JP4050207B2 - Water-based photocatalyst paint - Google Patents
Water-based photocatalyst paint Download PDFInfo
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- JP4050207B2 JP4050207B2 JP2003313453A JP2003313453A JP4050207B2 JP 4050207 B2 JP4050207 B2 JP 4050207B2 JP 2003313453 A JP2003313453 A JP 2003313453A JP 2003313453 A JP2003313453 A JP 2003313453A JP 4050207 B2 JP4050207 B2 JP 4050207B2
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- titanium oxide
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Description
本発明は、物体の表面を保護し、環境の浄化を目的に使用する常温硬化型の水性光触媒塗料に関するものである。 The present invention relates to a room-temperature curable aqueous photocatalyst coating used for the purpose of protecting the surface of an object and purifying the environment.
従来の常温硬化型の光触媒塗料は、塗布面に付着した有機物を分解することができるが、自ら微生物や大気汚染物質を吸着する機能はない。しかも、接触する有機物を分解するため、光触媒塗料を木やプラスチックに直接塗布することが出来なかった。近年、有機物に直接塗布することが出来るアパタイト被覆酸化チタンを配合した光触媒塗料が開発されたが、有機溶剤を溶媒とする、いわゆる溶剤系の塗料は施工時に溶剤臭と可燃性ガスが発生するため使用条件が限られている。アパタイト被覆酸化チタンと有機物（樹脂類）を配合した水性光触媒塗料は軟らかい塗膜を形成するため傷が付きやすく、又水に接すると硬度が低下し塗布面を指でこすった程度で容易に剥れる。したがって実用的見地からは、人が触る部分や、水と接する部分にこれらの光触媒塗料を使用することが出来ないのが実状であった。しかも有機物を配合した塗料は火災時に有毒ガスと煙を発生させながら燃え、伝炎を加速する結果となる． Conventional room temperature curing photocatalyst paints can decompose organic substances adhering to the coated surface, but do not have the function of adsorbing microorganisms and air pollutants themselves. In addition, the photocatalytic coating could not be applied directly to wood or plastic because it decomposes the organic matter that comes into contact. In recent years, photocatalyst paints containing apatite-coated titanium oxide that can be applied directly to organic substances have been developed. However, solvent-based paints that use organic solvents as solvents generate solvent odors and flammable gases during construction. Usage conditions are limited. Aqueous photocatalyst paints containing apatite-coated titanium oxide and organic substances (resins) form a soft coating that is easily scratched, and when in contact with water, the hardness decreases and the coated surface can be easily removed by rubbing with a finger. It is. Therefore, from a practical point of view, the actual situation is that these photocatalyst paints cannot be used in parts that are touched by humans or in contact with water. In addition, paints that contain organic materials burn in a fire while generating toxic gases and smoke, resulting in accelerated flame transmission.
これら従来の公知発明には、つぎの特許文献が挙げられる。
従来技術による常温で硬化する光触媒塗料が形成した塗膜が剥れる最大の原因は塗膜の硬化不良と、加水分解であった。本発明は、アパタイト被覆酸化チタンと無機物を水に分散させ、無色半透明で不燃性の硬い塗膜を常温で形成持続する水性光触媒塗料を提供することを目的とする。すなわち、アパタイト被覆酸化チタンとコロイダルシリカを配合した常温硬化型の光触媒塗料であって、これにシランカップリング剤を添加し、疎水性の硬い塗膜を形成することにより加水分解と剥離を防ぐ。 The greatest causes of peeling of the coating film formed by the photocatalyst coating material cured at room temperature according to the prior art were poor curing of the coating film and hydrolysis. An object of the present invention is to provide an aqueous photocatalyst coating material in which apatite-coated titanium oxide and an inorganic substance are dispersed in water, and a colorless and translucent and non-flammable hard coating film is formed and maintained at room temperature. That is, it is a room temperature curable photocatalyst paint containing apatite-coated titanium oxide and colloidal silica, and a silane coupling agent is added thereto to form a hydrophobic hard coating, thereby preventing hydrolysis and peeling.
本発明は、塗布して形成された塗膜が常温で硬化する水性光触媒塗料であって、酸化チタンとコロイダルシリカを含み、耐水性の塗膜を形成する水性光触媒塗料である。酸化チタンの一部にアパタイトを被覆したアパタイト被覆酸化チタンを使用してもよい。 The present invention is an aqueous photocatalyst coating material in which a coating film formed by coating is cured at room temperature, and includes an aqueous photocatalyst coating material containing titanium oxide and colloidal silica to form a water-resistant coating film. Apatite-coated titanium oxide in which apatite is coated on a part of titanium oxide may be used.
本発明は、酸化チタンとコロイダルシリカのほか、水とアルコールを含む、常温で硬い塗膜を形成する水性光触媒塗料である。ケイ酸ナトリウムを配合することにより塗料のｐHを安定させることができる。シランカップリング剤を併せ用いると酸化チタンを塗膜の表面により効果的に配列することができる。ここでいうアルコールはイソプロピルアルコールである。 The present invention is an aqueous photocatalyst coating material that forms a hard coating film at room temperature, containing water and alcohol in addition to titanium oxide and colloidal silica. By adding sodium silicate, the pH of the paint can be stabilized. When a silane coupling agent is used in combination, titanium oxide can be effectively arranged on the surface of the coating film. The alcohol here is isopropyl alcohol.
そして、以下に示す組成範囲で好ましい水性光触媒塗料が得られる。すなわち、いずれも重量％（以下において同じ）でアパタイト被覆酸化チタン０．４〜１．０、コロイダルシリカ２．５〜４．０、イソプロピルアルコール１．０〜２．５、ケイ酸ナトリウム０．０３〜０．０９、シランカップリング剤０．０１〜０．１残余が水である。 And a preferable aqueous photocatalyst coating material is obtained in the composition range shown below. That is, all are apatite-coated titanium oxide 0.4 to 1.0, colloidal silica 2.5 to 4.0, isopropyl alcohol 1.0 to 2.5, sodium silicate 0.03 by weight% (the same applies hereinafter). -0.09, 0.01-0.1 remainder of silane coupling agent is water.
以上説明したように、本発明の水性光触媒塗料は、常温で硬化し、無色半透明な硬い硬膜を形成するため、剥がれにくく、塗布面の劣化と損傷を防ぐ。本発明の水性光触媒塗料は、塗膜の透明度を保つことにより表面に照射された光を光触媒反応に効率よく利用できるため、酸化還元反応による有機物を分解する効果が持続し、汚物と微生物の付着を防止して、塗布面と環境を清浄に保つ。 As described above, the aqueous photocatalyst coating material of the present invention cures at room temperature and forms a colorless and translucent hard film, so that it is difficult to peel off and prevents deterioration and damage of the coated surface. The aqueous photocatalyst paint of the present invention can efficiently use the light irradiated on the surface for photocatalytic reaction by maintaining the transparency of the coating film, so that the effect of decomposing organic substances by oxidation-reduction reaction is maintained, and the adhesion of dirt and microorganisms To keep the coated surface and environment clean.
本発明の水性光触媒塗料は、アパタイト被覆酸化チタンとコロイダルシリカを基本構成とする。すなわち、本発明の水性光触媒塗料は、水とイソプロピルアルコールにコロイダルシリカを分散した液にアパタイト被覆酸化チタンとシランカップリング剤、およびケイ酸ナトリウムを添加して構成される。 The aqueous photocatalyst coating material of the present invention is basically composed of apatite-coated titanium oxide and colloidal silica. That is, the aqueous photocatalyst coating material of the present invention is constituted by adding apatite-coated titanium oxide, a silane coupling agent, and sodium silicate to a liquid in which colloidal silica is dispersed in water and isopropyl alcohol.
本発明の水性光触媒塗料を塗布し乾燥させて形成される塗膜は常温で硬化し、表面に付着した水滴との間に大きな接触角を発現することにより、優れた耐水性を有する。 The coating film formed by applying and drying the aqueous photocatalyst paint of the present invention is cured at room temperature, and exhibits a large contact angle with water droplets attached to the surface, thereby having excellent water resistance.
さらに、アパタイト被覆酸化チタンとコロイダルシリカの配合比率を調整することにより、水性光触媒塗料の塗膜の硬度、硬化速度、光触媒反応の強弱、塗膜と水滴との接触角を広範に制御することができる。シランカップリング剤は水とアパタイト被覆酸化チタンおよびコロイダルシリカを馴染ませると共に、アパタイト被覆酸化チタンを塗膜の表面に押し上げる機能をもつ。コロイダルシリカはアパタイト被覆酸化チタンの分散性の向上と沈降防止および硬膜形成に有用であり、ケイ酸ナトリウムは塗料のｐHを９．０〜１０．５に保ちゲル化と分離を防ぐ。 Furthermore, by adjusting the blending ratio of apatite-coated titanium oxide and colloidal silica, it is possible to extensively control the hardness of the coating film of the aqueous photocatalyst paint, the curing rate, the intensity of photocatalytic reaction, and the contact angle between the coating film and water droplets. it can. The silane coupling agent has a function of blending water, apatite-coated titanium oxide and colloidal silica, and pushing the apatite-coated titanium oxide onto the surface of the coating film. Colloidal silica is useful for improving the dispersibility of apatite-coated titanium oxide, preventing sedimentation, and forming a dura film, and sodium silicate maintains the pH of the paint at 9.0 to 10.5 to prevent gelation and separation.
以下の配合によって、本発明の水性光触媒塗料を得ることができる。
アパタイト被覆酸化チタン ０．４〜１．０（重量％）
コロイダルシリカ ２．５〜４．０
シランカップリング剤 ０．０１〜０．１
イソプロピルアルコール １．０〜２．５
ケイ酸ナトリウム ０．０３〜０．０９
イオン交換水 残余
The aqueous photocatalyst coating material of the present invention can be obtained by the following formulation.
Apatite-coated titanium oxide 0.4-1.0 (wt%)
Colloidal silica 2.5-4.0
Silane coupling agent 0.01-0.1
Isopropyl alcohol 1.0-2.5
Sodium silicate 0.03-0.09
Ion exchange water
以下に、実施例をもって本発明をさらに説明する。 The present invention will be further described below with reference to examples.
アパタイト被覆酸化タチン０．５（重量％）、コロイダルシリカ２．７、シランカップリング剤０．０１、イソプロピルアルコール１．０、ケイ酸ナトリウム０．０４および水(残余)の配合とした水性光触媒塗料を調製した。 Aqueous photocatalyst paint comprising apatite-coated tatin oxide 0.5 (% by weight), colloidal silica 2.7, silane coupling agent 0.01, isopropyl alcohol 1.0, sodium silicate 0.04 and water (residue) Was prepared.
前記調製による水性光触媒塗料をガラス板表面に塗布し、常温で２４時間乾燥させて試料とした。塗膜は常温乾燥で硬化しており、ＪＩＳ Ｋ５４０４規格にもとづく硬度測定により鉛筆硬度９Ｈを呈した。 The aqueous photocatalyst paint prepared as described above was applied to the surface of a glass plate and dried at room temperature for 24 hours to prepare a sample. The coating film was cured at room temperature and exhibited a pencil hardness of 9H by hardness measurement based on JIS K5404 standard.
本発明による水性光触媒塗料をガラスに塗布して硬化させた試料を水中に５０時間浸した後、塗膜の硬度測定をした結果、鉛筆硬度５Hを保ち、剥れない。 A sample cured by applying the aqueous photocatalyst coating material according to the present invention to glass was immersed in water for 50 hours, and then the hardness of the coating film was measured. As a result, the pencil hardness was kept at 5H and did not peel off.
本発明による水性光触媒塗料の塗布面に付着した水は水玉になる。光の照射により起きた反応で塗布面の吸着水を安定させている疎水分子が分解され、塗布面に付着した水玉を支持する要因がなくなり不安定になる。そのためわずかな傾斜や振動で、水玉は滑落するので塗布面に水滴や汚物が付着しにくくなると推測される。 The water adhering to the application surface of the aqueous photocatalyst paint according to the present invention becomes polka dots. Hydrophobic molecules that stabilize the adsorbed water on the coated surface are decomposed by the reaction caused by the light irradiation, and the factor that supports the polka dots attached to the coated surface disappears and becomes unstable. For this reason, the polka dots slide down with a slight inclination or vibration, and it is assumed that water droplets and dirt are less likely to adhere to the coated surface.
本実施例の水性光触媒塗料（WY-２７）をガラス（１．４ｃｍ×２．５ｃｍ）の片面に塗布した試料を使用して，光触媒活性の比較試験を以下の方法で行い、臭いを分解する効力を検証した。 Using a sample in which the aqueous photocatalyst paint (WY-27) of this example was applied to one side of glass (1.4 cm × 2.5 cm), a photocatalytic activity comparison test was conducted by the following method to decompose odors. The efficacy was verified.
容積３００ｃｃの透明容器内に試料とイソプロピルアルコール（気化した濃度を６ｐｐｍに調整）を入れて密封した後，波長３６５ｎｍの紫外線（１ｍＷ）を照射した。容器内のイソプロピルアルコールが試料に接触し、光触媒反応により分解されて生成したアセトンの量を一定時間毎にガスクロマトグラフイーで測定することにより光触媒の活性力を比較試験した。その結果市販されているアルコール系光触媒塗料（TA、KO3）の性能と同等以上の成績を得たので表１に示す。 A sample and isopropyl alcohol (vaporized concentration was adjusted to 6 ppm) were sealed in a 300 cc transparent container, and then irradiated with ultraviolet light (1 mW) having a wavelength of 365 nm. The activity of the photocatalyst was comparatively tested by measuring the amount of acetone produced by contact of the isopropyl alcohol in the container with the sample and being decomposed by the photocatalytic reaction at regular intervals. As a result, results equivalent to or better than the performance of commercially available alcohol photocatalyst paints (TA, KO3) are shown in Table 1.
表１
本発明による水性光触媒塗料を７６×２６ｍｍのガラスに塗布した試料と、比較対照のためのガラス板を用意した。試料をシャーレ内の培地に接地し黄色ブドウ球菌を接種し、紫外線（波長３６０nm，紫外線強度１００μＷ）を照射しながら培養し、１時間後に洗い出し法により殺菌効果を試験した。洗い出した液を培地に接種し、培養後に菌数を測定した。その結果、コントロールを洗い出した液を接種した培地には試験菌（４．５×１０２）が繁殖したが、本発明を塗布した試料を洗い出した液を接種した培地には、試験菌が全く繁殖しなかった。この結果から、試料の表面に付着している菌液中の試験菌を光触媒反応による酸化力で殺滅したことが証明された。 A sample in which the aqueous photocatalyst coating material according to the present invention was applied to 76 × 26 mm glass and a glass plate for comparison were prepared. The sample was grounded on the medium in the petri dish, inoculated with Staphylococcus aureus, cultured while irradiating with ultraviolet rays (wavelength 360 nm, ultraviolet intensity 100 μW), and tested for bactericidal effect by washing out after 1 hour. The washed liquid was inoculated into the medium, and the number of bacteria was measured after the culture. As a result, the test bacteria (4.5 × 10 2 ) propagated in the medium inoculated with the liquid from which the control was washed out, but the test bacteria were not present in the medium inoculated with the liquid in which the sample applied with the present invention was washed out. Did not breed. From this result, it was proved that the test bacteria in the bacterial solution adhering to the surface of the sample were killed by the oxidizing power by the photocatalytic reaction.
本実施例による水性光触媒塗料をガラスに塗布した試料をガスバーナーでガラスが割れるまで加熱（温度５００℃）したが塗膜からガスや煙の発生が見られず炎の発生もなかった。加熱によりアパタイトが茶色に変色したが塗膜は不燃であることを実証した。 The sample in which the aqueous photocatalyst coating material according to this example was applied to glass was heated (temperature 500 ° C.) with a gas burner until the glass was broken, but no gas or smoke was observed from the coating film, and no flame was generated. It was proved that the apatite turned brown by heating, but the coating was nonflammable.
なお、アパタイト被覆酸化チタンを０．４％未満とした組成の場合には十分な光触媒効果が得られない。１．０％を超えるアパタイト被覆酸化チタンを含む組成とすると、塗膜の硬度が低下しキズが付きやすくなる．コロイダルシリカの総量を２．５％未満としたときには塗料中の酸化チタンが沈降分離し、４．０％以上とすると塗布後固形分が表面に凝集し均一で硬質な塗膜が形成されなくなる。シランカップリング剤を０．１％以上に配合すると酸化チタンが塗膜の中に埋没しやすくなり、光触媒反応が起きなくなる。ケイ酸ナトリウムの配合量を０．０３％未満としたときには塗料のｐHを９．０以上に保つことが出来なくなり塗料はゲル化し、０．０９％以上配合すると塗料のｐHが１２以上になりコロイダルシリカが分解する。
In the case of a composition in which the apatite-coated titanium oxide is less than 0.4%, a sufficient photocatalytic effect cannot be obtained. When the composition contains apatite-coated titanium oxide exceeding 1.0%, the hardness of the coating film is lowered and scratches are easily formed. When the total amount of colloidal silica is less than 2.5%, titanium oxide in the paint settles and separates, and when it is 4.0% or more, the solid content after application is aggregated on the surface and a uniform and hard coating film is not formed. When the silane coupling agent is blended in an amount of 0.1% or more, titanium oxide is easily embedded in the coating film, and the photocatalytic reaction does not occur. When the amount of sodium silicate is less than 0.03%, the paint pH cannot be maintained at 9.0 or more, and the paint gels. When 0.09% or more is added, the paint pH becomes 12 or more and colloidal. Silica decomposes.
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| KR100819519B1 (en) | 2006-08-11 | 2008-04-07 | (주)알엔씨 | Photocatalytic coating composition for accessory of automobiles and method for coating the same on an object |
| WO2008057029A1 (en) * | 2006-11-09 | 2008-05-15 | Akzo Nobel N.V. | Pigment dispersion |
| US7919425B2 (en) | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP4092714B1 (en) | 2007-03-26 | 2008-05-28 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid therefor |
| JP2008307528A (en) * | 2007-03-30 | 2008-12-25 | Toto Ltd | Coated-photocatalyst object and photocatalyst coating liquid therefor |
| KR100958371B1 (en) | 2007-09-18 | 2010-05-17 | 이승규 | Luster Manufacturing Method for Automobile |
| JP4897781B2 (en) * | 2008-03-28 | 2012-03-14 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid therefor |
| UA100571C2 (en) * | 2008-06-24 | 2013-01-10 | Энэрджи Корея Инк. | Coating composition comprising photocatalyst coated with apatite and radiant heating system having the same |
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