを形成する際の塩素イオン濃度と温度を制御することが重要である。その際、加水分解により塩化水素が生成する四塩化チタンを原料として用いることが好ましい。つまり、四塩化チタンを特定の条件で加水分解することにより本発明のゾルを効率的に得ることができる。四塩化チタンの加水分解において生成する塩化水素は、反応槽からの逸出を防止し、できるだけゾル中に残留させることが好ましい。発生する塩化水素を逸出させながら四塩化チタンの加水分解を行うと、ゾル中の酸化チタンは粒子径が小さくなりにくく、また結晶性もよくない場合がある。
Although there is no restriction | limiting in particular about the manufacturing method of sol of this invention, The method described below can be illustrated.
The brookite crystal-containing titanium oxide sol can be produced by the method of Patent Document 1. In order to obtain a sol of brookite crystal-containing titanium oxide, it is important to control the chlorine ion concentration and temperature when forming titanium oxide. At that time, it is preferable to use titanium tetrachloride, which generates hydrogen chloride by hydrolysis, as a raw material. That is, the sol of the present invention can be efficiently obtained by hydrolyzing titanium tetrachloride under specific conditions. It is preferable that hydrogen chloride generated in the hydrolysis of titanium tetrachloride is prevented from escaping from the reaction vessel and remains in the sol as much as possible. When the titanium tetrachloride is hydrolyzed while escaping the generated hydrogen chloride, the titanium oxide in the sol is unlikely to have a small particle size and may not have good crystallinity.
加水分解により発生する塩化水素は完全に逸出が防止されていなくても抑制されていればよい。またその抑制方法も、塩化水素の逸出が抑制できるものであれば特に限定されず、例えば加圧することによっても可能であるが、最も容易にして効果的な方法は加水分解の反応槽に還流冷却器を設置して加水分解を行う方法である。加水分解反応によって水及び塩化水素の蒸気が発生するが、その大部分は還流冷却器により凝縮し、反応槽に戻されるので反応槽から外に塩化水素が逸出することは殆どない。 Hydrogen chloride generated by hydrolysis may be suppressed even if escape is not completely prevented. The suppression method is not particularly limited as long as escape of hydrogen chloride can be suppressed. For example, it is possible to apply pressure, but the easiest and most effective method is to return to the hydrolysis reaction tank. This is a method of performing hydrolysis by installing a cooler. Although water and hydrogen chloride vapor are generated by the hydrolysis reaction, most of them are condensed by the reflux condenser and returned to the reaction tank, so that hydrogen chloride hardly escapes from the reaction tank.
加水分解する四塩化チタン水溶液中の四塩化チタンの濃度は低過ぎると生産性が悪くなる場合があり、生成する酸化チタンゾルから薄膜を形成する際の効率が低下する場合がある。また四塩化チタンの濃度が高過ぎると反応が激しくなって、得られる酸化チタンの粒子が微細になりにくく、かつ酸化チタン粒子の分散性も悪くなる場合があるために透明薄膜形成材としては適さない可能性がある。従って、加水分解により酸化チタンの濃度の高いゾルを生成させ、これを多量の水で希釈して酸化チタンの濃度を０．０５〜１０ｍｏｌ／Ｌに調整する方法は好ましくない。ゾルの生成時において酸化チタンの濃度を０．０５〜１０ｍｏｌ／Ｌに調整する方法が好ましく、そのためには加水分解される四塩化チタン水溶液中の四塩化チタンの濃度は生成する酸化チタンの濃度と大差ない値、約０．０５〜１０ｍｏｌ／Ｌとすればよい。ただし、必要ならば以後の工程で少量の水の添加もしくは濃縮することで濃度を０．０５〜１０ｍｏｌ／Ｌに調整してもよい。 If the concentration of titanium tetrachloride in the aqueous solution of titanium tetrachloride to be hydrolyzed is too low, the productivity may be deteriorated, and the efficiency at the time of forming a thin film from the titanium oxide sol to be produced may be lowered. In addition, if the concentration of titanium tetrachloride is too high, the reaction becomes intense, and the resulting titanium oxide particles are less likely to be fine and the dispersibility of the titanium oxide particles may be poor. There is no possibility. Therefore, it is not preferable to produce a sol having a high titanium oxide concentration by hydrolysis and diluting the sol with a large amount of water to adjust the titanium oxide concentration to 0.05 to 10 mol / L. A method of adjusting the concentration of titanium oxide to 0.05 to 10 mol / L at the time of forming the sol is preferable. For this purpose, the concentration of titanium tetrachloride in the aqueous solution of titanium tetrachloride to be hydrolyzed is the same as the concentration of titanium oxide to be generated. What is necessary is just to set it as the value which is not large difference, about 0.05-10 mol / L. However, if necessary, the concentration may be adjusted to 0.05 to 10 mol / L by adding or concentrating a small amount of water in the subsequent steps.
加水分解における温度は７５℃から四塩化チタン水溶液の沸点迄の範囲が好ましい。７５℃未満では加水分解反応に長時間を要する場合があり、さらに、ブルッカイト型酸化チタンを得にくい場合がある。加水分解は、１０分から１２時間程度、所定の温度に保持して行う。この保持時間は加水分解の温度が高温である程短くてよい。四塩化チタン水溶液の加水分解は、四塩化チタンと水との混合溶液を反応槽中で所定の温度に加熱してもよく、また水を反応槽中で予め加熱しておき、これに四塩化チタンを添加し、所定の温度にしてもよい。この加水分解により一般的にはブルッカイト型にアナターゼ型及び／又はルチル型が混合した酸化チタンが得られる。ブルッカイト型の酸化チタンの含有率を高めるには水を反応槽で予め７５〜１００℃に加熱しておき、これに四塩化チタン水溶液を添加し、７５℃〜溶液の沸点の温度範囲で加水分解する方法が適する。 The temperature in the hydrolysis is preferably in the range from 75 ° C. to the boiling point of the aqueous titanium tetrachloride solution. If it is less than 75 degreeC, a hydrolysis reaction may require a long time, and also, it may be difficult to obtain brookite type titanium oxide. Hydrolysis is carried out by maintaining at a predetermined temperature for about 10 minutes to 12 hours. This holding time may be shorter as the hydrolysis temperature is higher. Hydrolysis of the aqueous solution of titanium tetrachloride may be performed by heating a mixed solution of titanium tetrachloride and water to a predetermined temperature in the reaction vessel, or by preheating water in the reaction vessel. Titanium may be added to a predetermined temperature. By this hydrolysis, titanium oxide in which anatase type and / or rutile type are mixed with brookite type is generally obtained. In order to increase the content of brookite-type titanium oxide, water is heated in advance to 75 to 100 ° C. in a reaction vessel, and an aqueous solution of titanium tetrachloride is added thereto, followed by hydrolysis in a temperature range of 75 ° C. to the boiling point of the solution. The method to do is suitable.
ここで、窒素原子を含有するブルッカイト結晶含有酸化チタンのゾルを得るには、四塩化チタンの加水分解の際に、窒素原子含有化合物を反応系内に共存させる方法がある。例えば、窒素原子含有化合物を含む水を反応槽で予め７５〜１００℃に加熱しておき、これに四塩化チタン水溶液を添加し、７５℃〜溶液の沸点の温度範囲で加水分解する。
この際の窒素原子含有化合物は、特に限定されないが、物質中に窒素原子を含んでいれば良く、単体でも複数の化合物の混合物でも良い。
Here, in order to obtain a brookite crystal-containing titanium oxide sol containing nitrogen atoms, there is a method in which a nitrogen atom-containing compound is allowed to coexist in the reaction system during the hydrolysis of titanium tetrachloride. For example, water containing a nitrogen atom-containing compound is previously heated to 75 to 100 ° C. in a reaction vessel, and an aqueous titanium tetrachloride solution is added thereto, and hydrolyzed in a temperature range of 75 ° C. to the boiling point of the solution.
The nitrogen atom-containing compound at this time is not particularly limited, but may be any substance as long as it contains a nitrogen atom, and may be a single substance or a mixture of a plurality of compounds.
例として、アンモニア、尿素、ヒドラジン、メチルアミン塩酸塩、ジメチルアミン塩酸塩、ジメチルアミン水溶液、トリメチルアミン塩酸塩、トリメチルアミン水溶液、エチルアミン塩酸塩、エチルアミン水溶液、ジエチルアミン塩酸塩、ジエチルアミン、トリエチルアミン塩酸塩、トリエチルアミン、アニリン、アセトニトリル、アクリロニトリル、ベンゾニトリル、イソフタロニトリル、テレフタロニトリル、ニトロベンゼン、ピリジン、ヒダントイン、グリシン、グリシン塩酸塩、グリシンナトリウム塩水和物、グリシンアミド、アラニン、アラニンアミド塩酸塩、塩化アンモニウム、臭化アンモニウム、アクリルアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ヘキサメチレンジアミン、アミノフェノール、ピコリン酸、ピコリン、ニコチン酸、クロロアニリン、クロロニトロアニリンなどが挙げられる。 Examples include ammonia, urea, hydrazine, methylamine hydrochloride, dimethylamine hydrochloride, dimethylamine aqueous solution, trimethylamine hydrochloride, trimethylamine aqueous solution, ethylamine hydrochloride, ethylamine aqueous solution, diethylamine hydrochloride, diethylamine, triethylamine hydrochloride, triethylamine, aniline. , Acetonitrile, acrylonitrile, benzonitrile, isophthalonitrile, terephthalonitrile, nitrobenzene, pyridine, hydantoin, glycine, glycine hydrochloride, glycine sodium salt hydrate, glycinamide, alanine, alaninamide hydrochloride, ammonium chloride, ammonium bromide , Acrylamide, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylenediamine, aminophenol Picolinic acid, picoline, nicotinic acid, chloroaniline, etc. chloro nitro aniline.
ここで用いる窒素原子含有化合物は水溶性である方が好ましく、例として、アンモニア、尿素、ヒドラジン、メチルアミン塩酸塩、ジメチルアミン塩酸塩、ジメチルアミン水溶液、トリメチルアミン塩酸塩、トリメチルアミン水溶液、エチルアミン塩酸塩、エチルアミン水溶液、ジエチルアミン塩酸塩、ジエチルアミン、トリエチルアミン塩酸塩、トリエチルアミン、アニリン、アセトニトリル、グリシン、グリシン塩酸塩、グリシンナトリウム塩水和物、アラニン、アラニンアミド塩酸塩、塩化アンモニウム、臭化アンモニウム、ピコリン酸、ニコチン酸などが挙げられる。 The nitrogen atom-containing compound used here is preferably water-soluble, and examples include ammonia, urea, hydrazine, methylamine hydrochloride, dimethylamine hydrochloride, dimethylamine aqueous solution, trimethylamine hydrochloride, trimethylamine aqueous solution, ethylamine hydrochloride, Ethylamine aqueous solution, diethylamine hydrochloride, diethylamine, triethylamine hydrochloride, triethylamine, aniline, acetonitrile, glycine, glycine hydrochloride, glycine sodium salt hydrate, alanine, alaninamide hydrochloride, ammonium chloride, ammonium bromide, picolinic acid, nicotinic acid Etc.
より好ましくは、アンモニア、尿素、ヒドラジン、メチルアミン塩酸塩、ジメチルアミン塩酸塩、ジメチルアミン水溶液、トリメチルアミン塩酸塩、トリメチルアミン水溶液、エチルアミン塩酸塩、エチルアミン水溶液、ジエチルアミン塩酸塩、ジエチルアミン、トリエチルアミン塩酸塩、トリエチルアミンの群から選ばれた1種類以上の化合物である。 More preferably, ammonia, urea, hydrazine, methylamine hydrochloride, dimethylamine hydrochloride, dimethylamine aqueous solution, trimethylamine hydrochloride, trimethylamine aqueous solution, ethylamine hydrochloride, ethylamine aqueous solution, diethylamine hydrochloride, diethylamine, triethylamine hydrochloride, triethylamine One or more compounds selected from the group.
さらに好ましくは、アンモニア、尿素、ヒドラジンの群から選ばれた1種類以上の化合物であり、中でも、もっとも好ましいのは尿素である。 More preferred is one or more compounds selected from the group consisting of ammonia, urea and hydrazine, and of these, urea is most preferred.
窒素原子含有化合物から窒素原子が酸化チタンに取り込まれる機構について、詳細は不明であるが、窒素原子含有化合物が熱分解されて四塩化チタンの加水分解中に取り込まれ、窒素原子含有酸化チタンになるものと思われる。 The details of the mechanism by which nitrogen atoms are incorporated into titanium oxide from nitrogen atom-containing compounds are unknown, but the nitrogen atom-containing compounds are thermally decomposed and incorporated during the hydrolysis of titanium tetrachloride to become nitrogen atom-containing titanium oxides. It seems to be.
加水分解の際に塩化水素の逸出を防ぐために還流冷却管を使用する方法を説明したが、この方法は窒素含有化合物あるいはその熱分解によって生じる窒素含有成分の逸出を防ぎ、酸化チタン中に窒素原子を取り込み易くする目的でも有効である。 The method of using a reflux condenser to prevent escape of hydrogen chloride during hydrolysis has been described, but this method prevents escape of nitrogen-containing compounds or nitrogen-containing components caused by thermal decomposition of the tubes, and is contained in titanium oxide. It is also effective for the purpose of facilitating incorporation of nitrogen atoms.
窒素は、酸化チタン中の酸素の一部を置換しているものと考えられる。酸化チタンの酸素が窒素で置換された場合、Ｘ線光電子分光分析におけるＴｉ−Ｎの結合エネルギーが３９６ｅＶであると報告されているが（非特許文献７）、本発明で得られた窒素原子含有酸化チタンにおいても、３９６ｅＶにおけるピークが確認された。 Nitrogen is considered to substitute a part of oxygen in titanium oxide. When the oxygen of titanium oxide is replaced with nitrogen, it has been reported that the binding energy of Ti—N in X-ray photoelectron spectroscopy analysis is 396 eV (Non-patent Document 7). Also in titanium oxide, a peak at 396 eV was confirmed.
本発明において生成したゾルは脱塩素処理やあるいは支障ない範囲で水の添加、脱水等により塩素イオン濃度を任意に調整することができる。塩素イオンは、該ゾルから薄膜を形成した際の基材への密着性および薄膜の透明性に影響を与える。ゾル中の塩素イオンは、塩素元素として５０〜１０，０００質量ｐｐｍに調整することが好ましく、より好ましくは１００〜４，０００質量ｐｐｍである。５０質量ｐｐｍ未満では基材に形成した酸化チタン薄膜の基材との密着性が十分でない場合がある。１０，０００質量ｐｐｍを越えると薄膜の透明性が劣る可能性がある。 In the sol produced in the present invention, the chlorine ion concentration can be arbitrarily adjusted by dechlorination treatment or addition of water, dehydration and the like within a range that does not hinder. Chlorine ions affect the adhesion to the substrate and the transparency of the thin film when a thin film is formed from the sol. The chlorine ion in the sol is preferably adjusted to 50 to 10,000 mass ppm as the elemental chlorine, more preferably 100 to 4,000 mass ppm. If it is less than 50 mass ppm, the adhesiveness with the base material of the titanium oxide thin film formed in the base material may not be enough. If it exceeds 10,000 mass ppm, the transparency of the thin film may be inferior.
上記の塩素イオンの作用については定かでないが、酸化チタンゾル中において酸化チタン粒子間の電気的な反発が多くなって、粒子の分散性が良好となり、高い透明性が得られると推定される。さらに、ゾル中の塩素イオン濃度は、基材に薄膜を形成した場合の膜強度および剥離強度にも影響を与える。 Although the action of the above chlorine ions is not clear, it is presumed that the electrical repulsion between the titanium oxide particles increases in the titanium oxide sol, the dispersibility of the particles becomes good, and high transparency is obtained. Furthermore, the chloride ion concentration in the sol also affects the film strength and peel strength when a thin film is formed on the substrate.
生成したゾルに後から塩素イオンを塩素元素として５０〜１０，０００質量ｐｐｍ含めることも可能である。これによって該ゾルから形成された薄膜は触媒機能に優れ、基材との密着性も高いものとなる。 It is also possible to later contain 50 to 10,000 ppm by mass of chlorine ions as elemental chlorine in the generated sol. As a result, the thin film formed from the sol has an excellent catalytic function and high adhesion to the substrate.
脱塩素処理は一般的に使用される公知の手段でよく、例えば、電気透析、イオン交換樹脂、電気分解などが採用可能である。脱塩素の程度はゾルのｐＨを目安にすればよく、塩素イオンが５０〜１０，０００質量ｐｐｍの場合、ｐＨは約５〜０．５、塩素イオンが１００〜４，０００質量ｐｐｍの場合、ｐＨは約４〜１である。 The dechlorination treatment may be a known means that is generally used. For example, electrodialysis, ion exchange resin, electrolysis, etc. can be employed. The degree of dechlorination may be based on the pH of the sol. When the chlorine ion is 50 to 10,000 mass ppm, the pH is about 5 to 0.5, and the chlorine ion is 100 to 4,000 mass ppm. The pH is about 4-1.
本発明のゾルに有機溶媒を加え、水と有機溶媒の混合物に酸化チタン粒子を分散させることもできる。 An organic solvent can be added to the sol of the present invention, and the titanium oxide particles can be dispersed in a mixture of water and the organic solvent.
本発明の酸化チタンゾルの製造方法はバッチ式に限らず、反応槽を連続槽にして四塩化チタンと水を連続投入しながら、投入口の反対側で反応液を取り出し、引き続き脱塩素処理するような連続方式も可能である。 The production method of the titanium oxide sol of the present invention is not limited to a batch type, and while continuously adding titanium tetrachloride and water with the reaction tank as a continuous tank, the reaction solution is taken out on the opposite side of the inlet, and subsequently dechlorinated. A continuous system is also possible.
本発明の酸化チタンゾルから酸化チタンの薄膜を形成する場合、加水分解反応で生成したゾルをそのまま用いるのが好ましい。本発明で得られたゾルは、粒子の一次粒子径が小さいと同時に分散性が良好であるので、ゾルの状態で白濁している場合であっても、薄膜を形成した場合には透明なものとできる。 When forming a thin film of titanium oxide from the titanium oxide sol of the present invention, it is preferable to use the sol produced by the hydrolysis reaction as it is. Since the sol obtained in the present invention has a small primary particle size and good dispersibility, it is transparent when a thin film is formed even when it is clouded in the sol state. And can.
本発明で得られた窒素を含有するブルッカイト結晶含有酸化チタンのゾルを薄膜形成に用いる場合、塗膜の成膜性を高めるためにゾルに水溶性高分子を少量、例えば１０〜１０，０００質量ｐｐｍ程度添加してもよい。水溶性高分子としてはポリビニルアルコール、メチルセルロース、エチルセルロース、ＣＭＣ、澱粉などが好適である。 When the brookite crystal-containing titanium oxide sol containing nitrogen obtained in the present invention is used for thin film formation, a small amount of water-soluble polymer, for example, 10 to 10,000 mass, is added to the sol in order to improve the film formability of the coating film. About ppm may be added. As the water-soluble polymer, polyvinyl alcohol, methyl cellulose, ethyl cellulose, CMC, starch and the like are suitable.
本発明の窒素を含有するブルッカイト結晶含有酸化チタンのゾルを各種の材料、成形体等の基材に塗布することによって、基材の表面に酸化チタン薄膜を容易に形成することができる。基材としてはセラミックス、ガラス、金属、プラスチック、木材、紙等殆ど制限なく対象とすることができる。基材をアルミナ、ジルコニア等からなる触媒担体とし、これに酸化チタン薄膜の触媒を担持して触媒として使用することもできる。 By applying the nitrogen-containing brookite crystal-containing titanium oxide sol of the present invention to a substrate such as various materials and molded articles, a titanium oxide thin film can be easily formed on the surface of the substrate. As the substrate, ceramics, glass, metal, plastic, wood, paper, etc. can be used without any limitation. The base material may be a catalyst carrier made of alumina, zirconia or the like, and a titanium oxide thin film catalyst may be supported on the base material and used as a catalyst.
また蛍光ランプ等の照明器具のガラスやそのプラスチックカバー等を基材としてこれに酸化チタン薄膜を形成すれば薄膜は透明であり、かつ光触媒作用を有するので光を遮蔽することなく油煙等の有機物を分解することができ、ガラスやカバーの汚れを防止するのに有効である。また建築用ガラスや壁材に酸化チタン薄膜を形成すれば同様に汚れを防止することが可能になるので、高層ビルなどの窓材や壁材に用いることができ、清掃作業を必要としなくなるためビル管理コスト削減に役立つ。 In addition, if a titanium oxide thin film is formed on a glass or plastic cover of a lighting fixture such as a fluorescent lamp as a base material, the thin film is transparent and has a photocatalytic action, so that organic substances such as oil and smoke can be removed without shielding light. It can be disassembled and is effective in preventing dirt on the glass and cover. In addition, if a titanium oxide thin film is formed on architectural glass or wall materials, it becomes possible to prevent contamination as well, so it can be used for window materials and wall materials for high-rise buildings, etc., and cleaning work is not required. Helps reduce building management costs.
本発明で得られる光触媒薄膜は、可視光に対する応答性も高いため、特に室内での微弱光に対しても光触媒能を発現できる特長を持つ。ここで言う光触媒能は、防汚性、防曇性、超親水性、有機物の光分解性などを示す。 Since the photocatalytic thin film obtained by the present invention has a high response to visible light, the photocatalytic thin film has a feature that the photocatalytic ability can be expressed especially for weak light in a room. The photocatalytic ability mentioned here indicates antifouling properties, antifogging properties, super hydrophilicity, organic photodegradability, and the like.
酸化チタンゾルを基材に塗布するには基材をゾル中に浸漬する方法、基材にゾルをスプレーする方法、ゾルを刷毛で基材に塗布する方法などが採用される。ゾルの塗布量は液状の厚さにして０．０１〜０．２ｍｍが適当である。塗布後乾燥して水分を除去すれば薄膜が得られ、このままでも触媒等の用途に供することができる。また、成膜後に紫外線を照射することは光触媒能を高めるために有効である。表面近傍に残存する有機物が紫外線照射による光触媒作用で分解して、光触媒粒子が膜表面により存在しやすくなるためであろうと考えられる。 In order to apply the titanium oxide sol to the substrate, a method of immersing the substrate in the sol, a method of spraying the sol on the substrate, a method of applying the sol to the substrate with a brush, and the like are employed. The coating amount of the sol is suitably 0.01 to 0.2 mm in terms of liquid thickness. A thin film can be obtained by removing moisture by drying after coating, and it can be used for applications such as a catalyst. In addition, irradiation with ultraviolet rays after film formation is effective for enhancing the photocatalytic activity. This is probably because the organic matter remaining in the vicinity of the surface is decomposed by the photocatalytic action by the ultraviolet irradiation, and the photocatalytic particles are more likely to exist on the film surface.
本発明の窒素を含有するブルッカイト結晶含有酸化チタンのゾルの場合は、安定したゾルでありながら、ゾル中の酸化チタン微粒子はある程度の結晶性を有している点も一つの特長である。従って、本発明のゾルは、プラスチック、紙など、熱に弱い基材に対しても光触媒能を有する薄膜を形成しやすいという効果を発揮する。 In the case of the titanium oxide-containing titanium oxide sol containing nitrogen according to the present invention, the titanium oxide fine particles in the sol have a certain degree of crystallinity while being a stable sol. Therefore, the sol of the present invention exhibits an effect that it is easy to form a thin film having a photocatalytic activity even on a heat-sensitive substrate such as plastic and paper.
さらに本発明の薄膜は、可視光応答性が高いという顕著な特長を併せ持つ光触媒体となる。 Furthermore, the thin film of the present invention becomes a photocatalyst having a remarkable feature of high visible light responsiveness.
基材が金属やセラミックス、例えばガラス等の耐熱性である場合は酸化チタン薄膜を形成後焼成することができ、これによって薄膜は一層強く基材に密着し、薄膜の硬度も上る。この焼成温度は２００℃以上が好ましい。焼成温度の上限には特に制限はなく、基材の耐熱性に応じて定めればよいが、あまり温度を高くしても薄膜の硬度や基材との密着性は増さないので８００℃以下が適当である。また、ブルッカイト型の結晶構造を維持するには７００℃以下の温度で焼結するのがよい。焼成の雰囲気は特に制限されず、大気中でも構わない。焼成時間は特に制限はなく、例えば１〜６０分の範囲で行えばよい。 When the base material is heat resistant such as metal or ceramics, for example, glass, it can be fired after forming the titanium oxide thin film, whereby the thin film adheres more strongly to the base material and the hardness of the thin film increases. The firing temperature is preferably 200 ° C. or higher. The upper limit of the firing temperature is not particularly limited and may be determined according to the heat resistance of the base material. However, even if the temperature is increased too much, the hardness of the thin film and the adhesion to the base material do not increase, so 800 ° C. or lower. Is appropriate. In order to maintain the brookite-type crystal structure, sintering is preferably performed at a temperature of 700 ° C. or lower. The firing atmosphere is not particularly limited and may be in the air. There is no restriction | limiting in particular in baking time, For example, what is necessary is just to carry out in the range of 1 to 60 minutes.
本発明の透明薄膜をより強固で基材に対する接着力を高めるために、適当な接着剤を酸化チタンゾルに添加することもできる。例えば、有機シリカ化合物、ジルコニウム化合物、アルミニウムアルコキシド、チタニウムアルコキシドの群から選ばれた１種類または２種類以上の混合物が好適である。添加量は本発明の酸化チタンゾル中の酸化チタンに対し、加水分解されて得られる金属酸化物換算にして１〜５０重量％程度が好ましい。添加量が１重量％未満であると、接着剤の添加効果が低い可能性がある。また、５０重量％を越えると、基材に対する接着強度は非常に強固になるが、酸化チタン粒子が接着剤に覆われて光触媒能が低下する場合がある。 In order to make the transparent thin film of the present invention stronger and increase the adhesion to the substrate, an appropriate adhesive can be added to the titanium oxide sol. For example, one type or a mixture of two or more types selected from the group of organic silica compounds, zirconium compounds, aluminum alkoxides, and titanium alkoxides are suitable. The addition amount is preferably about 1 to 50% by weight in terms of metal oxide obtained by hydrolysis with respect to the titanium oxide in the titanium oxide sol of the present invention. If the addition amount is less than 1% by weight, the effect of adding the adhesive may be low. On the other hand, if it exceeds 50% by weight, the adhesive strength to the substrate becomes very strong, but the titanium oxide particles are covered with an adhesive and the photocatalytic ability may be lowered.
この場合成膜直前に混合するか、あらかじめゾルに混合した状態にするかは、接着剤の性質により選択すればよく、どちらを採用しても本発明の効果には影響しない。 In this case, whether it is mixed immediately before film formation or in a state of being mixed in advance with the sol may be selected depending on the properties of the adhesive, and whichever is adopted does not affect the effect of the present invention.
この接着剤を含む薄膜は焼成しなくてもよいが焼成することもできる。また、成膜後に紫外線を照射することは光触媒能を高めるために有効である。 The thin film containing the adhesive does not need to be fired, but can be fired. In addition, irradiation with ultraviolet rays after film formation is effective for enhancing the photocatalytic activity.
光触媒性や親水性を付与する対象となる物品としては、とくに制限されないが、各種建材、窓ガラス、機械、車両、ガラス製品、家電製品、農業資材、電子機器、工具、純水製造器、食器、風呂用品、トイレ用品、家具、衣類、布製品、繊維、革製品、紙製品、スポーツ用品、美容器具、健康増進器具、医療用具、蒲団、容器、眼鏡、看板、配管、配線、金具、衛生資材、自動車用品などを例示することができる。また、シックハウス対策や、水・大気・土壌中のＰＣＢやダイオキシン類のような有機塩素化合物の分解、水・土壌中の残留農薬や環境ホルモンの分解、温泉の浄化などに有効な環境浄化機器・装置にも応用できる。その際には、あらかじめブルッカイト結晶含有酸化チタンを樹脂に練りこんだり、繊維に混合したりしたものを物品等成形時の原料に混合することも可能であるが、特に限定されない。 There are no particular restrictions on the articles to which photocatalytic or hydrophilic properties are imparted, but various building materials, window glass, machinery, vehicles, glass products, household appliances, agricultural materials, electronic equipment, tools, pure water producers, tableware , Bath products, toilet products, furniture, clothing, fabric products, textiles, leather products, paper products, sports equipment, beauty equipment, health promotion equipment, medical equipment, baskets, containers, glasses, signs, piping, wiring, metal fittings, sanitary materials An automobile article etc. can be illustrated. In addition, environmental purification equipment effective for sick house measures, decomposition of organic chlorine compounds such as PCBs and dioxins in water, air and soil, decomposition of residual agricultural chemicals and environmental hormones in water and soil, purification of hot springs, etc. It can also be applied to equipment. In that case, it is possible to mix a brookite crystal-containing titanium oxide in advance with a resin, or a fiber mixed with a fiber, but it is not particularly limited.
また、物品が効果的にその光触媒性や親水性を発現することができる光源として、太陽、蛍光灯、白熱電球、水銀ランプ、キセノンランプ、ハロゲンランプ、水銀キセノンランプ、メタルハライドランプ、発光ダイオード、レーザー、有機物の燃焼炎などを例示することができる。また蛍光灯としては、白色蛍光灯、昼白色蛍光灯、昼光色蛍光灯、温白色蛍光灯、電球色蛍光灯、ブラックライト、などを例示することができるが、特にこれらに限定されない。 In addition, as a light source that can effectively develop its photocatalytic property and hydrophilicity, the sun, fluorescent lamp, incandescent lamp, mercury lamp, xenon lamp, halogen lamp, mercury xenon lamp, metal halide lamp, light emitting diode, laser Examples include organic combustion flames. Examples of the fluorescent lamp include a white fluorescent lamp, a daylight white fluorescent lamp, a daylight fluorescent lamp, a warm white fluorescent lamp, a light bulb fluorescent lamp, and a black light, but are not particularly limited thereto.
本発明による酸化チタンゾルを用いて製造される酸化チタン薄膜は、不純物が非常に少なく、酸化チタン微粒子が非常に微細な粒子あり、さらにこの酸化チタン微粒子が１次粒子に限りなく近い状態にまで分散しているという顕著な特徴を有している。また、結晶性が高いことから光触媒能力が高く、可視光に対する応答性も高い。 The titanium oxide thin film produced using the titanium oxide sol according to the present invention has very few impurities, the titanium oxide fine particles are very fine particles, and the titanium oxide fine particles are dispersed to a state close to the primary particles. It has the remarkable feature of being. In addition, since the crystallinity is high, the photocatalytic ability is high and the response to visible light is also high.
窒素を含むブルッカイト結晶含有酸化チタンおよびその薄膜を、さらにアンモニア気流中でアニ−ルしたり、スパッタリングすることも可能である。また、窒素原子以外の原子（イオウ、遷移金属元素など）を導入することも可能である。 The brookite crystal-containing titanium oxide containing nitrogen and its thin film can be further annealed or sputtered in an ammonia stream. It is also possible to introduce atoms other than nitrogen atoms (such as sulfur and transition metal elements).
以下、実施例により具体的に説明するが、本発明は実施例に限定されるものではない。 Hereinafter, although an example explains concretely, the present invention is not limited to an example.
実施例１
（窒素含有ブルッカイト結晶含有酸化チタンゾルの合成、固形分の分析）
反応槽にイオン交換水７００ｍＬと尿素１１．３ｇを加え、攪拌しながら加熱して温度を９５℃に保持した。そこへＴｉ濃度１５質量％の四塩化チタン水溶液（住友チタニウム株式会社）１２０ｇを６０分間かけて滴下した。滴下終了後に温度を１０１℃とし、攪拌しながら６０分間保持した。得られた白色懸濁液を電気透析機にかけてｐＨを４．０にした。さらに限外濾過膜で濃縮して白色スラリーを得た。この白色スラリーの一部をガラス製密閉容器に入れ、室温にて２４０時間静置し、８０体積％の液量をデカンテーションで分離し、残りを１２０℃の恒温乾燥器内に３０時間入れて乾燥させた。こうして得られた粉末の質量を測定し、「下層固形分量」を求めた。
Example 1
(Synthesis of nitrogen-containing brookite crystal-containing titanium oxide sol, analysis of solid content)
700 mL of ion exchange water and 11.3 g of urea were added to the reaction tank, and the temperature was maintained at 95 ° C. by heating with stirring. 120 g of titanium tetrachloride aqueous solution (Sumitomo Titanium Co., Ltd.) having a Ti concentration of 15% by mass was dropped therein over 60 minutes. After completion of the dropping, the temperature was set to 101 ° C. and held for 60 minutes with stirring. The resulting white suspension was subjected to an electrodialysis machine to adjust the pH to 4.0. Furthermore, it concentrated with the ultrafiltration membrane and obtained the white slurry. A portion of this white slurry is placed in a glass sealed container and allowed to stand at room temperature for 240 hours. The 80% by volume liquid is separated by decantation, and the rest is placed in a constant temperature dryer at 120 ° C. for 30 hours. Dried. The mass of the powder thus obtained was measured, and the “lower solid content” was determined.
別途、白色スラリーの一部を採取し、乾燥恒量法により固形分濃度を測定した。以上の結果、全体の固形分濃度は４．２質量％、下層固形分は、全体の固形分の２２質量％であった。その際、得られた固形分は黄色味を帯びていた。この固形分をメノウ乳鉢で粉砕し、粉末Ｘ線回折の測定を行った。測定装置としてＲｉｇａｋｕ−Ｒｉｎｔ Ｕｌｔｉｍａ+を使用した。Ｘ線源はＣｕＫα１を使用し、出力は４０ｋＶ−２０ｍＡ、スリットはＤＳ１°−ＳＳ１°−ＲＳ０．３ｍｍとし、スキャンスピード２°／ｍｉｎで１０°〜８０°の範囲について測定した。得られた回析チャートを図１に示す。ｄ＝２．９０（２θ＝３０．８）のピーク高さＡと、ｄ＝２．３８（２θ＝３７．７）のピーク高さＢとの比Ａ／Ｂは、１．５で、ブルッカイト結晶構造を有する酸化チタンを含んでいることを確認した。 Separately, a part of the white slurry was collected and the solid content concentration was measured by a dry constant weight method. As a result, the total solid content concentration was 4.2% by mass, and the lower layer solid content was 22% by mass of the total solid content. At that time, the obtained solid was yellowish. This solid content was pulverized with an agate mortar and measured for powder X-ray diffraction. Rigaku-Rint Ultimate + was used as a measuring device. CuKα1 was used as the X-ray source, the output was 40 kV-20 mA, the slit was DS1 ° -SS1 ° -RS 0.3 mm, and measurement was performed in the range of 10 ° -80 ° at a scan speed of 2 ° / min. The obtained diffraction chart is shown in FIG. The ratio A / B between the peak height A of d = 2.90 (2θ = 30.8) and the peak height B of d = 2.38 (2θ = 37.7) is 1.5, and brookite It was confirmed that titanium oxide having a crystal structure was included.
この酸化チタン中の窒素含有量を、日本工業規格（ＪＩＳ）Ｈ１６１２に準ずる方法で測定したところ、０．４７質量％であった。さらに、この粉末のＸ線光電子分光分析を行ったところ、３９６ｅＶのピークの存在が確認され、Ｔｉ−Ｎ結合が確認された。 It was 0.47 mass% when the nitrogen content in this titanium oxide was measured by the method according to Japanese Industrial Standard (JIS) H1612. Furthermore, when X-ray photoelectron spectroscopy analysis of this powder was performed, the presence of a 396 eV peak was confirmed, and a Ti—N bond was confirmed.
また、酸化チタンの一次粒子の平均粒子径はＢＥＴ比表面積値を用い、粒子を真球と仮定することにより（１）式より求めたところ０．０４μｍであった。 Further, the average particle diameter of the primary particles of titanium oxide was 0.04 μm as determined from the formula (1) by using the BET specific surface area value and assuming the particles to be true spheres.
Ｄ１＝６／ρＳ（１） （ρ：粒子の真比重、Ｓ：ＢＥＴ比表面積）
（光触媒活性評価）
酸化チタン粉末０．１ｇを直径９０ｍｍのガラス製シャーレ上に広げ、テドラー（登録商標）バッグ５Ｌ（ジーエル サイエンス（株）製）内に置き、アセトアルデヒド２０体積ｐｐｍを含む空気約５Ｌを封入した。これを３つ用意し、一つは暗所に置き、別の一つは昼光色蛍光灯（東芝ライテック（株）製、メロウホワイト（登録商標）、２０Ｗ）下で照度が６０００ルックスとなる所に置き、別の一つは紫外線吸収膜付蛍光灯（東芝ライテック（株）製、紫外線吸収膜付蛍光ランプ、２０W）下で照度が６０００ルックスとなる所に置いた。２時間経過後のテドラー（登録商標）バッグ内のアセトアルデヒド濃度を、ガス検知管（（株）ガステック製、Ｎｏ．９２L）で測定した。その結果、暗所に置いたものは１５体積ｐｐｍ、昼光色蛍光灯下に置いたものは体積３ｐｐｍ、紫外線吸収膜付蛍光灯下に置いたものは６体積ｐｐｍであった。
D1 = 6 / ρS (1) (ρ: true specific gravity of particles, S: BET specific surface area)
(Photocatalytic activity evaluation)
0.1 g of titanium oxide powder was spread on a glass petri dish having a diameter of 90 mm, placed in a Tedlar (registered trademark) bag 5 L (manufactured by GL Sciences), and about 5 L of air containing 20 ppm by volume of acetaldehyde was enclosed. Prepare three of these, one in the dark, and the other in the place where the illuminance is 6000 lux under daylight fluorescent lamp (Toshiba Lighting & Technology Co., Ltd., Mellow White (registered trademark), 20W). Another one was placed under a fluorescent lamp with an ultraviolet absorbing film (Toshiba Lighting & Technology Co., Ltd., fluorescent lamp with an ultraviolet absorbing film, 20 W) at an illuminance of 6000 lux. The acetaldehyde concentration in the Tedlar (registered trademark) bag after 2 hours was measured with a gas detector tube (manufactured by Gastec Co., Ltd., No. 92L). As a result, 15 ppm by volume was placed in a dark place, 3 ppm by volume placed under a daylight fluorescent lamp, and 6 ppm by volume placed under a fluorescent lamp with an ultraviolet absorbing film.
実施例２
（薄膜の作成）
実施例１で得られたゾル２０ｇに、ヒドロキシ塩化ジルコニウム水溶液（ＺｒＯ2として５質量％含有）４ｇとエチルアルコール１０ｇを加え、混合し、コーティング液を調製した。このコーティング液４ｍＬを２０ｃｍ×２０ｃｍのガラス板上に垂らし、ガラス棒で全体に広げた後に、垂直に１０分間保持して余分なコーティング液を流下除去した。これを、１５０℃の恒温乾燥器に入れ、１０分間保持した。得られた薄膜は、無色透明であり、３Ｈの鉛筆で引っ掻いても剥がれなかった。
Example 2
(Creation of thin film)
To 20 g of the sol obtained in Example 1, 4 g of a hydroxyzirconium chloride aqueous solution (containing 5% by mass as ZrO 2 ) and 10 g of ethyl alcohol were added and mixed to prepare a coating solution. 4 mL of this coating solution was dropped on a 20 cm × 20 cm glass plate, spread over the whole with a glass rod, and then held vertically for 10 minutes to remove the excess coating solution. This was placed in a constant temperature dryer at 150 ° C. and held for 10 minutes. The obtained thin film was colorless and transparent and was not peeled off even when scratched with a 3H pencil.
（光触媒活性評価）
上記で得た薄膜付ガラス板を、テドラー（登録商標）バッグ５Ｌ（ジーエル サイエンス（株）製）内に置き、アセトアルデヒド２０体積ｐｐｍを含む空気約５Ｌを封入した。これを３つ用意し、実施例１で記載した方法で光に照射させ、４時間経過後のアセトアルデヒド濃度を同様に測定した。その結果、暗所に置いたものは１９体積ｐｐｍ、昼光色蛍光灯下に置いたものは５体積ｐｐｍ、紫外線吸収膜付蛍光灯下に置いたものは８体積ｐｐｍであった。
(Photocatalytic activity evaluation)
The glass plate with a thin film obtained above was placed in a Tedlar (registered trademark) bag 5L (manufactured by GL Science Co., Ltd.), and about 5 L of air containing 20 ppm by volume of acetaldehyde was enclosed. Three of these were prepared, irradiated with light by the method described in Example 1, and the acetaldehyde concentration after 4 hours was measured in the same manner. As a result, 19 vol ppm was placed in the dark, 5 vol ppm was placed under the daylight fluorescent lamp, and 8 vol ppm was placed under the fluorescent lamp with the ultraviolet absorbing film.
実施例３
（バインダー溶液の調製）
還流冷却器を備えた２００ｍＬフラスコにイオン交換水９０ｍＬとメタノール３０ｍＬとアセチルアセトン５ｇと酢酸５ｇとを入れて、攪拌しながら加熱して７０℃に保持した。そこへアルミニウムトリイソプロポキシド１２ｇを添加して、２時間還流した。その後、攪拌下放冷してバインダー溶液とした。
Example 3
(Preparation of binder solution)
In a 200 mL flask equipped with a reflux condenser, 90 mL of ion-exchanged water, 30 mL of methanol, 5 g of acetylacetone, and 5 g of acetic acid were added and heated to 70 ° C. while stirring. Thereto, 12 g of aluminum triisopropoxide was added and refluxed for 2 hours. Thereafter, the mixture was allowed to cool with stirring to obtain a binder solution.
（薄膜の作成）
実施例１で得られたゾル２０ｇに、イオン交換水５０ｇと上記で得られたバインダー溶液３０ｇを加え、混合し、コーティング液を調製した。このコーティング液４ｍＬを２０ｃｍ×２０ｃｍのガラス板上に垂らし、ガラス棒で全体に広げた後に、垂直に１０分間保持して余分なコーティング液を流下除去した。これを、室温（１５℃〜２５℃の範囲内）で２４時間乾燥、硬化させた。得られた薄膜は、無色透明であり、３Ｈの鉛筆で引っ掻いても剥がれなかった。
(Creation of thin film)
To 20 g of the sol obtained in Example 1, 50 g of ion-exchanged water and 30 g of the binder solution obtained above were added and mixed to prepare a coating solution. 4 mL of this coating solution was dropped on a 20 cm × 20 cm glass plate, spread over the whole with a glass rod, and then held vertically for 10 minutes to remove the excess coating solution. This was dried and cured at room temperature (in the range of 15 ° C. to 25 ° C.) for 24 hours. The obtained thin film was colorless and transparent and was not peeled off even when scratched with a 3H pencil.
（光触媒活性評価）
実施例２に記載したのと同様の方法で、得られた薄膜の光触媒活性評価を行った。その結果、暗所に置いたものは１９体積ｐｐｍ、昼光色蛍光灯下に置いたものは８体積ｐｐｍ、紫外線吸収膜付蛍光灯下に置いたものは１１体積ｐｐｍであった。
(Photocatalytic activity evaluation)
The photocatalytic activity of the obtained thin film was evaluated in the same manner as described in Example 2. As a result, 19 vol ppm was placed in a dark place, 8 vol ppm was placed under a daylight fluorescent lamp, and 11 vol ppm was placed under a fluorescent lamp with an ultraviolet absorbing film.
比較例１
（窒素を含有しないブルッカイト結晶含有酸化チタンのゾルの合成、固形分の分析）
反応槽に尿素を加えずに、実施例１に記載したのと同様の方法で、酸化チタンのゾルを調製した。この白色スラリーについて、実施例１と同様方法で、ゾルの固形分と下層固形分を求めた。ゾル全体の固形分は４．４質量％、下層固形分は、ゾル全体の固形分の２１質量％であった。その際、得られた固形分は白色であった。この固形分をメノウ乳鉢で粉砕し、実施例１に記載したのと同じ条件で粉末Ｘ線回折の測定を行った。得られた回折チャートを図２に示す。実施例１で定義したピーク高さ比（Ａ／Ｂ）は３．０であり、ブルッカイト結晶構造の酸化チタンを含んでいることを確認した。この酸化チタン中の窒素含有量を、日本工業規格（ＪＩＳ）Ｈ１６１２に準ずる方法で測定したところ、測定限界（０．０１質量％）未満であった。また、この酸化チタンの平均一次粒子径を（１）式から求めたところ０．０４μｍであった。これらの結果から、窒素を含んでいないことを除けば、実施例１で得られたのとほぼ同様のゾル、並びに酸化チタンが得られたと判断した。
Comparative Example 1
(Synthesis of brookite-containing titanium oxide sol containing no nitrogen and analysis of solid content)
A titanium oxide sol was prepared in the same manner as described in Example 1 without adding urea to the reaction vessel. About this white slurry, the solid content and lower layer solid content of the sol were determined in the same manner as in Example 1. The solid content of the entire sol was 4.4% by mass, and the lower layer solid content was 21% by mass of the solid content of the entire sol. At that time, the obtained solid content was white. This solid content was pulverized in an agate mortar, and powder X-ray diffraction was measured under the same conditions as described in Example 1. The obtained diffraction chart is shown in FIG. The peak height ratio (A / B) defined in Example 1 was 3.0, and it was confirmed that titanium oxide having a brookite crystal structure was included. When the nitrogen content in this titanium oxide was measured by a method according to Japanese Industrial Standard (JIS) H1612, it was less than the measurement limit (0.01% by mass). Moreover, it was 0.04 micrometer when the average primary particle diameter of this titanium oxide was calculated | required from (1) Formula. From these results, it was judged that a sol and titanium oxide almost the same as those obtained in Example 1 were obtained except that nitrogen was not included.
（光触媒活性評価）
実施例１に記載したのと同様の方法で、光触媒活性評価を行った。その結果、暗所に置いたものは１５体積ｐｐｍ、昼光色蛍光灯下に置いたものは０体積ｐｐｍ、紫外線吸収膜付蛍光灯下に置いたものは１３体積ｐｐｍであった。昼光色蛍光灯下での光触媒活性は実施例１のものよりも優れていたが、可視光に対する応答性は、明らかに劣っていた。
(Photocatalytic activity evaluation)
Photocatalytic activity was evaluated in the same manner as described in Example 1. As a result, 15 vol ppm was placed in the dark, 0 vol ppm was placed under the daylight fluorescent lamp, and 13 vol ppm was placed under the fluorescent lamp with the ultraviolet absorbing film. The photocatalytic activity under daylight fluorescent lamps was superior to that of Example 1, but the response to visible light was clearly inferior.
比較例２
（窒素含有酸化チタンのゾルの合成、固形分の分析）
反応槽にイオン交換水７００ｍＬと尿素１１．３ｇを加え、室温下、Ｔｉ濃度１５質量％の四塩化チタン水溶液（住友チタニウム株式会社）１２０ｇを加えた。攪拌しながら、２８％アンモニア水を加えていき、ｐＨを８とした。このとき、白色の酸化チタンが得られた。続いて、温度を１０１℃とし、攪拌しながら６０分間保持した。得られた白色懸濁液を限外濾過膜で洗浄、濃縮して白色スラリーを得た。この白色スラリーの一部をガラス製密閉容器に入れ、室温にて静置しておいたところ、２４時間後には、透明な上澄液と白色沈澱とに完全に分離した。すなわち、安定なゾルとはならなかった。そのまま、２４０時間静置しておき、実施例１で記載した「下層固形分」を測定した。
Comparative Example 2
(Synthesis of nitrogen-containing titanium oxide sol, analysis of solid content)
700 mL of ion exchange water and 11.3 g of urea were added to the reaction tank, and 120 g of titanium tetrachloride aqueous solution (Sumitomo Titanium Co., Ltd.) having a Ti concentration of 15% by mass was added at room temperature. While stirring, 28% aqueous ammonia was added to adjust the pH to 8. At this time, white titanium oxide was obtained. Subsequently, the temperature was set to 101 ° C. and held for 60 minutes with stirring. The obtained white suspension was washed with an ultrafiltration membrane and concentrated to obtain a white slurry. A portion of this white slurry was placed in a glass sealed container and allowed to stand at room temperature. After 24 hours, it was completely separated into a transparent supernatant and a white precipitate. That is, it was not a stable sol. It was allowed to stand for 240 hours as it was, and the “lower layer solid content” described in Example 1 was measured.
これを良く攪拌した状態で、別途、白色スラリーの一部を採取し、乾燥恒量法により固形分濃度を測定した。その結果、ゾル全体の固形分は４．８質量％、下層固形分は、ゾル全体の固形分の９６質量％であった。その際、得られた固形分は黄色味を帯びていた。この固形分をメノウ乳鉢で粉砕し、実施例１に記載したのと同様の条件で、粉末Ｘ線回折の測定を行った。得られた回析チャートを図３に示す。実施例１で定義したピーク高さ比（Ａ／Ｂ）は０．１未満であり、得られた粉末は明らかにアナターゼ結晶構造の酸化チタンであって、ブルッカイト結晶構造酸化チタンは含まれていないことがわかった。 With this well stirred, a part of the white slurry was separately collected, and the solid content concentration was measured by a dry constant weight method. As a result, the solid content of the entire sol was 4.8% by mass, and the solid content of the lower layer was 96% by mass of the solid content of the entire sol. At that time, the obtained solid was yellowish. This solid content was pulverized in an agate mortar, and powder X-ray diffraction was measured under the same conditions as described in Example 1. The obtained diffraction chart is shown in FIG. The peak height ratio (A / B) defined in Example 1 is less than 0.1, and the resulting powder is clearly anatase crystal structure titanium oxide and does not contain brookite crystal structure titanium oxide. I understood it.
この酸化チタン中の窒素含有量を、日本工業規格（ＪＩＳ）Ｈ１６１２に準ずる方法で測定したところ、０．３３質量％であった。この粉末のＸ線光電子分光分析を行ったところ、３９６ｅＶのピークの存在が確認され、Ｔｉ−Ｎ結合が確認された。 It was 0.33 mass% when the nitrogen content in this titanium oxide was measured by the method according to Japanese Industrial Standard (JIS) H1612. When X-ray photoelectron spectroscopic analysis of this powder was performed, the presence of a 396 eV peak was confirmed, and a Ti—N bond was confirmed.
また、この酸化チタンの平均一次粒子径を（１）式から求めたところ０．１２μｍであった。
（光触媒活性評価）
実施例１に記載したのと同様の方法で、光触媒活性評価を行った。その結果、暗所に置いたものは１７体積ｐｐｍ、昼光色蛍光灯下に置いたものは１３体積ｐｐｍ、紫外線吸収膜付蛍光灯下に置いたものは１６体積ｐｐｍであった。光触媒活性は実施例１のものよりも明らかに劣っていた。
Moreover, it was 0.12 micrometer when the average primary particle diameter of this titanium oxide was calculated | required from (1) Formula.
(Photocatalytic activity evaluation)
Photocatalytic activity was evaluated in the same manner as described in Example 1. As a result, 17 vol ppm was placed in a dark place, 13 vol ppm was placed under a daylight fluorescent lamp, and 16 vol ppm was placed under a fluorescent lamp with an ultraviolet absorbing film. The photocatalytic activity was clearly inferior to that of Example 1.
比較例３
（薄膜の作成）
実施例２に記載したのと同様の方法で、比較例２で得られたゾルをガラス上にコートし、薄膜を作成した。得られた薄膜は明らかに白濁しており、３Ｈの鉛筆で引っ掻いたところ、剥がれてしまった。
Comparative Example 3
(Creation of thin film)
In the same manner as described in Example 2, the sol obtained in Comparative Example 2 was coated on glass to form a thin film. The obtained thin film was clearly cloudy and was peeled off when scratched with a 3H pencil.
Claims (25)
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| JP2006265970A (en) * | 2005-03-24 | 2006-10-05 | Matsushita Electric Works Ltd | Habitable room equipped with harmful substance reduction system |
| WO2006109705A1 (en) * | 2005-04-07 | 2006-10-19 | Kao Corporation | Coating agent for optical instrument |
| WO2007026387A2 (en) * | 2005-09-01 | 2007-03-08 | NM TECH LTD. - Nanomaterials and Microdevices Technology | Photocatalytic filters that are coated with titanium dioxide suspensions and other substances and methods for obtaining such filters |
| JP2007063050A (en) * | 2005-08-30 | 2007-03-15 | Tanaka Chemical Corp | Method for manufacturing titanium oxide |
| JP2007199656A (en) * | 2005-06-23 | 2007-08-09 | Kao Corp | Coating agent for optical instrument |
| JP2007253148A (en) * | 2006-02-24 | 2007-10-04 | Osaka Prefecture Univ | Photocatalyst, method for manufacturing photocatalyst, method for electrolyzing water, method for producing hydrogen, electrolyzer, and hydrogen produing device |
| JP2009214055A (en) * | 2008-03-11 | 2009-09-24 | National Institute Of Advanced Industrial & Technology | Method of preparing visible light response type titania based photocatalytic body using sol-gel method and ultraviolet ray irradiation method |
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| JP2006265970A (en) * | 2005-03-24 | 2006-10-05 | Matsushita Electric Works Ltd | Habitable room equipped with harmful substance reduction system |
| JP4696629B2 (en) * | 2005-03-24 | 2011-06-08 | パナソニック電工株式会社 | A room with a hazardous substance reduction system |
| WO2006109705A1 (en) * | 2005-04-07 | 2006-10-19 | Kao Corporation | Coating agent for optical instrument |
| AU2006234416B2 (en) * | 2005-04-07 | 2010-01-28 | Kao Corporation | Coating agent for optical instrument |
| JP2007199656A (en) * | 2005-06-23 | 2007-08-09 | Kao Corp | Coating agent for optical instrument |
| JP2007063050A (en) * | 2005-08-30 | 2007-03-15 | Tanaka Chemical Corp | Method for manufacturing titanium oxide |
| WO2007026387A2 (en) * | 2005-09-01 | 2007-03-08 | NM TECH LTD. - Nanomaterials and Microdevices Technology | Photocatalytic filters that are coated with titanium dioxide suspensions and other substances and methods for obtaining such filters |
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| JP2007253148A (en) * | 2006-02-24 | 2007-10-04 | Osaka Prefecture Univ | Photocatalyst, method for manufacturing photocatalyst, method for electrolyzing water, method for producing hydrogen, electrolyzer, and hydrogen produing device |
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