JP2005138059A - Quick hardening photocatalyst body - Google Patents
Quick hardening photocatalyst body Download PDFInfo
- Publication number
- JP2005138059A JP2005138059A JP2003379173A JP2003379173A JP2005138059A JP 2005138059 A JP2005138059 A JP 2005138059A JP 2003379173 A JP2003379173 A JP 2003379173A JP 2003379173 A JP2003379173 A JP 2003379173A JP 2005138059 A JP2005138059 A JP 2005138059A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- fast
- curing
- layer
- compound
- 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.)
- Pending
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 130
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- 239000000758 substrate Substances 0.000 claims abstract description 27
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- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
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Landscapes
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、防汚、脱臭、水中や空気中の汚染物質の分解、黴、細菌等、微生物の繁殖抑制及び藻の生育抑制等に利用される基材の表面に設けられ、基材上に形成した直後から硬化し取扱いに優れた速硬化性光触媒体に関する。 The present invention is provided on the surface of a base material used for antifouling, deodorization, decomposition of pollutants in water and air, soot, bacteria, etc. The present invention relates to a fast-curing photocatalyst that is cured immediately after formation and excellent in handling.
従来から、建造物外壁の汚れ、窓ガラスの汚れ、自動車の排気ガスによる道路遮音壁や看板の汚れ、室内や車内のたばこ等の悪臭、空気中のＮＯxやＳＯx、室内外の細菌や黴等の微生物等の有害物、水中の環境ホルモン様物質等の分解、除去に光触媒体が使用されている。 Conventionally, building external wall of dirt, glazing dirt, dirt road sound insulation walls or billboards by the exhaust gas of an automobile, malodor, such as room or car cigarette, NO x and SO x in the air, indoor and outdoor bacteria and mold Photocatalysts are used to decompose and remove harmful substances such as microorganisms and environmental hormone-like substances in water.
特に、二酸化チタンは広範囲の波長の光の照射により励起されエネルギーを放出すると共に、化学的に安定で、透明又は白色、無害であることから、光触媒として多用されている（例えば、非特許文献１，２参照。）。二酸化チタンの結晶にはルチル型、アナターゼ型、ブルッカイト型の三種類があるが、アナターゼ型酸化チタンは光触媒活性が高く、最も一般的に利用されている。 In particular, titanium dioxide is widely used as a photocatalyst because it is excited by irradiation with light of a wide range of wavelengths and emits energy, and is chemically stable, transparent, white, and harmless (for example, Non-Patent Document 1). , 2). There are three types of crystals of titanium dioxide: rutile type, anatase type, and brookite type. Anatase type titanium oxide has a high photocatalytic activity and is most commonly used.
このような光触媒を汚れ等の付着を抑制する基材の表面に固定する方法としては、基材上に酸化チタンの縣濁液を塗布し焼結して酸化チタンを固着させる方法や、酸化分解耐性のある樹脂をバインダーとして用い、バインダーに分散させた酸化チタンを基材に接合させる方法等が提案されている。具体的には、酸化チタン粒子とフッ素系樹脂との混合物を積層または圧着する方法（例えば、特許文献１参照。）、水ガラス、コロイダルシリカ、ポリオルガノシロキサンなどのケイ素化合物、リン酸亜鉛、リン酸アルミニウムなどのリン酸塩、重リン酸塩、セメント、石灰、セッコウ、ほうろう用フリット、グラスライニング用うわぐすり、プラスターなどの無機系結着剤や、ポリフッ化ビニル、ポリフッ化ビニリデン等のフッ素系ポリマー等の難分解性有機系結着剤をバインダーとして酸化チタン粒子を接合させる方法（例えば、特許文献２参照。）、酸化チタン等の光触媒とアモルファス型ペルオキソチタン酸ゾルとを混合した液を基体に塗布し、アモルファス型ペルオキソチタン酸ゾルをバインダーとして利用して光触媒を基体上に担持させる方法（例えば、特許文献３参照。）等がある。 As a method of fixing such a photocatalyst to the surface of a substrate that suppresses adhesion of dirt, etc., a method of applying a titanium oxide suspension on the substrate and sintering it to fix the titanium oxide, or an oxidative decomposition A method has been proposed in which a resistant resin is used as a binder and titanium oxide dispersed in the binder is bonded to a substrate. Specifically, a method of laminating or pressure-bonding a mixture of titanium oxide particles and a fluororesin (see, for example, Patent Document 1), silicon compounds such as water glass, colloidal silica, and polyorganosiloxane, zinc phosphate, phosphorus Phosphate such as aluminum phosphate, heavy phosphate, cement, lime, gypsum, frit for enamel, glaze for glass lining, plaster and other inorganic binders, fluorine such as polyvinyl fluoride and polyvinylidene fluoride A method in which titanium oxide particles are bonded using a hard-to-decompose organic binder such as a polymer based on a binder (see, for example, Patent Document 2), a liquid in which a photocatalyst such as titanium oxide and an amorphous peroxotitanate sol are mixed. The photocatalyst is coated on the substrate using an amorphous peroxotitanate sol as a binder. Method for lifting (e.g., see Patent Document 3.), And the like.
また、光触媒が固定された基材が有機基材である場合、光の照射により活性化された光触媒の酸化分解作用により生じる表面の劣化を抑制するために、保護層を介して光触媒を基材に接合する方法が提案されている。このような保護層を有する光触媒体として、具体的には、基材上に光触媒を含有しないシリコン系ポリマー又はフッ素系ポリマーの結着剤からなる第一層を設け、その上層に光触媒を含有する第二層を設けた光触媒体（例えば、特許文献２参照。）や、表面に形成され光触媒層と、樹脂層と、光触媒層と樹脂層との間に形成された中間層とを積層してなる光触媒性被膜であって、中間層がケイ素化合物、リン酸塩、重リン酸塩、過酸化チタン等の無機系結着剤や、フッ素系ポリマー、シリコン系ポリマー等の有機系結着剤の難分解性結着剤からなる光触媒性被膜（例えば、特許文献４参照。）や、有機基体表面に、乾燥前は親油性であって有機基体との密着性が高く乾燥後は親水性を呈する中間被膜を設け、その上に過酸化チタンを含有するアナターゼ型酸化チタン分散液を塗布してなる酸化チタン膜を形成することで、光触媒粒子が結着剤に埋没せず光の照射や経時による劣化が大幅に改善され、有機基体表面の色、光沢等が損われることがない多層体（例えば、特許文献５参照。）等が知られている。 In addition, when the base material on which the photocatalyst is fixed is an organic base material, the photocatalyst is attached to the base material through a protective layer in order to suppress surface degradation caused by the oxidative decomposition action of the photocatalyst activated by light irradiation. There has been proposed a method of joining to the substrate. Specifically, as a photocatalyst body having such a protective layer, a first layer made of a binder of a silicon-based polymer or a fluorine-based polymer that does not contain a photocatalyst is provided on the substrate, and the photocatalyst is contained in the upper layer. A photocatalyst body provided with a second layer (see, for example, Patent Document 2), a photocatalyst layer formed on the surface, a resin layer, and an intermediate layer formed between the photocatalyst layer and the resin layer are laminated. The intermediate layer is made of an inorganic binder such as a silicon compound, phosphate, heavy phosphate, titanium peroxide, or an organic binder such as a fluorine polymer or a silicon polymer. A photocatalytic film made of a hardly decomposable binder (see, for example, Patent Document 4) and the surface of an organic substrate are lipophilic before drying, have high adhesion to the organic substrate and exhibit hydrophilicity after drying. An intermediate coating is provided and contains titanium peroxide. By forming a titanium oxide film formed by applying a natase-type titanium oxide dispersion, the photocatalyst particles are not embedded in the binder, and light irradiation and deterioration over time are greatly improved. A multilayer body (for example, refer to Patent Document 5) that does not damage the above is known.
しかしながらこれらの方法はいずれもプライマーの乾燥や、密着のために加熱を必要とし、建築物外壁への適用は実際的ではない。更に、無機酸化物を使用した場合、塗布膜を薄く形成することが困難であり、透明感がなくなるという問題があり、また塗布膜表面に存在する光触媒が経時に伴い減少し光触媒活性が低下するという問題がある。また、無機酸化物の光触媒を水に分散させるためには強酸性にする必要があり、取扱い及び施工上の問題がある。かかる問題点に対し、アモルファス型ペルオキソチタン酸ゾルをバインダーとし、アナターゼ型酸化チタンを基材に接合させる方法は、常温乾燥で密着性が得られ、透明であり光触媒の経時変化もなく、優れた方法であるが、初期塗膜表面の硬度が低く、実用的硬度に達するまでに数日〜数週間を要する。そのため、塗布作業中や塗布直後に誤って塗布面に触れると光触媒膜が破れたり剥離したりするので、作業に細心の注意が必要である。更に、光触媒表面はコロイド状の微粒子の酸化チタンとペルオキソチタン酸であるため吸着性が高く、脱臭やガス吸着等には好適であるが、汚れも付着しやすく、防汚には場合によっては難点がある。 However, these methods all require heating for drying and adhesion of the primer, and application to the building outer wall is not practical. Furthermore, when an inorganic oxide is used, it is difficult to form a thin coating film, and there is a problem that the transparency is lost, and the photocatalyst present on the surface of the coating film decreases with time and the photocatalytic activity decreases. There is a problem. Moreover, in order to disperse | distribute the inorganic oxide photocatalyst to water, it is necessary to make it strong acidity, and there exists a problem on handling and construction. For this problem, the method of bonding anatase-type titanium oxide to a base material using an amorphous-type peroxotitanate sol as a binder is excellent in adhesiveness obtained at room temperature drying, transparent and without change in the photocatalyst over time. Although it is a method, the hardness of the initial coating film surface is low, and it takes several days to several weeks to reach a practical hardness. Therefore, since the photocatalyst film is torn or peeled off if it is accidentally touched during or immediately after the coating operation, the work needs to be taken with great care. Furthermore, the photocatalyst surface is made of colloidal fine particles of titanium oxide and peroxotitanic acid, so it has high adsorptivity and is suitable for deodorization and gas adsorption. There is.
光触媒膜表面を硬くして、耐磨耗性にする方法としては、チタニアゾルとコロイダルシリカ等の金属酸化物のコロイド溶液との複合ゾル溶液をガラス基板上に塗布・焼成する方法（例えば、特許文献６参照）、光透過性と光触媒機能を有するＴｉＯ2膜と、光透過性および親水性を有する多孔質ＳｉＯ2膜とを積層した積層膜を形成する方法（例えば、特許文献７参照）、酸化チタン上に、酸化チタンと酸化ケイ素との混合層、および酸化ケイ素層とが順に積層された可視光線応答型光触媒を構成する方法（例えば、特許文献８参照）等がある。しかしながら、これらの方法は、６００℃以上の温度で燒結する必要があり、また酸化チタンと酸化ケイ素の膜を生成するのに真空蒸着法で行われており、ガラスミラーのような比較的小さい対象物には適用できるが、大きい窓ガラスや建造物の外壁等への適用は難しい。
本発明は、ペルオキソチタン酸とアナターゼ型酸化チタンとを含有し、無機基材にも有機基材にも塗布により密着性よく設けることができ、光触媒を強固に固着して脱落を抑制し、透明感があり、光触媒自体による基材の劣化を抑制しつつ一方において光触媒活性が高く、汚染性が低く、しかも、加熱を必要とせず常温で塗布直後から硬度が高く、優れた施工性を有し、作業中の接触による塗膜の敗れ、剥離を抑制することができ、建造物等広範囲の塗膜形成が容易な光触媒体を提供することを目的とする。 The present invention contains peroxotitanic acid and anatase-type titanium oxide, and can be provided with good adhesion to both inorganic and organic substrates by coating. The photocatalyst is firmly fixed to prevent dropping and is transparent. There is a feeling, while suppressing deterioration of the substrate due to the photocatalyst itself, the photocatalytic activity is high, the contamination property is low, and the hardness is high immediately after application at room temperature without requiring heating, and it has excellent workability. An object of the present invention is to provide a photocatalyst which can suppress the loss and peeling of a coating film due to contact during work and can easily form a wide range of coating film such as a building.
本発明者らは上記課題を解決するため鋭意検討を重ねた結果、基材表面に設けられたペルオキソチタン酸とアナターゼ型酸化チタンとを含有する光触媒層上に、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応させて得られるポリシロキサン化合物を含有する被覆層を設けることにより、加熱をしなくとも光触媒が強固に固着し、表面硬度が塗布直後から高く、汚染性が低く、基材が有機基材の場合においても、光触媒それ自体の作用によって基材が劣化されることを抑制することができると共に光触媒活性を高く維持することができ、透明性を有するとの知見を得て、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have found that an alkoxysilane compound and / or an alkoxysiloxane are formed on a photocatalyst layer containing peroxotitanic acid and anatase-type titanium oxide provided on the substrate surface. By providing a coating layer containing a polysiloxane compound obtained by reacting the compound in water and an organic solvent, the photocatalyst is firmly fixed without heating, the surface hardness is high immediately after coating, and the contamination is low. Even when the base material is an organic base material, it is possible to suppress the base material from being deteriorated by the action of the photocatalyst itself and to maintain a high photocatalytic activity and to have transparency. The present invention was completed.
すなわち本発明は、基材表面に設けられ、ペルオキソチタン酸及びアナターゼ型酸化チタンを含有する光触媒層と、該光触媒層上に設けられ、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応させて得られるポリシロキサン化合物を含有する被覆層とを有することを特徴とする速硬化性光触媒体に関し、好ましくは、被覆層の厚さが、０．０１〜０．５μｍであることを特徴とする請求項１記載の速硬化性光触媒体（請求項２）や、光触媒層の厚さが、０．２〜１０μｍであることを特徴とする請求項１又は２記載の速硬化性光触媒体（請求項３）や、光触媒層と被覆層の２層積層構造体、又は、該２層積層構造体が２以上積層された多層積層構造体であることを特徴とする請求項１〜３のいずれか記載の速硬化性光触媒体（請求項４）や、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物が、一般式（Ｉ）
ＳｉＯxＲy （Ｉ）
［式中、ＲはＣ１〜Ｃ４のアルコキシ基を表し、ｘ、ｙは０≦ｘ≦１．２、１．６≦ｙ≦４であり、且つ２ｘ＋ｙ＝４である数値を表す。］で示される化合物であることを特徴とする請求項１〜４のいずれか記載の速硬化性光触媒体（請求項５）や、一般式（Ｉ）におけるＲが、メトキシ基を表し、ｘが０．８であることを特徴とする請求項５記載の速硬化性光触媒体（請求項６）や、ペルオキソチタン酸が、ペルオキソチタン酸ゾルであることを特徴とする請求項１〜６のいずれか記載の速硬化性光触媒体（請求項７）や、ペルオキソチタン酸ゾルが、水溶性チタン化合物と塩基性物質との反応による水酸化チタンの生成工程と、水酸化チタンの洗浄工程と、洗浄した水酸化チタンと過酸化水素との反応工程により製造されたことを特徴とする請求項７記載の速硬化性光触媒体（請求項８）や、水溶性チタン化合物が、四塩化チタンであることを特徴とする請求項８記載の速硬化性光触媒体（請求項９）や、塩基性物質が、アンモニア水であることを特徴とする請求項７又は８記載の速硬化性光触媒体（請求項１０）や、水酸化チタンの洗浄工程が、水酸化チタンを脱イオン水で洗浄した後、水酸化チタンを水に縣濁させ、この縣濁液に陽イオン交換樹脂及び陰イオン交換樹脂を添加し、水酸化チタンと陽イオン交換樹脂及び陰イオン交換樹脂とを直接接触させることにより不純物を除去する工程を含み、アンモニウムイオンの残留濃度が所定の範囲となるように反復して行われることを特徴とする請求項８〜１０のいずれか記載の速硬化性光触媒体（請求項１１）や、アンモニウムイオンの残留濃度が、５０〜６００ｐｐｍであることを特徴とする請求項１１記載の速硬化性光触媒体（請求項１２）や、アナターゼ型酸化チタンが、アナターゼ型酸化チタンゾルであることを特徴とする請求項１〜１２のいずれか記載の速硬化性光触媒体（請求項１３）や、アナターゼ型酸化チタンゾルが、ペルオキソチタン酸ゾルを８０℃以上の温度で加熱して調製されるアナターゼ型酸化チタンの分散液であることを特徴とする請求項１３記載の速硬化性光触媒体（請求項１４）に関する。
That is, the present invention provides a photocatalyst layer containing peroxotitanic acid and anatase-type titanium oxide provided on the surface of a substrate, and an alkoxysilane compound and / or alkoxysiloxane compound in water and an organic solvent provided on the photocatalyst layer. And a coating layer containing a polysiloxane compound obtained by reacting with a fast curing photocatalyst, wherein the coating layer preferably has a thickness of 0.01 to 0.5 μm. 3. The fast-curing photocatalyst (Claim 2) according to claim 1 or the photocatalyst layer having a thickness of 0.2 to 10 [mu] m. (Claim 3), a two-layer laminated structure of a photocatalyst layer and a coating layer, or a multilayer laminated structure in which two or more of the two-layer laminated structures are laminated. Any of The fast-curing photocatalyst described above (Claim 4), the alkoxysilane compound and / or the alkoxysiloxane compound are represented by the general formula (I).
SiO x R y (I)
[Wherein, R represents a C1 to C4 alkoxy group, and x and y represent 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, and 2x + y = 4. The fast-curing photocatalyst (Claim 5) according to any one of claims 1 to 4, wherein R in the general formula (I) represents a methoxy group, and x is a compound represented by the formula: The fast-curing photocatalyst according to claim 5 (claim 6) or the peroxotitanic acid is a peroxotitanate sol according to any one of claims 1 to 6. A fast-curing photocatalyst (Claim 7) or a peroxotitanate sol comprising a step of producing titanium hydroxide by a reaction between a water-soluble titanium compound and a basic substance, a step of washing titanium hydroxide, and a step of washing The fast-curing photocatalyst (claim 8) or the water-soluble titanium compound according to claim 7 or titanium tetrachloride, wherein the fast-curing photocatalyst (claim 8) or the water-soluble titanium compound is produced by a reaction step of titanium hydroxide and hydrogen peroxide. The quick-hardening according to claim 8, The photocurable photocatalyst (Claim 9), the basic substance is ammonia water, the fast curing photocatalyst (Claim 10) according to claim 7 or 8, and the step of washing titanium hydroxide. After washing the titanium hydroxide with deionized water, the titanium hydroxide is suspended in water, a cation exchange resin and an anion exchange resin are added to the suspension, and the titanium hydroxide and the cation exchange resin are added. 11. The method according to claim 8, comprising a step of removing impurities by direct contact with an anion exchange resin, wherein the step is repeatedly performed so that the residual concentration of ammonium ions falls within a predetermined range. The fast-curing photocatalyst according to claim 11 (claim 11), the residual concentration of ammonium ions is 50 to 600 ppm, the fast-curing photocatalyst according to claim 11 (claim 12), and anatase The fast-curing photocatalyst according to any one of claims 1 to 12, wherein the titanium oxide is an anatase type titanium oxide sol (claim 13) or the anatase type titanium oxide sol is a peroxotitanate sol at 80 ° C. The fast-curing photocatalyst (Claim 14) according to claim 13, which is a dispersion of anatase-type titanium oxide prepared by heating at the above temperature.
本発明の光触媒体は、無機基材、有機基材いずれの基材も劣化させず、基材に強固に固着し、膜強度が高く、透明感があり、光触媒活性が高く、しかも加熱をせずに塗布直後から硬化し、施工が容易であり、屋外の建造物の外壁や水中の構造物等に適用して、防汚、脱臭、水中や空気中に含まれる汚染物質の分解、雑菌や黴の繁殖の防止、藻の生育抑制等をすることができ、特に、施工中塗膜に接触しても塗膜の破損を抑制することができるため、建造物外壁等大規模な範囲に設けられる汚染抑制材として有用である。 The photocatalyst of the present invention does not deteriorate both inorganic and organic substrates, firmly adheres to the substrate, has high film strength, is transparent, has high photocatalytic activity, and is heated. It is hardened immediately after application, easy to install, and applied to the outer walls of outdoor buildings and underwater structures, etc. to prevent pollution, deodorization, decomposition of pollutants contained in water and air, It can prevent the growth of sea bream, suppress the growth of algae, etc. Especially, since it can suppress the damage of the coating film even if it touches the coating film during construction, it is provided in a large range such as the outer wall of the building It is useful as a pollution control material.
本発明の速硬化性光触媒体は、基材表面に設けられ、ペルオキソチタン酸及びアナターゼ型酸化チタンを含有する光触媒層と、該光触媒層上に設けられ、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応させて得られるポリシロキサン化合物を含有する被覆層とを有するものであれば、特に限定されるものではないが、かかる光触媒層に更に、無機系や有機系のバインダー、上記と同様のポリシロキサン化合物や、界面活性剤等を含有するものであってもよい。 The fast-curing photocatalyst of the present invention is provided on the surface of a substrate and contains a photocatalyst layer containing peroxotitanic acid and anatase-type titanium oxide, and an alkoxysilane compound and / or an alkoxysiloxane compound provided on the photocatalyst layer. Although it will not specifically limit if it has a coating layer containing the polysiloxane compound obtained by making it react in water and an organic solvent, In addition to this photocatalyst layer, an inorganic system and an organic system binder, It may contain the same polysiloxane compound as described above, a surfactant or the like.
本発明の速硬化性光触媒体の光触媒層に含有されるアナターゼ型酸化チタンは、ルチル型酸化チタン、ブルッカイト型酸化チタンと比較して優れた光触媒作用を有し、紫外線等の光が照射されることにより活性化され、酸化還元作用が惹起され、例えば、アナターゼ型酸化チタンの作用により表面に付着した有機物、無機物の汚れ等が効率よく酸化分解され除去される。かかるアナターゼ型酸化チタンはアナターゼ型酸化チタンゾルであることが、光触媒層を形成する際の施工性に優れるため好ましい。アナターゼ型酸化チタンゾルは、上記ペルオキソチタン酸ゾルを８０℃以上の温度で加熱して得ることができ、反応時の危険性をなくし穏やかな条件でアナターゼ型酸化チタンへの結晶化を図るために、９０〜２００℃の温度で加熱して調製したアナターゼ型酸化チタンゾルであることが好ましい。かかるアナターゼ型酸化チタンゾルの調製における加熱時間は加熱温度と相関関係があり、加熱温度が高いほど加熱時間は短くなり、９０〜２００℃の温度で加熱する場合、１〜２０時間が好ましく、より好ましくは２〜１０時間である。 The anatase-type titanium oxide contained in the photocatalyst layer of the fast-curing photocatalyst of the present invention has an excellent photocatalytic action as compared with rutile-type titanium oxide and brookite-type titanium oxide, and is irradiated with light such as ultraviolet rays. As a result, an oxidation-reduction action is induced, and for example, organic substances and inorganic soils adhered to the surface are efficiently oxidized and removed by the action of anatase-type titanium oxide. Such anatase-type titanium oxide is preferably anatase-type titanium oxide sol because it is excellent in workability when forming the photocatalyst layer. The anatase-type titanium oxide sol can be obtained by heating the above peroxotitanate sol at a temperature of 80 ° C. or higher, in order to eliminate the risk during reaction and to crystallize into anatase-type titanium oxide under mild conditions. An anatase-type titanium oxide sol prepared by heating at a temperature of 90 to 200 ° C. is preferable. The heating time in the preparation of such anatase-type titanium oxide sol correlates with the heating temperature. The higher the heating temperature, the shorter the heating time. When heating at a temperature of 90 to 200 ° C., 1 to 20 hours is preferable, more preferable. Is 2 to 10 hours.
本発明の速硬化性光触媒体の光触媒層に含有されるペルオキソチタン酸は、光触媒層を形成するための光触媒を含有する液において、光触媒として用いられる酸化チタンが沈降するのを抑制し、塗膜の密着性を向上させる。特に、ペルオキソチタン酸がペルオキソチタン酸ゾルであると、光触媒を含有する液のゲル化を抑制し光触媒層の形成のための塗布工程を容易とするため好ましい。ペルオキソチタン酸ゾルは水溶性チタン化合物と塩基性物質との反応による水酸化チタンの生成工程と、水酸化チタンの洗浄工程と、洗浄した水酸化チタンと過酸化水素との反応工程により製造することができる。かかるペルオキソチタン酸ゾルの製造における水酸化チタンの生成工程は、水溶性チタン化合物として四塩化チタンを用い、塩基性物質としてアンモニア水を用い、水存在下で、１〜４０℃、好ましくは、室温で反応させることが好ましい。例えば、５０％四塩化チタン水溶液にアンモニア水を滴下し攪拌後放置することにより、常温で反応させて水酸化チタンを沈殿として得ることができる。 The peroxotitanic acid contained in the photocatalyst layer of the fast-curing photocatalyst body of the present invention suppresses the precipitation of titanium oxide used as a photocatalyst in a liquid containing a photocatalyst for forming the photocatalyst layer. Improve the adhesion. In particular, it is preferable that the peroxotitanic acid is a peroxotitanate sol because gelation of the liquid containing the photocatalyst is suppressed and the coating process for forming the photocatalyst layer is facilitated. The peroxotitanate sol is manufactured by the production process of titanium hydroxide by the reaction of a water-soluble titanium compound and a basic substance, the washing process of titanium hydroxide, and the reaction process of washed titanium hydroxide and hydrogen peroxide. Can do. The production step of titanium hydroxide in the production of such a peroxotitanate sol uses titanium tetrachloride as the water-soluble titanium compound, ammonia water as the basic substance, and 1 to 40 ° C. in the presence of water, preferably at room temperature. It is preferable to make it react with. For example, by adding ammonia water dropwise to a 50% titanium tetrachloride aqueous solution and allowing it to stand after stirring, it is allowed to react at room temperature to obtain titanium hydroxide as a precipitate.
得られた水酸化チタンの洗浄工程は、生成した沈殿にイオン交換処理を行った脱イオン水を適量添加して、沈殿に残留するアンモニウムイオン等の不純物を溶解させ上澄みを除去する操作を反復して行うことができるが、得られた水酸化チタンをイオン交換処理を行った脱イオン水で洗浄した後、水酸化チタンを水に縣濁させ、この縣濁液に陽イオン交換樹脂及び陰イオン交換樹脂の混合イオン交換樹脂等を添加し、充分に攪拌してイオン交換樹脂を濾別する等、水酸化チタンとイオン交換樹脂とを直接接触させることにより不純物を除去する方法が、不純物の除去を効率よく行うことができるため好ましい。また、かかるイオン交換樹脂との接触による脱イオン処理は必要に応じて、反復して行い、アンモニウムイオン濃度が５０ｐｐｍから６００ｐｐｍになるように洗浄することが好ましい。 In the obtained titanium hydroxide washing step, an appropriate amount of deionized water subjected to ion exchange treatment was added to the generated precipitate to repeat the operation of dissolving impurities such as ammonium ions remaining in the precipitate and removing the supernatant. After washing the obtained titanium hydroxide with deionized water subjected to ion exchange treatment, the titanium hydroxide is suspended in water, and the cation exchange resin and anion are added to the suspension. The method of removing impurities by directly contacting titanium hydroxide and ion exchange resin, such as adding ion exchange resin mixed with an exchange resin, sufficiently stirring and separating the ion exchange resin by filtration, etc. Can be performed efficiently. Moreover, it is preferable to perform the deionization treatment by contact with the ion exchange resin repeatedly as necessary, and wash the ammonium ion concentration to be 50 ppm to 600 ppm.
洗浄した水酸化チタンと過酸化水素との反応工程は、水酸化チタンに過酸化水素水を添加することにより行うことができる。上記水溶性チタン化合物と塩基性物質との反応による水酸化チタンの生成工程及びこれに続く洗浄工程により得られた水酸化チタンの性状はゲル状であるが、かかる水酸化チタンゲルに過酸化水素を加えることにより、水酸化チタンゲルのヒドロキシ基の一部がＯＯＨ基となり、ペルオキソチタン酸イオンとなって溶解し、水酸化チタンゲルが分解してペルオキソチタン酸ゾルが生成される。かかるペルオキソチタン酸ゾルは、含有される溶液の安定性を高め、長期保存を可能とするため、光触媒体、光触媒層を調製するためのコーティング液におけるペルオキソチタン酸ゾルの含有量が、アナターゼ型酸化チタン１重量部に対して、１／９〜７／３重量部の範囲であることが好ましい。ペルオキソチタン酸の含有量がこの範囲であれば、ゾル状の塗布液等がゲル化することを抑制することができる。 The reaction process of the washed titanium hydroxide and hydrogen peroxide can be performed by adding hydrogen peroxide water to titanium hydroxide. The titanium hydroxide produced by the reaction of the water-soluble titanium compound with a basic substance and the subsequent washing step is gel-like, but hydrogen peroxide is added to the titanium hydroxide gel. By adding, a part of hydroxy groups of the titanium hydroxide gel becomes OOH groups and dissolves as peroxotitanate ions, and the titanium hydroxide gel is decomposed to generate a peroxotitanate sol. Such a peroxotitanate sol increases the stability of the contained solution and enables long-term storage. Therefore, the content of the peroxotitanate sol in the coating solution for preparing the photocatalyst and the photocatalyst layer is reduced by anatase oxidation. It is preferably in the range of 1/9 to 7/3 parts by weight with respect to 1 part by weight of titanium. If content of peroxotitanic acid is this range, it can suppress that a sol-like coating liquid etc. gelatinize.
本発明の速硬化性光触媒体の光触媒層には、必要に応じて、塗布性能や塗布膜の物性の向上を図るために酸化分解に強い界面活性剤、着色料、顔料、充填剤、タレ防止剤、レベリング剤、ハジキ防止剤や、防臭剤、防藻剤、防黴剤、防菌剤等を含有させてもよく、また、被覆層に含有されるポリシロキサン化合物と同様のものを含有させてもよい。かかるポリシロキサン化合物を含有した被覆層は、光触媒体の強度を向上させ、硬化速度をより速くすることができる。 In the photocatalyst layer of the fast-curing photocatalyst of the present invention, a surfactant, a colorant, a pigment, a filler, and a sag-preventing agent that are resistant to oxidative decomposition in order to improve the coating performance and physical properties of the coating film, if necessary Agents, leveling agents, anti-repellent agents, deodorants, anti-algae agents, anti-fungal agents, anti-bacterial agents, etc., and the same polysiloxane compounds contained in the coating layer. May be. The coating layer containing such a polysiloxane compound can improve the strength of the photocatalyst and increase the curing rate.
また、本発明の速硬化性光触媒体の光触媒層の厚さは、０．２〜１０μｍであることが好ましい。光触媒層の厚さがこの範囲であると、透明性を損なわず、防汚、脱臭、ガスの分解等充分な光触媒効果を得ることができる。 Moreover, it is preferable that the thickness of the photocatalyst layer of the fast-curing photocatalyst body of the present invention is 0.2 to 10 μm. When the thickness of the photocatalyst layer is within this range, sufficient photocatalytic effects such as antifouling, deodorization, and gas decomposition can be obtained without impairing transparency.
本発明の速硬化性光触媒体の被覆層に含有されるポリシロキサン化合物は、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応させて得られ、このポリシロキサン化合物を含有する被覆層は、汚れ等の除去効果を有し、光触媒体に表面強度を付与すると共に成形時において速硬化性を付与し、塗布等の施工中や施工直後に硬化し、塗膜に接触して塗膜に破損が生ずるのを抑制させる効果を奏する。かかる被覆層に含有されるポリシロキサン化合物を得るために用いられるアルコキシシラン化合物及び／又はアルコキシシロキサン化合物は、一般式（Ｉ）（式中、ＲはＣ１〜Ｃ４のアルキル基を表し、ｘ、ｙは０≦ｘ≦１．２、１．６≦ｙ≦４であり、且つ２ｘ＋ｙ＝４である数値を表す。）で示される化合物であることが好ましい。一般式（Ｉ）で示されるアルコキシシラン化合物は、式中、ｘ＝０、ｙ＝４で表され、ケイ素原子に４つのアルコキシ基が結合した化合物であり、式中のＲが表すＣ１〜Ｃ４のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｎ−ブトキシ基等を挙げることができる。かかるアルコキシ基は、アルキル基、アルコキシ基、アリール基等の置換基を有していてもよく、同一の分子内で４つが同一であっても、異なるものであってもよいが、炭素数が多くなると溶媒に対する溶解性が低下するため、炭素数は少ないものが好ましい。かかるアルコキシ基を有するテトラアルコキシシラン化合物としては、具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラ−ｎ−プロポキシシラン、テトライソプロプキシシラン、テトラ−ｎ−ブトキシシラン、テトラ−ｓｅｃ−ブトキシシラン、ジメトキシジエトキシシラン、ジメトキシジ−ｎ−プロポキシシラン、ジメトキシ−ｎ−ブトキシシラン等を挙げることができ、これらの１種又は２種以上を組み合わせて用いることができる。 The polysiloxane compound contained in the coating layer of the fast-curing photocatalyst of the present invention is obtained by reacting an alkoxysilane compound and / or an alkoxysiloxane compound in water and an organic solvent, and is a coating containing this polysiloxane compound. The layer has an effect of removing dirt and the like, imparts surface strength to the photocatalyst and imparts fast curability at the time of molding, cures immediately during construction such as coating, or immediately after construction, and touches the coating film to apply. There is an effect of suppressing the occurrence of breakage in the film. The alkoxysilane compound and / or the alkoxysiloxane compound used for obtaining the polysiloxane compound contained in the coating layer has the general formula (I) (wherein R represents a C1-C4 alkyl group, x, y Represents a numerical value of 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, and 2x + y = 4). The alkoxysilane compound represented by the general formula (I) is a compound represented by x = 0, y = 4 in the formula, wherein four alkoxy groups are bonded to a silicon atom, and C1 to C4 represented by R in the formula. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Such an alkoxy group may have a substituent such as an alkyl group, an alkoxy group, an aryl group, etc., and four may be the same or different within the same molecule, Since the solubility with respect to a solvent will fall when it increases, a thing with few carbon atoms is preferable. Specific examples of the tetraalkoxysilane compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxy. Silane, dimethoxydiethoxysilane, dimethoxydi-n-propoxysilane, dimethoxy-n-butoxysilane and the like can be mentioned, and one or more of these can be used in combination.
また、一般式（Ｉ）で示されるアルコキシシロキサン化合物は、ケイ素原子に、シロキサン結合を形成する酸素原子と、アルコキシ基が結合した化合物であり、式中、置換基Ｒが表すＣ１〜Ｃ４のアルコキシ基としては、上述のアルコキシシラン化合物におけるものと同様のものを例示することができ、かかるアルコキシ基はアルキル基、アリール基等の置換基を有していてもよく、また、同一分子内において、同一のものに限らず異なるものであってもよい。かかるアルコキシ基を有するアルコキシシロキサン化合物においては、１種又は２種以上を組み合わせて用いることができる。置換基ＲがＣ１〜Ｃ４のアルコキシ基を有するアルコキシシラン化合物や、アルコキシシロキサン化合物は、溶媒に対する溶解性が高く、有機溶媒の使用量を低減することができ、得られる光触媒体が優れた汚染抑制機能を有すると共に、安全性を確保できる。好ましくは、置換基Ｒがメトキシ基、エトキシ基を有するものを挙げることができ、特にメトキシ基を有するものは有機溶媒に対し易溶性、安定性を有し、少量の溶媒に溶解して容易に重縮合反応を生じると共に、貯蔵時のゲル化が抑制され、顕著な汚染抑制機能を有するため好ましい。 The alkoxysiloxane compound represented by the general formula (I) is a compound in which an oxygen atom that forms a siloxane bond and an alkoxy group are bonded to a silicon atom. In the formula, a C1-C4 alkoxy represented by a substituent R Examples of the group include the same groups as those in the alkoxysilane compound described above. The alkoxy group may have a substituent such as an alkyl group or an aryl group, and in the same molecule, It may be different not only in the same thing. In the alkoxysiloxane compound which has this alkoxy group, it can use 1 type or in combination of 2 or more types. The alkoxysilane compound or alkoxysiloxane compound in which the substituent R has a C1-C4 alkoxy group has high solubility in a solvent, can reduce the amount of organic solvent used, and the resulting photocatalyst is excellent in pollution control. It has functions and can secure safety. Preferable examples include those in which the substituent R has a methoxy group or an ethoxy group, and particularly those having a methoxy group are readily soluble in organic solvents and stable and easily dissolved in a small amount of solvent. It is preferable because it causes a polycondensation reaction, suppresses gelation during storage, and has a remarkable contamination suppressing function.
また、本発明の光触媒体に使用されるアルコキシシロキサン化合物は、一般式（Ｉ）中、シロキサン結合の縮合度を表すｘが、０＜ｘ≦１．２の範囲であることが好ましく、シロキサン結合を形成する酸素原子を除いたケイ素原子に結合するアルコキシ基の割合を示すｙは、２ｘ＋ｙ＝４との関係から定まり、１．６≦ｙ＜４の範囲であることが好ましい。かかるｘの値はＳｉ−ＮＭＲの測定値に基づき、テトラメチルシランのケミカルシフト値を０ｐｐｍとして、ケイ素原子が有するシロキサン結合の数に由来するケミカルシフト値−７５〜−１２０ｐｐｍの間に生じる５群のピークＱ０〜Ｑ４が、Ｑ０はシロキサン結合の数が０のモノマー、Ｑ１はシロキサン結合の数が１つ、Ｑ２はシロキサンの数が２つ、Ｑ３はシロキサン結合の数が３つ、Ｑ４はシロキサン結合の数が４つの化合物に対応するところから、各ピークＱ０、Ｑ１、Ｑ２、Ｑ３、Ｑ４の面積比をＡ：Ｂ：Ｃ：Ｄ：Ｅ（Ａ＋Ｂ＋Ｃ＋Ｄ＋Ｅ＝１）とし、ｘ＝Ａ×０＋Ｂ×０．５＋Ｃ×１．０＋Ｄ×１．５＋Ｅ×２から定められる値である。また、置換基Ｒとして相異なる２種以上の基を有する場合、ケミカルシフトの同定が容易な方法を適宜選択し、Ｈ−ＮＭＲあるいは13Ｃ−ＮＭＲにより各々の置換基の結合量を換算して定めることができる。 In the general formula (I), the alkoxysiloxane compound used in the photocatalyst of the present invention is preferably such that x representing the degree of condensation of the siloxane bond is in the range of 0 <x ≦ 1.2. Y which shows the ratio of the alkoxy group couple | bonded with the silicon atom except the oxygen atom which forms is determined from the relationship of 2x + y = 4, and it is preferable that it is the range of 1.6 <= y <4. The value of x is based on the measured value of Si-NMR, the chemical shift value of tetramethylsilane is 0 ppm, and the chemical shift value derived from the number of siloxane bonds possessed by silicon atoms is -75 to -120 ppm. Q0 is a monomer having 0 siloxane bonds, Q1 is 1 siloxane bond, Q2 is 2 siloxanes, Q3 is 3 siloxane bonds, and Q4 is siloxane Since the number of bonds corresponds to four compounds, the area ratio of each peak Q0, Q1, Q2, Q3, Q4 is A: B: C: D: E (A + B + C + D + E = 1), and x = A × 0 + B × This is a value determined from 0.5 + C × 1.0 + D × 1.5 + E × 2. In addition, when the substituent R has two or more different groups, a method that facilitates chemical shift identification is appropriately selected, and the amount of each substituent bonded is converted by H-NMR or 13 C-NMR. Can be determined.
上記一般式（Ｉ）で示されるアルコキシシロキサン化合物として、ジメトキシポリシロキサン、ジエトキシポリシロキサン、ジ−ｎ−プロポキシポリシロキサン、ジイソプロポキシポリシロキサン、ジ−ｎ−ブトキシポリシロキサン、ジイソブトキシポリシロキサン、ジ−ｓｅｃ−ブトキシポリシロキサン、ジ−ｔ−ブトキシポリシロキサン等を挙げることができ、これらのアルコキシシロキサン化合物を示す一般式（Ｉ）中、シロキサン結合の縮合度を表すｘが０．８であるものが好ましく、これらの１種又は２種以上を混合して用いることができる。このうち、ジメトキシポリシロキサン、ジエトキシポリシロキサンが有機溶媒に易溶であり、ゲル化が生じにくいため好ましく、特に、ジメトキシポリシロキサンが好ましい。かかるアルコキシシロキサン化合物としては、市販のもの、例えば、ＭＫＣシリケート（商品名：三菱化学（株））等を利用することができ、このうち特にＭＳ５１等のシリケート化合物を好適に使用することができる。 Examples of the alkoxysiloxane compound represented by the general formula (I) include dimethoxypolysiloxane, diethoxypolysiloxane, di-n-propoxypolysiloxane, diisopropoxypolysiloxane, di-n-butoxypolysiloxane, diisobutoxypolysiloxane, Di-sec-butoxypolysiloxane, di-t-butoxypolysiloxane, and the like can be mentioned. In general formula (I) representing these alkoxysiloxane compounds, x representing the degree of condensation of siloxane bonds is 0.8. A thing is preferable and these 1 type (s) or 2 or more types can be mixed and used. Of these, dimethoxypolysiloxane and diethoxypolysiloxane are preferable because they are easily soluble in an organic solvent and hardly cause gelation, and dimethoxypolysiloxane is particularly preferable. As the alkoxysiloxane compound, commercially available products such as MKC silicate (trade name: Mitsubishi Chemical Corporation) can be used, and among these, silicate compounds such as MS51 can be particularly preferably used.
尚、本発明の光触媒体の被覆層には、上記一般式（Ｉ）で表されるアルコキシシラン化合物や、アルコキシシロキサン化合物の他、他のケイ素化合物が含有されてもよい。かかるケイ素化合物としては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリイソプロポキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリイソプロポキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン等を挙げることができる。尚、これらのケイ素化合物の含有量は、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物のＳｉＯ2換算で１００重量部に対して２０重量部以下、好ましくは１０重量部以下である。 The coating layer of the photocatalyst of the present invention may contain other silicon compounds in addition to the alkoxysilane compound represented by the general formula (I) and the alkoxysiloxane compound. Such silicon compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane. Methoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, Examples include diphenyldiethoxysilane. The content of these silicon compounds, alkoxysilane compounds and / or alkoxy than 20 parts by weight per 100 parts by weight in terms of SiO 2 siloxane compounds, preferably at most 10 parts by weight.
上記アルコキシシラン化合物及び／又はアルコキシシロキサン化合物の反応に使用される水は、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物と容易に反応してアルコキシ基の総て又は一部を残してヒドロキシ基と置換したシラノール化合物を生成するものであり、水道水等いずれのものであってもよく、目的、用途によって脱イオン水、超純水を適宜選択して使用することができる。例えば、酸により特に腐食しやすい軟鋼、銅、アルミニウム等の基材や、耐熱性被膜、耐湿性被膜、耐薬品性被膜、耐バリア性被膜、電気絶縁性被膜の電気、電子材料等の基材に適用する場合は脱塩水を用いたり、不純物の混入を排除する必要がある場合は超純水を選択することができる。水の配合量は、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物中のＳｉ量のＳｉＯ2換算値１００重量部に対して、１００〜５００００重量部、好ましくは５００〜１００００重量部である。一般式（Ｉ）で表されるアルコキシシラン化合物及び／又はアルコキシシロキサン化合物のアルコキシ基を加水分解する理論値よりも大過剰の量の水を配合することにより、加水分解により生成したアルコールを多量の水と共存させ、再度アルコールとポリシロキサン化合物のヒドロキシ基とが反応するのを抑制し、貯蔵時の安定性を向上させ品質保持を図ると共に、有機溶媒の配合量を低くすることができ、引火点、燃焼点を低く抑えることが可能となり取扱い上有利である。また、この水の配合量がこの範囲であれば、生成物のポリシロキサン化合物の保存時のゲル化を抑制することができ、反応系を光触媒体等の成形用塗布液に利用すると、保存時に安定で、取扱いが容易であり、有機基材に光触媒体が設けられた場合でも、基材の劣化を抑制することができる。 The water used for the reaction of the alkoxysilane compound and / or alkoxysiloxane compound is easily reacted with the alkoxysilane compound and / or alkoxysiloxane compound to replace all or part of the alkoxy groups with the hydroxy groups. It produces a silanol compound and may be any one such as tap water, and deionized water or ultrapure water can be appropriately selected and used depending on the purpose and application. For example, base materials such as mild steel, copper, and aluminum that are particularly susceptible to corrosion by acids, and base materials such as heat resistant coatings, moisture resistant coatings, chemical resistant coatings, barrier resistant coatings, electrical insulating electronic coatings, and electronic materials. When applying to the above, demineralized water can be used, and when it is necessary to exclude contamination of impurities, ultrapure water can be selected. The compounding amount of water is 100 to 50000 parts by weight, preferably 500 to 10000 parts by weight with respect to 100 parts by weight of the SiO 2 value of Si in the alkoxysilane compound and / or alkoxysiloxane compound. By adding a large excess of water than the theoretical value for hydrolyzing the alkoxy group of the alkoxysilane compound and / or alkoxysiloxane compound represented by the general formula (I), a large amount of alcohol produced by hydrolysis is added. It can coexist with water to prevent the alcohol and the hydroxy group of the polysiloxane compound from reacting again, improve the stability during storage and maintain the quality, and reduce the blending amount of the organic solvent. The point and the combustion point can be kept low, which is advantageous in handling. Moreover, if the blending amount of this water is within this range, gelation at the time of storage of the product polysiloxane compound can be suppressed, and when the reaction system is used for a coating liquid for molding such as a photocatalyst, It is stable and easy to handle, and even when the photocatalyst is provided on the organic base material, the deterioration of the base material can be suppressed.
上記アルコキシシラン化合物及び／又はアルコキシシロキサン化合物の反応に使用される有機溶媒としては特に限定されるものではなく、各種の有機溶剤、例えば、アルコール類、グリコール誘導体、炭化水素類、エステル類、ケトン類、エーテル類等の１種、又は２種以上を混合して使用することができる。かかる有機溶媒として、具体的には、アルコール類として、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール等、グリコール誘導体としては、エチレングリコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等、炭化水素類としては、ベンゼン、トルエン、キシレン、ｎ−ヘキサン等、エステル類としては、酢酸メチル、酢酸エチル等を例示することができる。これらの溶剤のうち、メタノール、エタノール、イソプロパノール等のアルコール類がアルコキシシラン化合物及び／又はアルコキシシロキサン化合物の溶媒として好ましく、また、反応系を光触媒層又は保護層を形成するためのコーティング液に直接使用することができるため好ましく、特に、エタノールが、安全性や、生成物のゲル化を抑制する安定性に優れているため好適である。有機溶媒の配合量は、一般式（Ｉ）で示されるアルコキシシラン化合物及び／又はアルコキシシロキサン化合物のＳｉ量のＳｉＯ2換算値１００重量部に対して、１００〜５００００重量部、より好ましくは５００〜１００００重量部である。有機溶媒の添加量がこの範囲であれば、反応物を均一に溶解させることができ、光触媒体における汚染抑制効果が顕著であり好ましい。 The organic solvent used in the reaction of the alkoxysilane compound and / or alkoxysiloxane compound is not particularly limited, and various organic solvents such as alcohols, glycol derivatives, hydrocarbons, esters, ketones , Ethers and the like, or a mixture of two or more can be used. Specific examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol, and glycol derivatives such as ethylene glycol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Examples of hydrocarbons such as propylene glycol, propylene glycol monomethyl ether, and propylene glycol monoethyl ether include benzene, toluene, xylene, and n-hexane, and examples of esters include methyl acetate and ethyl acetate. . Among these solvents, alcohols such as methanol, ethanol, and isopropanol are preferable as the solvent for the alkoxysilane compound and / or alkoxysiloxane compound, and the reaction system is directly used as a coating solution for forming a photocatalytic layer or a protective layer. In particular, ethanol is preferable because it is excellent in safety and stability for suppressing gelation of the product. The compounding amount of the organic solvent is 100 to 50,000 parts by weight, more preferably 500 to 100 parts by weight with respect to 100 parts by weight of the Si 2 content of the alkoxysilane compound and / or alkoxysiloxane compound represented by the general formula (I). 10,000 parts by weight. If the addition amount of the organic solvent is within this range, the reaction product can be dissolved uniformly, and the effect of suppressing contamination in the photocatalyst is remarkable, which is preferable.
上記アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応して得られるポリシロキサン化合物は、アルコキシシラン化合物やアルコキシシロキサン化合物の重縮合物であって、アルコキシ基の一部ないし総てが加水分解されヒドロキシ基に変換されたシラノール化合物である。かかるポリシロキサン化合物を生成する反応は、上記アルコキシシラン化合物及び／又はアルコキシシロキサン化合物に上記量の有機溶媒及び水を添加し、適宜触媒を添加して、常温で攪拌、振動等による混合後、放置して行うことができる。かかる触媒としては、例えば、塩酸、硫酸、硝酸、リン酸等の無機酸、酢酸、ベンゼンスルホン酸、トルエンスルホン酸、キシレンスルホン酸、エチルベンゼンスルホン酸、安息香酸、フタル酸、マレイン酸、ギ酸、シュウ酸等の有機酸、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、アンモニア、有機アミン化合物等のアルカリ触媒、ジブチルスズジラウレート、ジブチルスズジオクチエート、ジブチルスズジアセテート等の有機スズ化合物、アルミニウムトリス（アセチルアセトネート）、アルミニウムモノアセチルアセトネートビス（エチルアセトアセテート）、アルミニウムトリス（エチルアセトアセテート）、エチルアセトアセテートアルミニウムジイソプロピレート等の有機アルミニウム化合物、チタニウムテトラキス（アセチルアセトネート）、チタニウムビス（ブトキシ）ビス（アセチルアセトネート）、チタニウムテトラ−ｎ−ブトキシド等の有機チタニウム化合物、ジルコニウムテトラキス（アセチルアセトネート）、ジルコニウムビス（ブトキシ）ビス（アセチルアセトネート）及びジルコニウム（イソプロポキシ）ビス（アセチルアセトネート）、ジルコニウムテトラ−ｎ−ブトキシド等の有機ジルコニウム化合物等の、オルガノシリケート以外の有機金属化合物又は金属アルコキシド化合物、ボロントリ−ｎ−ブトキシド、ホウ酸等のホウ素化合物等を挙げることができる。これらの触媒は、１種又は２種以上組み合わせたものも使用できる。触媒の添加量は、アルコキシシラン化合物及び／又はアルコキシシロキサン化合物のＳｉ量をＳｉＯ2 に換算した１００重量部に対して、０．１〜１０重量部であり、より好ましくは０．５〜５重量部である。 The polysiloxane compound obtained by reacting the alkoxysilane compound and / or the alkoxysiloxane compound in water and an organic solvent is a polycondensate of an alkoxysilane compound or an alkoxysiloxane compound, and a part or all of the alkoxy groups. Is a silanol compound that has been hydrolyzed and converted to a hydroxy group. The reaction for producing such a polysiloxane compound is carried out by adding the above-mentioned amount of organic solvent and water to the above-mentioned alkoxysilane compound and / or alkoxysiloxane compound, adding an appropriate catalyst, mixing at room temperature, stirring, vibration, etc. Can be done. Such catalysts include, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, ethylbenzenesulfonic acid, benzoic acid, phthalic acid, maleic acid, formic acid, oxalic acid. Organic acids such as acids, alkali catalysts such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, organic amine compounds, organotin compounds such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate, aluminum tris (acetylacetate) ), Aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (ethyl acetoacetate), organic aluminum compounds such as ethyl acetoacetate aluminum diisopropylate, titanium tetrakis (Acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), organic titanium compounds such as titanium tetra-n-butoxide, zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate) and Organometallic compounds other than organosilicates such as zirconium (isopropoxy) bis (acetylacetonate) and zirconium tetra-n-butoxide, or metal alkoxide compounds, boron compounds such as boron tri-n-butoxide and boric acid Etc. These catalysts may be used alone or in combination of two or more. The addition amount of the catalyst is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the Si content of the alkoxysilane compound and / or alkoxysiloxane compound converted to SiO 2. Part.
このようなアルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応して得られるポリシロキサン化合物を１〜１０重量％含有する反応系を本発明の光触媒体を調製するコーティング液等に使用することができ、このような反応系として、市販のもの、例えば、シンスイフロー（ＭＳ１２００及びＭＳ１２０８）（商品名：大日本色材工業（株））を適用することができる。 A reaction system containing 1 to 10% by weight of a polysiloxane compound obtained by reacting such an alkoxysilane compound and / or alkoxysiloxane compound in water and an organic solvent is used as a coating solution for preparing the photocatalyst of the present invention. As such a reaction system, a commercially available product such as Sinsui Flow (MS1200 and MS1208) (trade name: Dainippon Color Material Co., Ltd.) can be applied.
本発明の速硬化性光触媒体における被覆層には、必要に応じて、塗布性能や塗布膜の物性の向上を図るために酸化分解に強い界面活性剤、着色料、顔料、充填剤、タレ防止剤、レベリング剤、ハジキ防止剤や、防臭剤、防藻剤、防黴剤、防菌剤等を含有させてもよい。 The coating layer in the fast-curing photocatalyst of the present invention has a surface active agent, a colorant, a pigment, a filler, and a sag-preventing agent that are resistant to oxidative degradation in order to improve the coating performance and physical properties of the coating film, if necessary Agents, leveling agents, anti-repellent agents, deodorants, algae inhibitors, antifungal agents, antibacterial agents, and the like may be included.
また、本発明の速硬化性光触媒体の被覆層の厚さは、０．０１〜０．５μｍであることが好ましく、０．０１〜０．１μｍであることがより好ましく、更に、好ましくは０．０２〜０．０５μｍである。被覆層の厚さがこの範囲であると、透明性を損なわず、光触媒活性を高くし、且つ光触媒体に表面強度と速硬化性を付与することができる。 Moreover, the thickness of the coating layer of the fast-curing photocatalyst of the present invention is preferably 0.01 to 0.5 μm, more preferably 0.01 to 0.1 μm, and further preferably 0. 0.02-0.05 μm. When the thickness of the coating layer is within this range, transparency is not impaired, photocatalytic activity is increased, and surface strength and fast curability can be imparted to the photocatalyst.
本発明の光触媒体は、基材の上に設けられる光触媒層と被覆層の２層積層構造体であっても、該２層積層構造体が２以上積層された多層構造体であってもよい。多層構造体とすることにより光触媒による防汚、脱臭、ガス分解効果が長期間持続して得られる。 The photocatalyst of the present invention may be a two-layer laminated structure of a photocatalyst layer and a coating layer provided on a substrate, or a multilayer structure in which two or more of the two-layer laminated structures are laminated. . By using a multilayer structure, antifouling, deodorizing, and gas decomposition effects by the photocatalyst can be obtained for a long time.
本発明の光触媒体は光触媒層、被覆層のそれぞれの成形用コーティング液を調製し、コーティング液を基材に塗布する方法等により成形することができる。即ち、光触媒層成形用コーティング液はアナターゼ型酸化チタンゾル１〜２重量％の水分散液に、ペルオキソチタン酸をアナターゼ型酸化チタン１重量部に対して１／９〜７／３重量部を添加し、１〜４０℃、好ましくは室温で、混合攪拌することにより調製することができる。アナターゼ型酸化チタンとペルオキソチタン酸の含有量の割合がこの範囲であると、光触媒体が有効な光触媒作用を有し、基材に強固に固着し両者の剥離を抑制することができ、透明性を保持することができる。光触媒層にポリシロキサン化合物を含有させる場合は、上記光触媒層成形用コーティング液に、ポリシロキサン化合物として上記シンスイフロー（ＭＳ１２００又はＭＳ１２０８）（商品名：大日本色材工業（株））をアナターゼ型酸化チタンとペルオキソチタン酸との混合合計重量に対して、５〜７０重量％等添加して調製することができる。また、上記被覆層成形用コーティング液は、上記アルコキシシラン化合物及び／又はアルコキシシロキサン化合物を水及び有機溶媒中で反応させた反応系をそのまま用いることができる。 The photocatalyst of the present invention can be formed by a method of preparing a coating liquid for forming each of the photocatalyst layer and the coating layer and applying the coating liquid to a substrate. That is, the photocatalyst layer forming coating solution is prepared by adding 1/9 to 7/3 parts by weight of peroxotitanic acid to 1 part by weight of anatase type titanium oxide in an aqueous dispersion of 1-2% by weight of anatase type titanium oxide sol. 1 to 40 ° C., preferably at room temperature, by mixing and stirring. When the ratio of the content of anatase-type titanium oxide and peroxotitanic acid is within this range, the photocatalyst has an effective photocatalytic action, firmly adheres to the base material, and can be prevented from peeling off. Can be held. When a polysiloxane compound is contained in the photocatalyst layer, the thin film flow (MS1200 or MS1208) (trade name: Dainippon Color Material Co., Ltd.) is used as the polysiloxane compound in the photocatalyst layer molding coating solution. It can be prepared by adding 5 to 70% by weight or the like with respect to the total mixed weight of peroxotitanic acid. The coating liquid for forming the coating layer can be used as it is, a reaction system obtained by reacting the alkoxysilane compound and / or alkoxysiloxane compound in water and an organic solvent.
かかるコーティング液を用いて光触媒層や、保護層を基材に成形する方法としては、スプレーコーティング法、ディップコーティング法、スピンコーティング法、ローラーコーティング法、ブレードコーティング法、ワイヤーバーコーティング法、フローコーティング法等の通常の方法を挙げることができる。具体的には、上記コーティング液を上記コーティング方法により基材表面にコーティングし、自然乾燥あるいは熱風を吹き付ける等の方法で乾燥させ、このコーティングと乾燥を反復し目的の厚さを有する層を成形することができる。多層積層構造体の場合は、光触媒層成形用コーティング液と、被覆層成形用コーティング液を順次コーティングし積層体を形成することができる。尚、基材表面はこれらの塗布前に洗剤、アルコール等の溶剤等で十分に洗浄、脱脂することが望ましい。 As a method of forming a photocatalyst layer or a protective layer on a substrate using such a coating liquid, spray coating method, dip coating method, spin coating method, roller coating method, blade coating method, wire bar coating method, flow coating method The usual methods, such as these, can be mentioned. Specifically, the surface of the substrate is coated with the above coating method by the above coating method, dried by a method such as natural drying or blowing hot air, and this coating and drying are repeated to form a layer having a desired thickness. be able to. In the case of a multilayer laminate structure, a laminate can be formed by sequentially coating a photocatalyst layer forming coating solution and a coating layer forming coating solution. In addition, it is desirable that the surface of the base material be sufficiently washed and degreased with a solvent such as a detergent or alcohol before application.
本発明の速硬化性光触媒体が適用される基材はその材質を問わず何れのものであってもよい。かかる基材の材質としては、具体的に、セラミックス、ガラス、コンクリート等の無機材質、ポリアクリロニトリル、ポリカーボネート、ポリエチレン、ポリスチレン、ポリプロピレン、ポリアミド、ポリ塩化ビニル、ポリエチレンテレフタレート、ＡＢＳ樹脂、合成ゴム等の合成高分子や、天然ゴム、天然繊維、木、紙等の天然の有機材質、ステンレス、アルミニウム等の金属類等を挙げることができる。また、種々の塗料で塗装された基材にも適用され得る。 The substrate to which the fast-curing photocatalyst of the present invention is applied may be any material regardless of the material. Specific examples of the material of the base material include inorganic materials such as ceramics, glass, and concrete, polyacrylonitrile, polycarbonate, polyethylene, polystyrene, polypropylene, polyamide, polyvinyl chloride, polyethylene terephthalate, ABS resin, and synthetic rubber. Examples thereof include polymers, natural organic materials such as natural rubber, natural fibers, wood and paper, and metals such as stainless steel and aluminum. It can also be applied to substrates coated with various paints.
本発明の速硬化性光触媒体が適用される基材は特に制限されず、例えば、ビル、住宅等の外壁及び内壁、ダム、橋梁、道路、防波堤、護岸用設置体等の土木構造物の表面、銅像、石像、墓石、モニュメント、道路標識、信号、照明灯等の表面、車両、船舶、航空機等の外面及び内面、ガスタンク、水道タンク等の外壁面等を挙げることができる。 The base material to which the fast-curing photocatalyst of the present invention is applied is not particularly limited. For example, the surface of a civil engineering structure such as an outer wall and an inner wall of a building, a house, a dam, a bridge, a road, a breakwater, a seawall, etc. , Copper statues, stone statues, tombstones, monuments, road signs, signals, lighting lights and other surfaces, outer surfaces and inner surfaces of vehicles, ships, aircraft, etc., gas tanks, water tanks, etc.
本発明の光触媒体の実施例を示すが、本発明の技術的範囲は以下の実施例に限定されるものではない。 Examples of the photocatalyst of the present invention will be shown, but the technical scope of the present invention is not limited to the following examples.
調製例１
１００Ｌのイオン交換水に約５０重量％の四塩化チタン溶液１Ｌを添加し、これに２５重量％のアンモニア水を１Ｌ添加して充分攪拌した。静置後、生成した水酸化チタンが沈殿後、上澄み液を排出し、イオン交換水を適量添加して充分攪拌してから静置し、上澄み液を再度排出した。この洗浄操作を繰り返し、アンモニウムイオンを５００ｐｐｍにした。これに３５重量％過酸化水素を２Ｌ添加して攪拌したところ、黄色透明のペルオキソチタン酸ゾルを得た。
Preparation Example 1
1 L of about 50 wt% titanium tetrachloride solution was added to 100 L of ion exchange water, and 1 L of 25 wt% aqueous ammonia was added thereto and stirred sufficiently. After standing, after the formed titanium hydroxide was precipitated, the supernatant liquid was discharged, an appropriate amount of ion-exchanged water was added, and the mixture was sufficiently stirred and allowed to stand, and the supernatant liquid was discharged again. This washing operation was repeated to adjust the ammonium ion to 500 ppm. When 2 L of 35 wt% hydrogen peroxide was added thereto and stirred, a yellow transparent peroxotitanate sol was obtained.
調製例２
調製例１と同様にして四塩化チタンとアンモニア水を反応させた後、水酸化チタンの沈殿をアンモニウムイオンが約１０００ｐｐｍになるまでイオン交換水で洗浄した。この水酸化チタンの分散液に陽イオン交換樹脂と陰イオン交換樹脂の混合イオン交換樹脂（商品名：ＳＭＮＵＰＢ、日本錬水株式会社製）を６００ｇ添加し、よく攪拌した後ナイロン製の網でイオン交換樹脂を濾別した。このときのアンモニウムイオンは２００ｐｐｍであった。この液に３５重量％過酸化水素を２Ｌ添加して攪拌した。黄色透明のペルオキソチタン酸ゾルを得た。
Preparation Example 2
After reacting titanium tetrachloride and aqueous ammonia in the same manner as in Preparation Example 1, the precipitate of titanium hydroxide was washed with ion-exchanged water until the ammonium ion was about 1000 ppm. To this titanium hydroxide dispersion, 600 g of a mixed ion exchange resin of cation exchange resin and anion exchange resin (trade name: SMNUPB, manufactured by Nippon Nuisui Co., Ltd.) was added, stirred well, and then ionized with a nylon net. The exchange resin was filtered off. The ammonium ion at this time was 200 ppm. 2 L of 35 wt% hydrogen peroxide was added to this liquid and stirred. A yellow transparent peroxotitanate sol was obtained.
調製例３
調製例２で得られたペルオキソチタン酸ゾルを約９５℃で８時間加熱した。黄色白濁したアナターゼ型酸化チタンの分散液を得た。
Preparation Example 3
The peroxotitanate sol obtained in Preparation Example 2 was heated at about 95 ° C. for 8 hours. A yellow-turbid dispersion of anatase-type titanium oxide was obtained.
調製例３で得られたアナターゼ型酸化チタン１重量％分散水溶液６重量部と、調製例１で得られた１重量％ペルオキソチタン酸ゾル４重量部とを混合し混合液を得た。この混合液を、５％水酸化ナトリウム水溶液でよく洗浄した後、イオン交換水で洗浄し乾燥したガラス板に、スプレー法により表1に示す所定量を塗布し、約１０分間放置して乾燥させ、光触媒層を成形した。その後、光触媒層の表面にポリシロキサン化合物（商品名：ＭＳ１２００、大日本色材工業（株）製）１重量％、エタノール５０重量％、水４９重量％を含有する溶液を、スプレー法により１０ｇ／ｍ2の量を塗布し表面を被覆した。 6 parts by weight of the 1% by weight aqueous dispersion of anatase-type titanium oxide obtained in Preparation Example 3 and 4 parts by weight of the 1% by weight peroxotitanate sol obtained in Preparation Example 1 were mixed to obtain a mixed solution. After thoroughly washing this mixed solution with 5% aqueous sodium hydroxide solution, the prescribed amount shown in Table 1 is applied by spraying to a glass plate washed with ion-exchanged water and dried, and left to dry for about 10 minutes. A photocatalyst layer was formed. Thereafter, a solution containing 1% by weight of a polysiloxane compound (trade name: MS1200, manufactured by Dainippon Color Material Co., Ltd.), 50% by weight of ethanol, and 49% by weight of water on the surface of the photocatalyst layer was sprayed at 10 g / An amount of m 2 was applied to coat the surface.
得られたサンプル１、２について、被覆層形成後、６０分経過後鉛筆引っかき値試験（ＪＩＳ規格Ｋ５４００−１９９０−８−４−２）を行った。結果を表１に示す。
また、０．０２％メチレンブルー水溶液を表面にスプレーして着色し、１．０ｍｗ／ｃｍ2強度の紫外線を照射して、４時間以内の消色を観察し、光触媒活性を評価した。結果を表１に示す。
比較例として実施例と同様の光触媒層のみを成形したもの（比較例１、２）について、実施例と同様にして鉛筆引っかき値試験及び光触媒活性の評価を行った。結果を表１に示す。
Samples 1 and 2 were subjected to a pencil scratch test (JIS standard K5400-1990-8-4-2) after 60 minutes had elapsed after forming the coating layer. The results are shown in Table 1.
Further, 0.02% methylene blue aqueous solution was sprayed on the surface to be colored, and 1.0 mw / cm 2 intensity ultraviolet ray was irradiated to observe decoloring within 4 hours to evaluate the photocatalytic activity. The results are shown in Table 1.
As comparative examples, a pencil scratch test and evaluation of photocatalytic activity were performed in the same manner as in Examples, in which only the same photocatalyst layer as in Example was molded (Comparative Examples 1 and 2). The results are shown in Table 1.
結果から被覆層を設けた光触媒体は光触媒活性が高く、速硬化性であることが明らかである。 From the results, it is clear that the photocatalyst provided with the coating layer has high photocatalytic activity and is fast-curing.
調製例３で得られたアナターゼ型酸化チタン１重量％分散水溶液７重量部と、調製例２で得られた１重量％ペルオキソチタン酸ゾル３重量部とを混合し混合液を得た。この混合液を、５００℃で２時間加熱して有機質分を除去して、表面を親水性にした白色タイルに、スプレー法により表２に示す所定量を塗布し、約１０分間放置して乾燥させ、光触媒層を成形した。その後、ポリシロキサン化合物（商品名：ＭＳ１２０８、大日本色材工業（株）製）１重量％、エタノール７９重量％、水２０重量％を含有する溶液を、スプレー法により表２に示す所定量を塗布し表面を被覆した。 7 parts by weight of the 1% by weight aqueous dispersion of anatase-type titanium oxide obtained in Preparation Example 3 and 3 parts by weight of 1% by weight peroxotitanate sol obtained in Preparation Example 2 were mixed to obtain a mixed solution. This mixed solution is heated at 500 ° C. for 2 hours to remove organic matters, and a predetermined amount shown in Table 2 is applied to a white tile having a hydrophilic surface by a spray method, and left to dry for about 10 minutes. To form a photocatalyst layer. Thereafter, a solution containing 1% by weight of a polysiloxane compound (trade name: MS1208, manufactured by Dainippon Color Material Co., Ltd.), 79% by weight of ethanol, and 20% by weight of water was subjected to a predetermined amount shown in Table 2 by a spray method. The surface was coated by coating.
得られたサンプル３〜５について、被覆層形成後、１０分経過後実施例２と同様にして鉛筆筆引っかき値試験を行った。結果を表２に示す。
また、０．０２％メチレンブルー水溶液を表面にスプレーして着色し、２．７ｍｗ／ｃｍ2強度の紫外線を照射して、消色時間を測定した。結果を表２に示す。
比較例として実施例と同様の光触媒層のみを成形したもの（比較例３、４）について、実施例と同様にして鉛筆引っかき値試験及び消色時間を測定した。結果を表２に示す。
About the obtained samples 3-5, the pencil brush scratch value test was done like Example 2 after 10-minute progress after coating layer formation. The results are shown in Table 2.
Moreover, 0.02% methylene blue aqueous solution was sprayed on the surface to color it, and irradiated with ultraviolet rays having an intensity of 2.7 mw / cm 2 to measure the decoloring time. The results are shown in Table 2.
As a comparative example, the pencil scratch value test and the decoloring time were measured in the same manner as in the examples for those obtained by molding only the same photocatalyst layer as in the examples (Comparative Examples 3 and 4). The results are shown in Table 2.
結果から被覆層を設けた光触媒体は光触媒活性が高く、速硬化性であることが明らかである。 From the results, it is clear that the photocatalyst provided with the coating layer has high photocatalytic activity and is fast-curing.
白色ウレタン塗料で塗装された壁材２枚に、調製例２で得られた１重量％ペルオキソチタン酸ゾル３０ｇ／ｍ2を３回に分けてスプレー法で塗布した。表面が乾燥してから、調製例３で得られたアナターゼ型酸化チタン１重量％分散液６０ｇ／ｍ2を４回に分けてスプレー法で塗布した。１枚の壁材には、ポリシロキサン化合物（商品名：ＭＳ１２０８、大日本色材工業（株）製）１重量％、エタノール７９重量％、水２０重量％を含有する溶液を、スプレー法により１０ｇ／ｍ2を塗布し表面を被覆した。この２枚の壁材に、２．７ｍｗ／ｃｍ2強度の紫外線を２４時間照射した後、ディーゼルエンジンの排気ガスを３０ｃｍの距離から２４時間吹き付けたところ、黒く着色した。着色後の表面反射率を色差計（ＭＩＮＯＬＴＡ ＣＲ−３００）（ミノルタ社製）で測定したところ、ポリシロキサンで表面を被覆した壁材のＬ値は６１．２であったが、光触媒だけを塗布した壁材のＬ値は５５．８であった。
結果から、ポリシロキサンを塗布した壁材は防汚染性が高いことが明らかである。
The wall material two painted with white urethane paint was applied by spraying by dividing 1 by weight% peroxotitanate sol 30 g / m 2 obtained in Preparation Example 2 to 3 times. After the surface was dried, the anatase-type titanium oxide 1 wt% dispersion 60 g / m 2 obtained in Preparation Example 3 was applied in four portions by spraying. On one wall material, 10 g of a solution containing 1% by weight of a polysiloxane compound (trade name: MS1208, manufactured by Dainippon Color Material Co., Ltd.), 79% by weight of ethanol, and 20% by weight of water is obtained by a spray method. / M 2 was applied to coat the surface. The two wall materials were irradiated with ultraviolet rays having an intensity of 2.7 mw / cm 2 for 24 hours, and then the exhaust gas of the diesel engine was blown from a distance of 30 cm for 24 hours, resulting in black coloration. When the surface reflectance after coloring was measured with a color difference meter (MINOLTA CR-300) (manufactured by Minolta), the L value of the wall material whose surface was coated with polysiloxane was 61.2, but only the photocatalyst was applied. The L value of the finished wall material was 55.8.
From the results, it is clear that the wall material coated with polysiloxane has a high antifouling property.
Claims (14)
ＳｉＯxＲy （Ｉ）
［式中、ＲはＣ１〜Ｃ４のアルコキシ基を表し、ｘ、ｙは０≦ｘ≦１．２、１．６≦ｙ≦４であり、且つ２ｘ＋ｙ＝４である数値を表す。］で示される化合物であることを特徴とする請求項１〜４のいずれか記載の速硬化性光触媒体。 Alkoxysilane compounds and / or alkoxysiloxane compounds are represented by the general formula (I)
SiO x R y (I)
[Wherein, R represents a C1 to C4 alkoxy group, and x and y represent 0 ≦ x ≦ 1.2, 1.6 ≦ y ≦ 4, and 2x + y = 4. ] The fast-curing photocatalyst according to any one of claims 1 to 4, wherein
The fast-curing photocatalyst according to claim 13, wherein the anatase-type titanium oxide sol is a dispersion of anatase-type titanium oxide prepared by heating a peroxotitanate sol at a temperature of 80 ° C or higher.
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