JP2011078917A - Exterior cladding for building and coating fluid for exterior cladding for building - Google Patents
Exterior cladding for building and coating fluid for exterior cladding for building Download PDFInfo
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- JP2011078917A JP2011078917A JP2009233905A JP2009233905A JP2011078917A JP 2011078917 A JP2011078917 A JP 2011078917A JP 2009233905 A JP2009233905 A JP 2009233905A JP 2009233905 A JP2009233905 A JP 2009233905A JP 2011078917 A JP2011078917 A JP 2011078917A
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Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、建築用外装材および建築外装用コーティング液に関する。 The present invention relates to a building exterior material and a building exterior coating liquid.
酸化チタンなどの光触媒が、特に太陽光の利用できる屋外用途において近年広く利用されている。光触媒の利用により、光エネルギーを利用して種々の有害物質を分解したり、あるいは、光触媒が塗布された基材表面を親水化して表面に付着した汚れを容易に水で洗い流すことが可能となる。 In recent years, photocatalysts such as titanium oxide have been widely used particularly in outdoor applications where sunlight can be used. By using photocatalyst, it is possible to decompose various harmful substances using light energy, or to make the surface of the substrate coated with photocatalyst hydrophilic and easily wash away dirt adhering to the surface with water. .
例えば、バインダー成分としてのシリカゾルと光触媒性二酸化チタンとを含有する塗膜を基体に形成して光触媒体を得る技術が知られている（例えば、特開平１１−１６９７２７号公報（特許文献１））。この技術にあっては、シリカゾルの添加量がＳｉＯ２基準で二酸化チタンに対して２０〜２００重量部であるとされている。 For example, a technique for obtaining a photocatalyst by forming a coating film containing silica sol as a binder component and photocatalytic titanium dioxide on a substrate is known (for example, JP-A-11-169727 (Patent Document 1)). . In this technique, the amount of silica sol added is 20 to 200 parts by weight with respect to titanium dioxide on the basis of SiO 2 .
このような光触媒層を基材表面に形成する構成において、基材が有機材料であると、光触媒の光触媒活性により有機材料が分解または劣化するおそれがある。この問題に対処するため、光触媒層と担体との間にシリコン変性樹脂等の接着層を設け、下地の担体を光触媒作用による劣化から保護する技術が知られている（国際公開第９７／００１３４号（特許文献２））。この先行技術にあっては、光触媒量が２０重量％を超える量の例が具体的に開示され、また基材の分解または劣化が有効に防止されたとしている。 In the configuration in which such a photocatalyst layer is formed on the surface of the base material, if the base material is an organic material, the organic material may be decomposed or deteriorated due to the photocatalytic activity of the photocatalyst. In order to cope with this problem, a technique is known in which an adhesive layer such as a silicon-modified resin is provided between the photocatalyst layer and the carrier to protect the underlying carrier from deterioration due to photocatalysis (WO 97/00134). (Patent Document 2)). In this prior art, an example in which the amount of the photocatalyst exceeds 20% by weight is specifically disclosed, and the decomposition or deterioration of the base material is effectively prevented.
さらに、光触媒層と、基材との間に、シリコーン変性樹脂と有機防カビ剤とを含む中間層を設け、基剤の分解または劣化を防止する提案もなされている（特許第４０９２４３４号（特許文献３））。 Further, an proposal has been made to provide an intermediate layer containing a silicone-modified resin and an organic antifungal agent between the photocatalyst layer and the base material to prevent decomposition or deterioration of the base (Patent No. 4092434 (Patent No. Reference 3)).
光触媒層における光触媒量が少なければ、上述の基材の分解または劣化の可能性は小さくなるが、その結果、光触媒による諸作用も小さくなるおそれがある。従って、国際公開第９８／０３６０７号（特許文献４）、特開２００４−５１６４４号（特許文献５）などには、光触媒量が５重量％以下とされた光触媒層の開示があるが、これらは、諸特性、とりわけ有害ガス分解性に関して適切な組成または構造とされているとは言い難い。例えば、国際公開第９８／０３６０７号にあっては、光触媒量に対してシリカ粒子の存在量が本発明のそれよりも極めて少なく、また特開２００４−５１６４４号は疎水性樹脂の添加において本発明と相違する。 If the amount of the photocatalyst in the photocatalyst layer is small, the possibility of decomposition or deterioration of the above-described base material is reduced, but as a result, there is a possibility that various actions by the photocatalyst are also reduced. Accordingly, International Publication No. 98/03607 (Patent Document 4), Japanese Patent Application Laid-Open No. 2004-51644 (Patent Document 5), etc. disclose a photocatalyst layer whose photocatalyst amount is 5% by weight or less. It is difficult to say that the composition or structure is appropriate with respect to various characteristics, particularly harmful gas decomposability. For example, in International Publication No. 98/03607, the amount of silica particles relative to the amount of photocatalyst is much less than that of the present invention, and Japanese Patent Application Laid-Open No. 2004-51644 describes the present invention in the addition of a hydrophobic resin. Is different.
本発明者らは、今般、光触媒粒子と無機酸化物粒子とを特定の比率で含み、なおかつ加水分解性シリコーンを含まないかまたは極力少量に抑えた特定の組成で光触媒層を構成することにより、種々の特性、とりわけ良好な有害ガス分解性と、有機基材から生じると思われる成分の浸み出しによる親水性に基づくセルフクリーニング性への悪影響を抑制し、優れた耐候性を発現できるとの知見を得た。 The present inventors now comprise a photocatalyst layer with a specific composition that contains photocatalyst particles and inorganic oxide particles in a specific ratio, and that does not contain hydrolyzable silicone or minimizes the amount as much as possible. Various properties, especially good harmful gas decomposability, and can suppress the adverse effect on the self-cleaning property based on hydrophilicity due to the leaching of components that are supposed to arise from organic base materials, and can exhibit excellent weather resistance Obtained knowledge.
したがって、本発明は、種々の特性、とりわけ有害ガス分解性および長期に亘る光触媒親水性に基づくセルフクリーニング性の維持性と耐候性とに優れた建築用外装材およびその形成のために用いられる建築外装用コーティング液の提供をその目的としている。 Therefore, the present invention provides a building exterior material excellent in various properties, particularly, maintenance of self-cleaning property and weather resistance based on the decomposability of harmful gas and long-term photocatalytic hydrophilicity, and the building used for the formation thereof. Its purpose is to provide exterior coating solutions.
そして、本発明による建築用外装材は、基材と、該基材上に設けられた光触媒層とを備えてなる。光触媒層は、該光触媒層全体を１００質量％としたときに、３質量％を超え５質量％未満の光触媒粒子と、８５質量％を超え９７質量％未満の無機酸化物粒子と、０質量％以上１０質量％未満のバインダーを含んでなる。 And the building exterior material by this invention is equipped with a base material and the photocatalyst layer provided on this base material. The photocatalyst layer has a photocatalyst particle of more than 3% by mass and less than 5% by mass, inorganic oxide particles of more than 85% by mass and less than 97% by mass, and 0% by mass when the entire photocatalyst layer is 100% by mass. More than 10 mass% binder is included.
また、本発明による建築外装用コーティング液は、上記建築用外装材の製造に用いられるものであって、建築外装用コーティング液の乾燥物質量を１００質量％としたときに、溶媒と、３質量％を超え５質量％未満の光触媒粒子と、８５質量％を超え９７質量％未満の無機酸化物粒子と、０質量％以上１０質量％未満のバインダーを含んでなる。 Moreover, the coating liquid for building exteriors according to the present invention is used for the production of the building exterior material described above. When the dry substance amount of the coating liquid for building exteriors is 100% by mass, the solvent and 3% by mass are used. % And less than 5% by mass of photocatalyst particles, more than 85% by mass and less than 97% by mass of inorganic oxide particles, and 0% by mass or more and less than 10% by mass of binder.
本発明による建築用外装材は、基材、特に有機基材への浸食を有効に防止しながら、種々の特性、とりわけ有害ガス分解性および長期に亘る光触媒親水性に基づくセルフクリーニング性の維持および耐候性とに優れる。さらに、本発明の好ましい態様によれば、所望の各種被膜特性（透明性、膜強度等）にも優れた建築用外装材が提供される。 The architectural exterior material according to the present invention is capable of maintaining self-cleaning properties based on various characteristics, particularly harmful gas decomposability and long-term photocatalytic hydrophilicity, while effectively preventing the erosion of the base material, particularly the organic base material. Excellent weather resistance. Furthermore, according to the preferable aspect of this invention, the exterior material for buildings excellent also in various desired film characteristics (transparency, film | membrane strength, etc.) is provided.
建築用外装材
本発明の一形態によれば、建築用外装材は、基材と、該基材上に設けられた光触媒層とを備えてなる。光触媒層は、該光触媒層全体を１００質量％としたときに、３．０質量％を超え５．０質量％未満の光触媒粒子と、８５．０質量％を超え９７．０質量％未満の無機酸化物粒子と、０質量％以上１０．０質量％未満のバインダーを含んでなる。
Architectural Exterior Material According to one aspect of the present invention, an architectural exterior material includes a base material and a photocatalyst layer provided on the base material. The photocatalyst layer has a photocatalyst particle of more than 3.0% by mass and less than 5.0% by mass, and an inorganic compound of more than 85.0% by mass and less than 97.0% by mass when the entire photocatalyst layer is 100% by mass. It comprises oxide particles and a binder of 0% by mass or more and less than 10.0% by mass.
本発明による光触媒層は、従来、光触媒塗装体に対して一般的に必要と認識されてきた光触媒の量、さらには無機酸化物粒子に対する量に比較して、かなり少ない光触媒量を含んでなる。このような少ない光触媒量により、光触媒と基材との直接的な接触を抑えることができ、それにより基材の分解または浸食が有効に抑制されると考えられる。一方で、高い耐候性が実現されながら、光触媒活性、とりわけ有害ガス分解性は、光触媒量が少ない量にもかかわらず、維持されあるいはむしろ改善が図られており、このことは当業者にとり意外な事実であるといえる。さらに本発明者らの得た知見によれば、光触媒塗装体の劣化には、基材である有機材料から、光触媒の作用または紫外線の作用による分解産物、例えば高分子が分解されたモノマー成分が少なからず影響していた。特に、この成分が疎水性の成分であると、光触媒塗装体の親水性の発現にも悪影響をあたえる。本発明の光触媒塗装体によれば、この基材から浸みだした成分の影響を抑え、優れた光触媒親水性能を長期に亘り維持できる。
すなわち、透明意匠を含めた意匠パネル等の外装材において、長期に亘り有害ガス分解性が維持されるとともに意匠上の色落ち等の意匠変化に代表される外観上の変化も呈しにくくなる。
The photocatalyst layer according to the present invention comprises a photocatalyst amount that is considerably smaller than the amount of photocatalyst that has been generally recognized to be generally necessary for a photocatalyst-coated body, and further to the amount of inorganic oxide particles. By such a small amount of photocatalyst, direct contact between the photocatalyst and the substrate can be suppressed, and it is considered that decomposition or erosion of the substrate is effectively suppressed. On the other hand, photocatalytic activity, particularly harmful gas decomposability, is maintained or rather improved despite the low amount of photocatalyst, while high weather resistance is achieved, which is surprising to those skilled in the art. It can be said that it is a fact. Furthermore, according to the knowledge obtained by the present inventors, the degradation of the photocatalyst-coated body is caused by degradation products such as a monomer component obtained by decomposing a polymer, such as a photocatalyst or an ultraviolet ray, from an organic material as a base material. It had a considerable influence. In particular, if this component is a hydrophobic component, the hydrophilicity of the photocatalyst-coated body is also adversely affected. According to the photocatalyst-coated body of the present invention, it is possible to suppress the influence of the component that has oozed out from the base material and maintain excellent photocatalytic hydrophilic performance over a long period of time.
That is, in exterior materials such as design panels including transparent designs, harmful gas decomposability is maintained over a long period of time, and changes in appearance typified by design changes such as color fading on designs are less likely to occur.
本発明による建築用外装材の上述のような意外な作用効果が得られる理由は定かではないが、それは以下の通りと考えられる。しかし、以下の説明はあくまで仮説であり、本発明はこれにより何ら限定されるものではない。 The reason why the above-described unexpected effects of the building exterior material according to the present invention can be obtained is not clear, but it is considered as follows. However, the following explanation is only a hypothesis, and the present invention is not limited by this.
まず、本発明において光触媒層は、光触媒粒子および無機酸化物粒子の二種類の粒子から基本的に構成されるため、粒子間の隙間が豊富に存在する。光触媒層のバインダーとして広く用いられる加水分解性シリコーンを多量に使用した場合にはそのような粒子間の隙間を緻密に埋めてしまうため、ガスの拡散を妨げるものと考えられる。本発明において光触媒層は加水分解性シリコーンを含まないか、含むとしても該光触媒層全体を１００質量％としたときに、その量に対して少ない量であるため、粒子間の隙間を十分に確保することができる。そして、この隙間によってＮＯｘやＳＯｘ等の有害ガスが光触媒層中に拡散しやすい構造が実現され、その結果、有害ガスが光触媒粒子と効率良く接触して光触媒活性により分解されるのではないかと考えられる。さらに、光触媒層に存在する光触媒量が、基材からの浸みだし成分を効率よく分解しているものと思われ、光触媒親水性能を長期に亘り維持できるものと考えられる。 First, in the present invention, since the photocatalyst layer is basically composed of two types of particles, photocatalyst particles and inorganic oxide particles, there are abundant gaps between the particles. When a large amount of hydrolyzable silicone widely used as a binder for the photocatalyst layer is used, the gaps between the particles are densely filled, which is considered to hinder gas diffusion. In the present invention, the photocatalyst layer does not contain hydrolyzable silicone, or even if it contains it, the total amount of the photocatalyst layer is 100% by mass. can do. This gap realizes a structure in which harmful gases such as NOx and SOx are easily diffused into the photocatalyst layer, and as a result, the harmful gas is efficiently contacted with the photocatalyst particles and decomposed by the photocatalytic activity. It is done. Furthermore, it is considered that the amount of photocatalyst present in the photocatalyst layer efficiently decomposes the components oozing out from the base material, and it is considered that the photocatalytic hydrophilic performance can be maintained over a long period of time.
上記のような作用効果および特性ゆえ、本発明による建築用外装材は、特に低緯度の熱帯、亜熱帯地方などの紫外線量が多く、かつ高温・多湿の気象条件下においても、優れた光触媒分解機能に基づく有害ガス除去機能および光触媒親水機能に基づくセルフクリーニング機能を長期に亘り発揮することが可能である。 Due to the effects and characteristics as described above, the building exterior material according to the present invention has a high photocatalytic decomposition function even under high-temperature and high-humidity weather conditions, especially in the low-latitude tropical and subtropical regions. The self-cleaning function based on the harmful gas removing function based on the photocatalyst and the photocatalytic hydrophilic function can be exhibited over a long period of time.
基材
本発明において、基材はその表面が有機物質を含む樹脂を含有しているのが好ましい。
特に、アクリル成形体、ポリカーボネート成形体等の樹脂成形体やエナメル塗装やクリア塗装を有する塗装板、意匠性フィルムを有する積層板等が好適に利用できる。
Substrate In the present invention, the substrate preferably contains a resin whose surface contains an organic substance.
In particular, resin molded bodies such as acrylic molded bodies and polycarbonate molded bodies, coated plates having enamel coating or clear coating, laminated plates having designable films, and the like can be suitably used.
用途の観点からみた基材の好ましい例としては、外壁材、屋根材、雨樋、窓枠及び上記物品表面に貼着させるためのフィルム、シート、シール等といった外装材全般が挙げられる。 Preferable examples of the base material from the viewpoint of the application include exterior wall materials, roofing materials, rain gutters, window frames, and general exterior materials such as films, sheets, seals and the like for attaching to the surface of the article.
本発明の好ましい態様によれば、基材は、基材の表面が、有機物質を含む樹脂を含有しているのが好ましい。基材全体が有機材料で構成されているものであってもよく、また無機材料で構成された基材の表面が有機材料で被覆されたもの（例えば化粧板）であってもよい。さらに、有機材料を含む樹脂以外に無機顔料や無機質の体質顔料等が添加されていてもよい。本発明による建築用外装材は、光触媒活性により損傷を受けやすい有機材料を浸食し難いものであることから、中間層を介在させることなく、光触媒層という一つの層で優れた機能を有する建築用外装材を製造することができる。 According to a preferred aspect of the present invention, it is preferable that the base material contains a resin containing an organic substance on the surface of the base material. The whole substrate may be composed of an organic material, or the surface of a substrate composed of an inorganic material may be coated with an organic material (for example, a decorative board). Furthermore, in addition to the resin containing an organic material, an inorganic pigment, an inorganic extender pigment, or the like may be added. The architectural exterior material according to the present invention is difficult to erode organic materials that are easily damaged by photocatalytic activity, and therefore has an excellent function in a single layer called a photocatalytic layer without interposing an intermediate layer. An exterior material can be manufactured.
従来、光触媒塗装体にあっては、光触媒層の光触媒活性による基材への影響を、シリコーン系樹脂からなる層を基材との間に設けることで抑えることが一般的に行われてきた。本発明によれば、このような従来一般的に設けられてきたシリコーン系樹脂ではなく、有機材料からなる基材に直接光触媒層を設けることが出来る。その結果、本発明は、その利用、適用範囲が大きく拡大されるとの点で極めて有利となる。 Conventionally, in a photocatalyst-coated body, it has been generally performed to suppress the influence on the base material due to the photocatalytic activity of the photocatalyst layer by providing a layer made of a silicone resin between the base material and the base material. According to the present invention, the photocatalyst layer can be directly provided on a base material made of an organic material, instead of the silicone resin which has been generally provided conventionally. As a result, the present invention is extremely advantageous in that its use and application range are greatly expanded.
建築用外装材の光触媒層
本発明の一形態によれば、光触媒層は、該光触媒層全体を１００質量％としたときに、３．０質量％を超え５．０質量％未満の光触媒粒子と、８５．０質量％を超え９７．０質量％未満の無機酸化物粒子と、０質量％以上１０．０質量％未満のバインダーを含んでなる。
本発明の好ましい態様によれば、光触媒粒子を３．１質量％以上４．９質量％以下、無機酸化物粒子を８５．１質量％以上９６．９質量％以下としてなるものが好ましい。
Photocatalyst layer of building exterior material According to one embodiment of the present invention, the photocatalyst layer comprises a photocatalyst particle of more than 3.0% by mass and less than 5.0% by mass when the entire photocatalyst layer is 100% by mass. , 85.0% by mass and less than 97.0% by mass of inorganic oxide particles, and 0% by mass or more and less than 10.0% by mass of binder.
According to a preferred embodiment of the present invention, it is preferable that the photocatalyst particles are 3.1% by mass to 4.9% by mass and the inorganic oxide particles are 85.1% by mass to 96.9% by mass.
本発明の好ましい態様によれば、光触媒層は０．５μｍ以上３μｍ以下の膜厚を有するのが好ましい。より好ましい膜厚の範囲は０．５μｍ以上３．０μｍ以下であり、さらに好ましくは１．０μｍ以上２．０μｍ以下である。このような範囲内であると、光触媒層と基材の界面に到達する紫外線が充分に減衰されるので耐候性が向上する。また、無機酸化物粒子よりも含有比率が低い光触媒粒子を膜厚方向に増加させることができるので、有害ガス分解性も向上する。さらには、透明性、膜強度においても優れた特性が得られる。 According to a preferred embodiment of the present invention, the photocatalyst layer preferably has a film thickness of 0.5 μm or more and 3 μm or less. A more preferable range of the film thickness is 0.5 μm or more and 3.0 μm or less, and further preferably 1.0 μm or more and 2.0 μm or less. Within such a range, the ultraviolet rays that reach the interface between the photocatalyst layer and the substrate are sufficiently attenuated, thereby improving the weather resistance. Moreover, since the photocatalyst particles having a lower content ratio than the inorganic oxide particles can be increased in the film thickness direction, harmful gas decomposability is also improved. Furthermore, excellent characteristics can be obtained in terms of transparency and film strength.
本発明に用いる光触媒粒子は、光触媒活性を有する粒子であれば特に限定されないが、その好ましい例としては、酸化チタン（ＴｉＯ２）、ＺｎＯ、ＳｎＯ２、ＳｒＴｉＯ３、ＷＯ３、Ｂｉ２Ｏ３、Ｆｅ２Ｏ３のような金属酸化物の粒子が挙げられ、より好ましくは酸化チタン粒子、最も好ましくはアナターゼ型酸化チタン粒子である。また、酸化チタンはバンドギャップエネルギーが高く、従って、光励起には紫外線を必要とし、光励起の過程で可視光を吸収しないので、補色成分による発色が起こらない点で有利である。酸化チタンは、粉末状、ゾル状、溶液状など様々な形態で入手可能であるが、光触媒活性を示すものであれば、いずれの形態でも使用可能である。 The photocatalyst particles used in the present invention are not particularly limited as long as the particles have photocatalytic activity. Preferred examples thereof include titanium oxide (TiO 2 ), ZnO, SnO 2 , SrTiO 3 , WO 3 , Bi 2 O 3 , Examples thereof include metal oxide particles such as Fe 2 O 3 , more preferably titanium oxide particles, and most preferably anatase-type titanium oxide particles. Titanium oxide is advantageous in that it has a high band gap energy and therefore requires ultraviolet light for photoexcitation and does not absorb visible light in the process of photoexcitation, so that no color formation due to complementary color components occurs. Titanium oxide is available in various forms such as powder, sol, and solution, but any form can be used as long as it exhibits photocatalytic activity.
本発明の好ましい態様によれば、光触媒粒子は１０ｎｍ以上１００ｎｍ以下の平均粒径を有するのが好ましく、より好ましくは１０ｎｍ以上６０ｎｍ以下である。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が好ましいが、略円形や楕円形でもよく、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 According to a preferred embodiment of the present invention, the photocatalyst particles preferably have an average particle diameter of 10 nm to 100 nm, more preferably 10 nm to 60 nm. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. The shape of the particle is preferably a true sphere, but may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
本発明に用いる無機酸化物粒子は、光触媒粒子と共に層を形成可能な無機酸化物の粒子であれば特に限定されず、その好ましい例としては、シリカ、アルミナ、ジルコニア、セリア、イットリア、ボロニア、マグネシア、カルシア、フェライト、無定型チタニア、ハフニア等の単一酸化物の粒子；およびチタン酸バリウム、ケイ酸カルシウム等の複合酸化物の粒子が挙げられ、より好ましくはシリカ粒子である。 The inorganic oxide particles used in the present invention are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with photocatalyst particles. Preferred examples thereof include silica, alumina, zirconia, ceria, yttria, boronia, magnesia. Single oxide particles such as calcia, ferrite, amorphous titania and hafnia; and composite oxide particles such as barium titanate and calcium silicate, and more preferably silica particles.
本発明の無機酸化物粒子は、平均粒径が５ｎｍを超え１００ｎｍ以下であることが好ましく、より好ましくは１０ｎｍ以上５０ｎｍ以下である。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も良いが、略円形や楕円形でも良く、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 The average particle diameter of the inorganic oxide particles of the present invention is preferably more than 5 nm and not more than 100 nm, more preferably not less than 10 nm and not more than 50 nm. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. As the shape of the particle, a true sphere is the best, but it may be approximately circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
本発明の光触媒層は、加水分解性シリコーンの乾燥物、加水分解性シランの乾燥物、無定形の無機酸化物、樹脂バインダー、アルカリシリケートの群から選ばれる少なくとも１種のバインダーを含むことができ、これらの物質はバインダーとして光触媒層の強度向上に寄与する。しかしながら、場合によって、その存在が光触媒活性の発現または有害ガス分解性に有利な間隙の形成に影響を与えることがある。従って、本発明にあっては、有害ガス分解性を確保できる程度であれば上記バインダーを任意成分として含有することは許容されるが、またその添加は控えるまたは少量とすることが好ましい。場合により全く含まないことが好ましい。具体的には、上記バインダー成分の含有量は、該光触媒層全体を１００質量％としたときに、０質量％以上１０．０質量％未満であり、好ましくは５．０質量％以下、最も好ましくは０質量％である。 The photocatalyst layer of the present invention can contain at least one binder selected from the group consisting of dried hydrolyzable silicone, dried hydrolyzable silane, amorphous inorganic oxide, resin binder, and alkali silicate. These substances contribute to improving the strength of the photocatalytic layer as a binder. However, in some cases, its presence can affect the formation of a gap that favors the development of photocatalytic activity or decomposability of harmful gases. Therefore, in the present invention, it is acceptable to contain the binder as an optional component as long as harmful gas decomposability can be secured, but it is preferable to refrain from adding it or to make it a small amount. It is preferable not to contain at all depending on the case. Specifically, the content of the binder component is 0% by mass or more and less than 10.0% by mass, preferably 5.0% by mass or less, most preferably when the entire photocatalyst layer is 100% by mass. Is 0% by mass.
ここで、加水分解性シリコーン及び／又は加水分解性シランとしては、４官能シリコーン化合物及び／又は４官能シランがよく使用され、例えば、エチルシリケート４０（オリゴマー、Ｒがエチル基）、エチルシリケート４８（オリゴマー、Ｒがエチル基）メチルシリケート５１（オリゴマー、Ｒがメチル基）（いずれもコルコート社製）、テトラメトキシシラン、テトラエトキシシラン、ジメトキシジエトキシシランの形で市販されている。これらの加水分解性シリコーン及び／又は加水分解性シランは、建築外装用コーティング液を塗布後、乾燥に伴い縮合が進み、乾燥物となる。 Here, as the hydrolyzable silicone and / or hydrolyzable silane, a tetrafunctional silicone compound and / or a tetrafunctional silane is often used. For example, ethyl silicate 40 (oligomer, R is an ethyl group), ethyl silicate 48 ( Oligomer, R is ethyl group) Methyl silicate 51 (oligomer, R is methyl group) (all manufactured by Colcoat Co.), tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane are commercially available. These hydrolyzable silicones and / or hydrolyzable silanes are dried after being applied with the coating liquid for building exteriors, resulting in a dry product.
上述したように、加水分解性シランモノマーとしては、テトラアルコキシシラン等の４官能性のシランモノマーが親水機能の面から好ましいが、トリアルコキシオルガノシラン等の３官能性モノマーやジアルコキシジオルガノシラン等の２官能性モノマーも利用できる。加水分解性シリコーンとしてもテトラアルコキシシラン等の４官能性のシランモノマーの加水分解・縮重合物が親水機能の面から好ましいが、２〜４官能加水分解性シラン単位を少なくとも１つ含む加水分解・縮重合物であれば好適に利用できる。 As described above, as the hydrolyzable silane monomer, a tetrafunctional silane monomer such as tetraalkoxysilane is preferable from the viewpoint of hydrophilic function, but a trifunctional monomer such as trialkoxyorganosilane, dialkoxydiorganosilane, etc. These bifunctional monomers can also be used. The hydrolyzable silicone is preferably a hydrolyzed / condensed product of a tetrafunctional silane monomer such as tetraalkoxysilane from the viewpoint of the hydrophilic function. However, the hydrolyzable silicone containing at least one 2- to 4-functional hydrolyzable silane unit is preferable. Any condensation polymer can be suitably used.
ここで、無定形の無機酸化物としては、粒子形状を伴わない無定形酸化チタン、無定形シリカ、無定形アルミナ等が好適に利用可能である。 Here, as the amorphous inorganic oxide, amorphous titanium oxide, amorphous silica, amorphous alumina, or the like without any particle shape can be suitably used.
また、樹脂バインダーとしては、フッ素樹脂バインダー、シリコーン変性アクリルバインダー、シリコーン変性エポキシバインダー、シリコーン変性ウレタンバインダー、シリコーン変性ポリエステルバインダー等の耐候性の強いバインダーが好ましいが、場合によっては、アクリルバインダー、エポキシバインダー等も利用可能である。 Further, as the resin binder, a binder having strong weather resistance such as a fluororesin binder, a silicone-modified acrylic binder, a silicone-modified epoxy binder, a silicone-modified urethane binder, and a silicone-modified polyester binder is preferable. Etc. are also available.
樹脂バインダーの一形態として樹脂エマルジョン重合体が好適に利用できる。樹脂エマルジョン重合体としても、シリコーンエマルジョン重合体、フッ素樹脂エマルジョン重合体、アクリルシリコーンエマルジョン重合体、シリコーン変性エマルジョン重合体、シリコーン変性ウレタンエマルジョン重合体、シリコーン変性ポリエステルエマルジョン重合体等の耐候性の強い重合体が好ましいが、場合によっては、アクリルエマルジョン重合体等も利用可能である。 A resin emulsion polymer can be suitably used as one form of the resin binder. As the resin emulsion polymer, a highly weatherable heavy polymer such as a silicone emulsion polymer, a fluororesin emulsion polymer, an acrylic silicone emulsion polymer, a silicone modified emulsion polymer, a silicone modified urethane emulsion polymer, a silicone modified polyester emulsion polymer, etc. The coalescence is preferable, but an acrylic emulsion polymer or the like can be used in some cases.
アルカリシリケートとしては、例えば、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸リチウム等が好適に利用できる。 As the alkali silicate, for example, sodium silicate, potassium silicate, lithium silicate and the like can be suitably used.
さらに、本発明の光触媒層には、バナジウム、鉄、コバルト、ニッケル、パラジウム、亜鉛、ルテニウム、ロジウム、銅、銀、白金および金からなる群より選ばれる少なくとも一種の金属又は金属化合物を添加することにより、さらに高い抗菌・防カビ性能を発現させることができる。ただし、その存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましく、従って、その添加量は微量でよく、またその作用の発現に必要な量は微量である。具体的には、光触媒に対して、０．０１〜１０質量％、より好ましくは０．０５〜５質量％程度の添加量が好ましい。また、金属化合物としては、例えば、上記金属のグルコン酸塩、硫酸塩、リンゴ酸塩、乳酸塩、硫酸塩、硝酸塩、ギ酸塩、酢酸塩、キレート等が好適に利用できる。 Furthermore, at least one metal or metal compound selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold is added to the photocatalyst layer of the present invention. Therefore, higher antibacterial / antifungal performance can be expressed. However, it is desirable that the presence thereof does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles, and therefore, the addition amount may be a very small amount and is an amount necessary for the expression of the action. Is a trace amount. Specifically, an addition amount of about 0.01 to 10% by mass, more preferably about 0.05 to 5% by mass is preferable with respect to the photocatalyst. As the metal compound, for example, gluconates, sulfates, malates, lactates, sulfates, nitrates, formates, acetates, chelates and the like of the above metals can be suitably used.
本発明の光触媒層には、光触媒粒子と、無機酸化物粒子と、任意成分としてのバインダーと、に加えてさらに、難水溶性又は非水溶性の無機塩や樹脂粒子が含有されて良く、その添加量は、該光触媒層全体を１００質量％としたときに、０質量％以上１０質量％未満であり、好ましくは５質量％以下、最も好ましくは０質量％で含有されていてもよい。ただし、 その存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましい。 In addition to the photocatalyst particles, the inorganic oxide particles, and the binder as an optional component, the photocatalyst layer of the present invention may further contain a hardly water-soluble or water-insoluble inorganic salt or resin particle, The addition amount may be 0% by mass or more and less than 10% by mass, preferably 5% by mass or less, and most preferably 0% by mass when the entire photocatalyst layer is 100% by mass. However, it is desirable that the presence does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles.
難水溶性又は非水溶性の無機塩としては、例えば、水酸化アルミニウム、ベーマイト、炭酸カルシウム等が好適に利用できる。 As the hardly water-soluble or water-insoluble inorganic salt, for example, aluminum hydroxide, boehmite, calcium carbonate and the like can be suitably used.
樹脂粒子としては、球状、板状等の粒子を利用することで意匠上艶調整が可能な場合があり、光触媒性能や耐候性を妨げない範囲での添加が可能である。 As the resin particles, there are cases where the gloss can be adjusted by design using spherical or plate-like particles, and the addition can be made within a range not impeding the photocatalytic performance and weather resistance.
その他、本発明の光触媒層には、光触媒粒子と、無機酸化物粒子と、任意成分としてのバインダーと、に加えてさらに、紫外線遮蔽剤や有機防カビ剤等が添加されていても良く、その添加量は、該光触媒層全体を１００質量％としたときに、０質量％以上１０質量％未満であり、好ましくは５質量％以下、最も好ましくは０質量％で含有されていてもよい。ただし、その存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましい。 In addition, in addition to the photocatalyst particles, the inorganic oxide particles, and the optional binder, the photocatalyst layer of the present invention may further contain an ultraviolet shielding agent, an organic antifungal agent, etc. The addition amount may be 0% by mass or more and less than 10% by mass, preferably 5% by mass or less, and most preferably 0% by mass when the entire photocatalyst layer is 100% by mass. However, it is desirable that the presence does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles.
本発明では、建築用外装材に設けられた光触媒層表面に１ｍＷ／ｃｍ２に調整したＢＬＢ光（輝線スペクトルの波長が３５１ｎｍのものを使用）下に光触媒塗装面を上にして８日間放置した後の、前記光触媒塗装面の表面の水との接触角が２０°未満であることが好ましい。そうすることで、長期に亘り安定的に、低緯度の熱帯、亜熱帯地方などの紫外線量が多くかつ高温・多湿の気象条件下においても、優れた光触媒親水機能に基づくセルフクリーニング機能を発揮することが可能である。 In the present invention, the surface of the photocatalyst layer provided on the building exterior material is left for 8 days with the photocatalyst coating surface facing up under BLB light adjusted to 1 mW / cm 2 (the wavelength of the emission line spectrum is 351 nm). It is preferable that the later contact angle with water on the surface of the photocatalyst coating surface is less than 20 °. By doing so, a self-cleaning function based on an excellent photocatalytic hydrophilic function can be demonstrated over a long period of time, even under high-temperature, high-humidity weather conditions such as low latitudes in the tropics and subtropics. Is possible.
本発明の光触媒層中の空隙率は、２０体積％以上３５体積％以下が好ましい。
空隙率は、大塚電子株式会社製の反射分光膜厚計：FE-3000を用いて１試料当たり５点以上、好ましくは１０点以上測定しその平均値を求める。基材にガラス板を用い、光触媒層の形成成分がTiO2およびSiO2の場合における空隙率の測定手順を以下に示す。
手順１．ガラス板の屈折率決定
１−１．ガラス板の波長230〜800nmにおける反射率を以下の条件で計測する。
測定手法 絶対反射率
レンズ Refrec.25X
標準反射板 Al-S-13
フィルター なし
スリット 0．2mm×2mm
サンプリングタイム 1000msec
積算回数 9回
ゲイン ノーマル
１−２．ガラス板の波長230〜800nmにおける反射率を、構成媒質＝空気、ガラス板、光の入射角φ＝０°とし、空気側から入射した光をガラス板で反射させた時の空気／ガラス板界面でのフレネル振幅反射係数と、n-Cauchyの分散式［nm=Cm1+Cm2/λ2+Cm3/λ4（ただし、nmはガラス板の屈折率、λは波長、Cm1、Cm2、Cm3は定数）］により算出する。なお、n-Cauchyの分散式においては、定数（Cm1、Cm2、Cm3）の初期値をそれぞれ、Cm1＝1.5、Cm2＝0、Cm3＝0とし、空気の屈折率を1、空気の消衰係数を0とする（小檜山光信，“光学薄膜の基礎理論”p1〜70， (2003， オプトロニクス社)）。
１−３．実測反射率（1-1）と計算反射率（1-2）を比較し、二乗残差の和が最小になる時のCm1、Cm2、Cm3を求めた。その際、二乗残差の和の上限を0.02とする。
１−４．１−３で求めたCm1、Cm2、Cm3をn-Cauchyの分散式に代入し、ガラス板の屈折率nmを決定する。
手順２．光触媒層の空隙率の決定
２−１．光触媒層の波長230〜800nmにおける反射率を以下の条件で計測する。
測定手法 絶対反射率
レンズ Refrec.25X
標準反射板 Al-S-13
フィルター なし
スリット 0．2mm×2mm
サンプリングタイム 1000msec
積算回数 9回
ゲイン ノーマル
２−２．構成媒質＝空気、光触媒層＝単層薄膜、ガラス板、光の入射角φ＝０°とし、空気側から入射した光を単層薄膜で反射した光と、単層薄膜内部に透過した光が単層薄膜の上下面（空気／単層薄膜界面、単層薄膜／ガラス板界面）で多重繰り返し反射した光を合計した時の空気／単層薄膜界面でのフレネル振幅反射係数と、Bruggemanの近似式
［C1{(ε1-ε)/(ε1+2ε)}+C2{(ε2-ε)/(ε2+2ε)}+C3{(ε3-ε)/(ε3+2ε)}=0、C1+C2+C3=1、（ただし、εは単層薄膜の誘電率、ε1はSiO2の誘電率、ε2はTiO2の誘電率、ε3は空気の誘電率、C1はSiO2の体積分率、C2はTiO2の体積分率、C3は空気の体積分率）］により、光触媒層の波長230〜800nmにおける反射率を算出する（小檜山光信，“光学薄膜の基礎理論”p1〜70， (2003， オプトロニクス社、D. E. Aspnes， Thin Solid Films， 89， 249 (1982))。
なお、C1（SiO2の体積分率）、C2（TiO2の体積分率）、C3（空気の体積分率）の初期値は、それぞれ、二乗残差の和が最小値に収束するような値を設定する。また、空気の屈折率を1とし、空気の消衰係数を0とする。SiO2、TiO2の屈折率（n1、n2）、消衰係数（k1、k2）は、E. D. Palik ， “Handbook of Optical Constants of Solids”， (1998， Academic Press， San Diego)より引用する。
２−３．膜厚d、SiO2、TiO2、空気の体積分率C1、C2、C3の値を変えながら実測反射率（2-1）と計算反射率（2-2）を比較し、二乗残差の和が最小になった時のC1、C2、C3を求める。二乗残差の和が0.02未満、かつ最小となった時のC3を空隙率として採用する。その他の条件は以下の通りである。
膜厚検索方法 最適化法
検索範囲（波長） 400〜800nm
検索範囲（膜厚） 0〜2000nm
膜厚ステップ 10nm
ここで求めたＣ３を本発明の光触媒層中の空隙率（体積％）とする。
The porosity in the photocatalyst layer of the present invention is preferably 20% by volume to 35% by volume.
The porosity is measured at 5 points or more, preferably 10 points or more per sample using a reflective spectral film thickness meter: FE-3000 manufactured by Otsuka Electronics Co., Ltd., and the average value is obtained. The procedure for measuring the porosity in the case where a glass plate is used as the substrate and the photocatalyst layer forming components are TiO 2 and SiO 2 is shown below.
Procedure 1. Determination of refractive index of glass plate 1-1. The reflectance of the glass plate at a wavelength of 230 to 800 nm is measured under the following conditions.
Measurement method Absolute reflectance Lens Refrec.25X
Standard reflector Al-S-13
No filter Slit 0. 2mm x 2mm
Sampling time 1000msec
Integration count 9 times Gain Normal 1-2. The air / glass plate interface when the reflectivity of the glass plate at a wavelength of 230 to 800 nm is configured medium = air, glass plate, light incident angle φ = 0 °, and light incident from the air side is reflected by the glass plate. Fresnel amplitude reflection coefficient and n-Cauchy dispersion equation [n m = C m1 + C m2 / λ 2 + C m3 / λ 4 (where n m is the refractive index of the glass plate, λ is the wavelength, C m1 , C m2 and C m3 are constants)]. In the n-Cauchy dispersion formula, the initial values of the constants (C m1 , C m2 , C m3 ) are C m1 = 1.5, C m2 = 0, C m3 = 0, and the refractive index of air is 1. The extinction coefficient of air is assumed to be 0 (Mitsunobu Koyama, “Basic theory of optical thin film” p1 to 70, (2003, Optronics)).
1-3. The measured reflectance (1-1) and the calculated reflectance (1-2) were compared, and C m1 , C m2 , and C m3 when the sum of the squared residuals was minimized were obtained. At that time, the upper limit of the sum of squared residuals is set to 0.02.
The C m1, C m2, C m3 obtained in 1-4.1-3 substituted into the dispersion equation n-Cauchy, to determine the refractive index n m of the glass plate.
Procedure 2. 2. Determination of porosity of photocatalyst layer 2-1. The reflectance at a wavelength of 230 to 800 nm of the photocatalyst layer is measured under the following conditions.
Measurement method Absolute reflectance Lens Refrec.25X
Standard reflector Al-S-13
No filter Slit 0. 2mm x 2mm
Sampling time 1000msec
Integration count 9 times Gain Normal 2-2. Constituent medium = air, photocatalyst layer = single layer thin film, glass plate, light incident angle φ = 0 °, light incident from the air side reflected by the single layer thin film, and light transmitted inside the single layer thin film Fresnel amplitude reflection coefficient at the air / single-layer thin film interface and the approximation of Bruggeman when the light repeatedly reflected by the upper and lower surfaces of the single-layer thin film (air / single layer thin film interface, single layer thin film / glass plate interface) is summed Formula [C 1 {(ε 1 -ε) / (ε 1 + 2ε)} + C 2 {(ε 2 -ε) / (ε 2 + 2ε)} + C 3 {(ε 3 -ε) / (ε 3 + 2ε)} = 0, C 1 + C 2 + C 3 = 1 (where ε is the dielectric constant of the single layer thin film, ε 1 is the dielectric constant of SiO 2 , ε 2 is the dielectric constant of TiO 2 , ε 3 is the dielectric constant of air, C 1 is the volume fraction of SiO 2 , C 2 is the volume fraction of TiO 2 , and C 3 is the volume fraction of air)] Calculate (Mitsunobu Koyama, “Basic Theory of Optical Thin Films” p1-70, (2003, Optronics, DE Aspnes, Thin Solid Films, 89 , 249 (1982)).
The initial values of C 1 (SiO 2 volume fraction), C 2 (TiO 2 volume fraction), and C 3 (air volume fraction) converge to the minimum sum of squared residuals, respectively. Set the value to be Also, the refractive index of air is 1, and the extinction coefficient of air is 0. Refractive indices (n 1 , n 2 ) and extinction coefficients (k 1 , k 2 ) of SiO 2 and TiO 2 are from ED Palik, “Handbook of Optical Constants of Solids” (1998, Academic Press, San Diego). Quote.
2-3. Compare the measured reflectance (2-1) and calculated reflectance (2-2) while changing the values of film thickness d, SiO 2 , TiO 2 , and air volume fractions C 1 , C 2 , C 3 , and square Find C 1 , C 2 , and C 3 when the sum of residuals is minimized. C 3 when the sum of squared residuals is less than 0.02 and minimum is adopted as the porosity. Other conditions are as follows.
Film thickness search method Optimization method Search range (wavelength) 400-800nm
Search range (film thickness) 0 ~ 2000nm
Film thickness step 10nm
The C 3 obtained here and the porosity of the photocatalyst layer of the present invention (% by volume).
建築外装用コーティング液
本発明の他の形態によれば、建築外装用コーティング液は、上述の本発明による建築用外装材の形成のために使用するものであり、建築外装用コーティング液の乾燥物質量を１００質量％としたときに、溶媒と、３．０質量％を超え５．０質量％未満の光触媒粒子と、８５．０質量％を超え９７．０質量％未満の無機酸化物粒子と、０質量％以上１０．０質量％未満のバインダーを含んでなる。
Architectural Exterior Coating Liquid According to another aspect of the present invention, an architectural exterior coating liquid is used for forming the above-described architectural exterior material according to the present invention, and is a dry substance of the architectural exterior coating liquid. When the amount is 100% by mass, a solvent, photocatalyst particles of more than 3.0% by mass and less than 5.0% by mass, inorganic oxide particles of more than 85.0% by mass and less than 97.0% by mass, The binder comprises 0% by mass or more and less than 10.0% by mass.
本発明の好ましい態様によれば、光触媒粒子を３．１質量％以上４．９質量％以下、前記無機酸化物粒子を８５．１質量％以上９６．９質量％以下としてなる組成がさらに好ましい。 According to a preferred embodiment of the present invention, a composition in which the photocatalyst particles are 3.1% by mass to 4.9% by mass and the inorganic oxide particles are 85.1% by mass to 96.9% by mass is more preferable.
本発明に用いる光触媒粒子は、光触媒活性を有する粒子であれば特に限定されないが、その好ましい例としては、酸化チタン（ＴｉＯ２）、ＺｎＯ、ＳｎＯ２、ＳｒＴｉＯ３、ＷＯ３、Ｂｉ２Ｏ３、Ｆｅ２Ｏ３のような金属酸化物の粒子が挙げられ、より好ましくは酸化チタン粒子、最も好ましくはアナターゼ型酸化チタン粒子である。また、酸化チタンはバンドギャップエネルギーが高く、従って、光励起には紫外線を必要とし、光励起の過程で可視光を吸収しないので、補色成分による発色が起こらない点で有利である。酸化チタンは、粉末状、ゾル状、溶液状など様々な形態で入手可能であるが、光触媒活性を示すものであれば、いずれの形態でも使用可能である。 The photocatalyst particles used in the present invention are not particularly limited as long as the particles have photocatalytic activity. Preferred examples thereof include titanium oxide (TiO 2 ), ZnO, SnO 2 , SrTiO 3 , WO 3 , Bi 2 O 3 , Examples thereof include metal oxide particles such as Fe 2 O 3 , more preferably titanium oxide particles, and most preferably anatase-type titanium oxide particles. Titanium oxide is advantageous in that it has a high band gap energy and therefore requires ultraviolet light for photoexcitation and does not absorb visible light in the process of photoexcitation, so that no color formation due to complementary color components occurs. Titanium oxide is available in various forms such as powder, sol, and solution, but any form can be used as long as it exhibits photocatalytic activity.
本発明の好ましい態様によれば、光触媒粒子は１０ｎｍ以上１００ｎｍ以下の平均粒径を有するのが好ましく、より好ましくは１０ｎｍ以上６０ｎｍ以下である。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が好ましいが、略円形や楕円形でもよく、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 According to a preferred embodiment of the present invention, the photocatalyst particles preferably have an average particle diameter of 10 nm to 100 nm, more preferably 10 nm to 60 nm. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. The shape of the particle is preferably a true sphere, but may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
本発明に用いる無機酸化物粒子は、光触媒粒子と共に層を形成可能な無機酸化物の粒子であれば特に限定されず、その好ましい例としては、シリカ、アルミナ、ジルコニア、セリア、イットリア、ボロニア、マグネシア、カルシア、フェライト、無定型チタニア、ハフニア等の単一酸化物の粒子；およびチタン酸バリウム、ケイ酸カルシウム等の複合酸化物の粒子が挙げられ、より好ましくはシリカ粒子である。 The inorganic oxide particles used in the present invention are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with photocatalyst particles. Preferred examples thereof include silica, alumina, zirconia, ceria, yttria, boronia, magnesia. Single oxide particles such as calcia, ferrite, amorphous titania and hafnia; and composite oxide particles such as barium titanate and calcium silicate, and more preferably silica particles.
本発明の無機酸化物粒子は、平均粒径が５ｎｍを超え１００ｎｍ以下であることが好ましく、より好ましくは１０ｎｍ以上５０ｎｍ以下である。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も良いが、略円形や楕円形でも良く、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。 The average particle diameter of the inorganic oxide particles of the present invention is preferably more than 5 nm and not more than 100 nm, more preferably not less than 10 nm and not more than 50 nm. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. As the shape of the particle, a true sphere is the best, but it may be approximately circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
本発明の建築外装用コーティング液は、加水分解性シリコーン、加水分解性シラン、無定形の無機酸化物、無定形の無機酸化物を形成するための前駆体、樹脂バインダー、アルカリシリケートの群から選ばれる少なくとも１種のバインダーを実質的に含まないのが好ましく、より好ましくは全く含まない。これの物質はバインダーとして光触媒層の強度向上に寄与する。しかしながら、場合によって、その存在が光触媒活性の発現または有害ガス分解性に有利な間隙の形成に影響を与えることがある。従って、本発明にあっては、有害ガス分解性を確保できる程度であれば上記バインダーを任意成分として含有することは許容されるが、またその添加は控えるまたは少量とすることが好ましい。具体的には、上記バインダー成分の含有量は、建築外装用コーティング液の乾燥物質量を１００質量％としたときに０質量％以上１０質量％未満、好ましくは５質量％以下、最も好ましくは０質量％である。 The coating liquid for exterior building of the present invention is selected from the group consisting of hydrolyzable silicone, hydrolyzable silane, amorphous inorganic oxide, precursor for forming amorphous inorganic oxide, resin binder, and alkali silicate. Is preferably substantially free of, and more preferably not at all. These substances contribute to improving the strength of the photocatalytic layer as a binder. However, in some cases, its presence can affect the formation of a gap that favors the development of photocatalytic activity or decomposability of harmful gases. Therefore, in the present invention, it is acceptable to contain the binder as an optional component as long as harmful gas decomposability can be secured, but it is preferable to refrain from adding it or to make it a small amount. Specifically, the content of the binder component is 0% by mass to less than 10% by mass, preferably 5% by mass or less, most preferably 0 when the amount of dry substance of the coating liquid for building exterior is 100% by mass. % By mass.
ここで、加水分解性シリコーン及び／又は加水分解性シランとしては、４官能シリコーン化合物及び／又は４官能シランがよく使用され、例えば、エチルシリケート４０（オリゴマー、Ｒがエチル基）、エチルシリケート４８（オリゴマー、Ｒがエチル基）メチルシリケート５１（オリゴマー、Ｒがメチル基）（いずれもコルコート社製）、テトラメトキシシラン、テトラエトキシシラン、ジメトキシジエトキシシランの形で市販されている。これらの加水分解性シリコーン及び／又は加水分解性シランは、建築外装用コーティング液を塗布後、乾燥に伴い縮合が進み、乾燥物となる。 Here, as the hydrolyzable silicone and / or hydrolyzable silane, a tetrafunctional silicone compound and / or a tetrafunctional silane is often used. For example, ethyl silicate 40 (oligomer, R is an ethyl group), ethyl silicate 48 ( Oligomer, R is ethyl group) Methyl silicate 51 (oligomer, R is methyl group) (all manufactured by Colcoat Co.), tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxysilane are commercially available. These hydrolyzable silicones and / or hydrolyzable silanes are dried after being applied with the coating liquid for building exteriors, resulting in a dry product.
上述したように、加水分解性シランモノマーとしては、テトラアルコキシシラン等の４官能性のシランモノマーが親水機能の面から好ましいが、トリアルコキシオルガノシラン等の３官能性モノマーやジアルコキシジオルガノシラン等の２官能性モノマーも利用できる。加水分解性シリコーンとしてもテトラアルコキシシラン等の４官能性のシランモノマーの加水分解・縮重合物が親水機能の面から好ましいが、２〜４官能加水分解性シラン単位を少なくとも１つ含む加水分解・縮重合物であれば好適に利用できる。 As described above, as the hydrolyzable silane monomer, a tetrafunctional silane monomer such as tetraalkoxysilane is preferable from the viewpoint of hydrophilic function, but a trifunctional monomer such as trialkoxyorganosilane, dialkoxydiorganosilane, etc. These bifunctional monomers can also be used. The hydrolyzable silicone is preferably a hydrolyzed / condensed product of a tetrafunctional silane monomer such as tetraalkoxysilane from the viewpoint of the hydrophilic function. However, the hydrolyzable silicone containing at least one 2- to 4-functional hydrolyzable silane unit is preferable. Any condensation polymer can be suitably used.
ここで、酸化物換算の無定形の無機酸化物については、粒子形状を伴わない無定形酸化チタン、無定形シリカ、無定形アルミナ等が好適に利用可能である。無定形の無機酸化物を形成するための前駆体としては、チタンアルコキシド、過酸化チタン等が好適に利用できる。 Here, as the amorphous inorganic oxide in terms of oxide, amorphous titanium oxide, amorphous silica, amorphous alumina and the like without any particle shape can be suitably used. As a precursor for forming an amorphous inorganic oxide, titanium alkoxide, titanium peroxide, or the like can be suitably used.
また、樹脂バインダーとしては、フッ素樹脂バインダー、シリコーン変性アクリルバインダー、シリコーン変性エポキシバインダー、シリコーン変性ウレタンバインダー、シリコーン変性ポリエステルバインダー等の耐候性の強いバインダーが好ましいが、場合によっては、アクリルバインダー、エポキシバインダー等も利用可能である。 Further, as the resin binder, a binder having strong weather resistance such as a fluororesin binder, a silicone-modified acrylic binder, a silicone-modified epoxy binder, a silicone-modified urethane binder, and a silicone-modified polyester binder is preferable. Etc. are also available.
樹脂バインダーとして樹脂エマルジョンを利用すると水に分散しやすく好ましい。樹脂エマルジョンとしては、例えば、シリコーンエマルジョン、フッ素樹脂エマルジョン、アクリルシリコーンエマルジョン、シリコーン変性エマルジョン、シリコーン変性ウレタンエマルジョン、シリコーン変性ポリエステルエマルジョン等の耐候性の強いエマルジョンが好ましいが、場合によっては、アクリルエマルジョン等も利用可能である。 It is preferable to use a resin emulsion as the resin binder because it is easily dispersed in water. As the resin emulsion, for example, an emulsion having strong weather resistance such as a silicone emulsion, a fluororesin emulsion, an acrylic silicone emulsion, a silicone-modified emulsion, a silicone-modified urethane emulsion, and a silicone-modified polyester emulsion is preferable. Is available.
アルカリシリケートとしては、例えば、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸リチウム等が好適に利用できる。 As the alkali silicate, for example, sodium silicate, potassium silicate, lithium silicate and the like can be suitably used.
さらに、本発明の建築外装用コーティング液には、バナジウム、鉄、コバルト、ニッケル、パラジウム、亜鉛、ルテニウム、ロジウム、銅、銀、白金および金からなる群より選ばれる少なくとも一種の金属又は金属化合物を添加することにより、さらに高い抗菌・防カビ性能を発現させることができる。ただしその存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましく、従って、その添加量は微量でよく、またその作用の発現に必要な量は微量である。具体的には、光触媒に対して、０．０１〜１０質量％、より好ましくは０．０５〜５質量％程度の添加量が好ましい。また、、金属化合物としては、例えば、上記金属のグルコン酸塩、硫酸塩、リンゴ酸塩、乳酸塩、硫酸塩、硝酸塩、ギ酸塩、酢酸塩、キレート等が好適に利用できる。 Furthermore, the coating liquid for building exterior of the present invention contains at least one metal or metal compound selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold. By adding, higher antibacterial / antifungal performance can be expressed. However, it is desirable that the presence thereof does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles, and therefore, the addition amount may be small, and the amount necessary for the expression of the action is Trace amount. Specifically, an addition amount of about 0.01 to 10% by mass, more preferably about 0.05 to 5% by mass is preferable with respect to the photocatalyst. Further, as the metal compound, for example, gluconate, sulfate, malate, lactate, sulfate, nitrate, formate, acetate, chelate and the like of the above metals can be suitably used.
さらに、本発明の建築外装用コーティング液には、光触媒粒子と、無機酸化物粒子と、任意成分としてのバインダーと、に加えてさらに、難水溶性又は非水溶性の無機塩や樹脂粒子が含有されて良く、その添加量は、建築外装用コーティング液の乾燥物質量を１００質量％としたときに、０質量％以上１０質量％未満であり、好ましくは５質量％以下、最も好ましくは０質量％で含有されていてもよい。 ただし、その存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましい。 Furthermore, in addition to the photocatalyst particles, the inorganic oxide particles, and the binder as an optional component, the coating liquid for building exterior of the present invention further contains a hardly water-soluble or water-insoluble inorganic salt or resin particles. The addition amount may be 0% by mass or more and less than 10% by mass, preferably 5% by mass or less, and most preferably 0% by mass, when the dry substance amount of the coating liquid for building exterior is 100% by mass. % May be contained. However, it is desirable that the presence does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles.
難水溶性又は非水溶性の無機塩としては、例えば、水酸化アルミニウム、ベーマイト、炭酸カルシウム等が好適に利用できる。 As the hardly water-soluble or water-insoluble inorganic salt, for example, aluminum hydroxide, boehmite, calcium carbonate and the like can be suitably used.
樹脂粒子としては、球状、板状等の粒子を利用することで意匠上艶調整が可能な場合があり、光触媒性能や耐候性を妨げない範囲での添加が可能である。 As the resin particles, there are cases where the gloss can be adjusted by design using spherical or plate-like particles, and the addition can be made within a range not impeding the photocatalytic performance and weather resistance.
本発明による建築外装用コーティング液は、光触媒層において記載した各成分を、上記質量比率で溶媒中に分散または溶解して製造される。ここで、酸化チタンは、粉末状、ゾル状、溶液状などいずれであってもよい。また、無機酸化物粒子は、水を分散媒とした水性コロイド；またはエチルアルコール、イソプロピルアルコール、もしくはエチレングリコールなどの親水性溶媒にコロイド状に分散させたオルガノゾルの形態であるのが好ましく、特に好ましくはコロイダルシリカである。 The coating solution for exterior building according to the present invention is produced by dispersing or dissolving each component described in the photocatalyst layer in a solvent at the above mass ratio. Here, the titanium oxide may be in the form of powder, sol, solution, or the like. The inorganic oxide particles are preferably in the form of an aqueous colloid using water as a dispersion medium; or an organosol dispersed in a colloidal form in a hydrophilic solvent such as ethyl alcohol, isopropyl alcohol, or ethylene glycol. Is colloidal silica.
その他、本発明の建築外装用コーティング液には、光触媒粒子と、無機酸化物粒子と、任意成分としてのバインダーと、に加えてさらに、紫外線遮蔽剤、有機防カビ剤、界面活性剤、消泡剤、ＰＨ調整剤、色素、増粘剤等が添加されていても良く、その添加量は、該建築外装用コーティング液の乾燥物質量を１００質量％としたときに、０質量％以上１０質量％未満であり、好ましくは５質量％以下、最も好ましくは０質量％で含有されていてもよい。ただし、その存在は、上述の光触媒粒子および無機酸化物粒子による粒子間の間隙の形成に影響を与えないことが望ましい。 In addition to the photocatalyst particles, the inorganic oxide particles, and the binder as an optional component, the coating liquid for building exterior of the present invention further includes an ultraviolet shielding agent, an organic antifungal agent, a surfactant, an antifoaming agent. An agent, a pH adjuster, a pigment, a thickener, and the like may be added. The addition amount is 0% by mass or more and 10% by mass when the dry substance amount of the coating liquid for building exterior is 100% by mass. %, Preferably 5% by mass or less, and most preferably 0% by mass. However, it is desirable that the presence does not affect the formation of gaps between the above-described photocatalyst particles and inorganic oxide particles.
本発明による建築外装用コーティング液は、任意成分として界面活性剤を含んでよく、その添加量は、建築外装用コーティング液の乾燥物質量を１００質量％としたときに、０質量％以上１０質量％未満であり、好ましくは０質量％以上８質量％以下であり、より好ましくは０質量％以上６質量％以下である。界面活性剤の添加により、レベリングすなわち塗工表面の平滑化、均一化を図ることが出来る。また、界面活性剤は建築外装用コーティング液の濡れ性を改善するために有効な成分であるが、濡れ性を問題にしないのであれば界面活性剤は実質的にあるいは一切含まないことが好ましい場合がある。 The coating liquid for building exterior according to the present invention may contain a surfactant as an optional component, and the added amount thereof is 0% by mass or more and 10% by mass when the dry substance amount of the coating liquid for building exterior is 100% by mass. %, Preferably 0 to 8% by mass, more preferably 0 to 6% by mass. By adding the surfactant, leveling, that is, smoothing and uniforming the coated surface can be achieved. In addition, the surfactant is an effective component for improving the wettability of the coating liquid for building exteriors, but it is preferable that the surfactant is substantially or not included if the wettability is not a problem. There is.
界面活性剤は、光触媒や無機酸化物粒子の分散安定性、中間層上に塗布した際の濡れ性を勘案し適宜選択されてよいが、非イオン性界面活性剤が好ましく、より好ましくは、エーテル型非イオン性界面活性剤、エステル型非イオン性界面活性剤、ポリアルキレングリコール非イオン性界面活性剤、フッ素系非イオン性界面活性剤、シリコン系非イオン性界面活性剤が挙げられる。 The surfactant may be appropriately selected in consideration of the dispersion stability of the photocatalyst and the inorganic oxide particles and the wettability when coated on the intermediate layer, but a nonionic surfactant is preferable, and ether is more preferable. Type nonionic surfactant, ester type nonionic surfactant, polyalkylene glycol nonionic surfactant, fluorine-based nonionic surfactant, and silicon-based nonionic surfactant.
溶媒は、上記構成成分を適切に分散または溶解可能なあらゆる溶媒が使用可能であり、水および／または有機溶媒であってよい。本発明による建築外装用コーティング液に適用可能な溶媒としては、環境に与える影響が小さい水を用いることが好ましい。さらに、成膜時におけるレベリング性向上や乾燥性の調整を目的に、有機溶媒を利用してもよい。有機溶媒の好ましい例としては、アルコール類、エーテル類、アセトン、２−ブタノン、メチルプロピルケトン、メチルブチルケトン、ジプロピルケトン等のケトン類、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸アミル、酪酸エチル等のエステル類、ベンゼン、トルエン、キシレン、クロロホルム、ペンタン、ヘキサン、シクロヘキサン等の脂肪族、芳香族、脂環式の炭化水素、石油類等の一般的な溶媒が挙げられ、これらを単独、もしくは混合して用いることができ、特に水溶性溶媒が好ましい。水溶性溶媒としては、メタノール、エタノール、変性エタノール、ｎ−プロパノ−ル、イソプロパノ−ル、ｎ−ブタノ−ル、イソブタノール、ｓ−ブタノール、ｔ−ブタノール、１，３−ブタンジオール、２，３−ブタンジオール、１，４−ブタンジオール、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノイソプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノイソプロピルエーテル、ジプロピレングリコールモノブチルエーテル、エチレングリコールジプチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジイソプロピルエーテル、トリエチレングリコールジメチルエーテル、グリセリンモノメチルエーテル、トリメチレングリコール、Ｎ−メチルピロリドン、エチ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、プロピレングリコールモノプロピルエーテル、３，５−ジメチル−１−ヘキシン−３−オール、ジアセトンアルコール、３−メチル−３−メトキシブタノール等のアルコール類やエーテル類、および、ケトン類などが挙げられ、これらを単独で、あるいは複数種類を混合して用いることができる。 As the solvent, any solvent capable of appropriately dispersing or dissolving the above components can be used, and it may be water and / or an organic solvent. As a solvent applicable to the coating liquid for building exterior according to the present invention, it is preferable to use water having a small influence on the environment. Furthermore, an organic solvent may be used for the purpose of improving the leveling property during film formation and adjusting the drying property. Preferred examples of the organic solvent include alcohols, ethers, acetone, 2-butanone, ketones such as methyl propyl ketone, methyl butyl ketone, and dipropyl ketone, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and amyl acetate. General solvents such as esters such as ethyl butyrate, aliphatic, aromatic and alicyclic hydrocarbons such as benzene, toluene, xylene, chloroform, pentane, hexane and cyclohexane, petroleums, etc. They can be used alone or in combination, and a water-soluble solvent is particularly preferable. Examples of water-soluble solvents include methanol, ethanol, denatured ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, 1,3-butanediol, 2,3 -Butanediol, 1,4-butanediol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, ethyl Glycol diptyl ether, diethylene glycol diethyl ether, diethylene glycol diisopropyl ether, triethylene glycol dimethyl ether, glycerin monomethyl ether, trimethylene glycol, N-methylpyrrolidone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl Examples include ethers such as ether, 3,5-dimethyl-1-hexyn-3-ol, diacetone alcohol, and 3-methyl-3-methoxybutanol, ethers, and ketones. Alternatively, a plurality of types can be mixed and used.
また、本発明の建築外装用コーティング液の固形分濃度は特に限定されないが、１〜１０質量％とするのが塗布し易さにおいて好ましい。なお、建築外装用コーティング組成物中の構成成分の分析は、コーティング液を限外ろ過によって粒子成分と濾液に分離し、それぞれを赤外分光分析、ゲルパーミエーションクロマトグラフィー、蛍光Ｘ線分光分析などで分析し、スペクトルを解析することによって評価することができる。 Moreover, the solid content concentration of the coating liquid for building exterior of the present invention is not particularly limited, but is preferably 1 to 10% by mass in terms of ease of application. In addition, the analysis of the structural component in the coating composition for building exteriors is performed by separating the coating liquid into a particle component and a filtrate by ultrafiltration, and each of them is infrared spectroscopic analysis, gel permeation chromatography, fluorescent X-ray spectroscopic analysis, etc. And can be evaluated by analyzing the spectrum.
建築用外装材の製造方法
本発明の建築用外装材は、本発明の建築外装用コーティング液を基材上に塗布することにより製造することができる。塗装方法は、刷毛塗り、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷等、一般に広く行われている方法を利用できる。コーティング液の基材への塗布後は、常温乾燥させればよく、あるいは必要に応じて加熱乾燥してもよい。しかし、焼結が進むまで加熱すると粒子間の空隙が減少し十分な光触媒活性を得ることができなくなるおそれがあるため、空隙形成に影響を与えないあるいは影響が少なくなる温度および時間を選択することが好ましい。例えば、乾燥温度は１０℃以上５００℃以下であり、基材の少なくとも一部に樹脂が含まれる場合、樹脂の耐熱温度等を考慮し、例えば好ましい乾燥温度は１０℃以上２００℃以下である。
Manufacturing method of building exterior material The building exterior material of the present invention can be manufactured by applying the coating liquid for building exterior of the present invention on a substrate. As a coating method, generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used. After applying the coating liquid to the substrate, it may be dried at room temperature, or may be heat-dried as necessary. However, if heating is performed until sintering proceeds, the voids between the particles may decrease, and sufficient photocatalytic activity may not be obtained, so select a temperature and time that do not affect or reduce the effect of void formation. Is preferred. For example, when the drying temperature is 10 ° C. or more and 500 ° C. or less and the resin is contained in at least a part of the substrate, the preferable drying temperature is, for example, 10 ° C. or more and 200 ° C. or less in consideration of the heat resistance temperature of the resin.
本発明による建築用外装材は、上述のとおり、基材との間に中間層を介在させる必要がないため、その製造に要する時間やコストを削減できるとの点で有利である。 As described above, the architectural exterior material according to the present invention does not require an intermediate layer to be interposed between the base material and the base material, which is advantageous in that the time and cost required for the production can be reduced.
本発明を以下の例に基づいて具体的に説明するが、本発明はこれらの例に限定されるものではない。 The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.
（実施例１）
まず、基材として５０ｍｍＸ１００ｍｍの平板状の着色有機塗装体を用意した。この着色有機塗装体は、シーラー処理した窯業系サイディング基材上にカーボンブラック粉末を添加した汎用シリコーン変性アクリル塗料（シリコーン変性アクリル樹脂中のケイ素原子含有量１質量％）を塗布して、十分に乾燥および硬化させたものである。
Example 1
First, a plate-like colored organic coated body of 50 mm × 100 mm was prepared as a substrate. This colored organic coated body was applied with a general-purpose silicone-modified acrylic paint (carbon atom content 1 mass% in the silicone-modified acrylic resin) in which carbon black powder was added onto a sealer-treated ceramic siding base, It has been dried and cured.
次いで、建築外装用コーティング液を用意した。この建築外装用コーティング液は、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分の質量比が３．１０：９６．９０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液である。 Next, an architectural exterior coating solution was prepared. This building exterior coating liquid comprises anatase-type titania aqueous dispersion (average particle size: 42 nm, basic), water-dispersed colloidal silica (average particle size: 14 nm, basic), and a solid content of TiO 2. It is a coating liquid for exterior building, in which the mass ratio of the solid content of SiO 2 is 3.10: 96.90, and the solvent is mixed with water to adjust the solid content concentration to 5.5 mass%.
得られた建築外装用コーティング液をあらかじめ加熱した上記着色有機塗装体上に２０ｇ／ｍ２スプレー塗布し、常温で乾燥した。こうして、光触媒層を形成させて、建築用外装材を得た。 The obtained coating liquid for building exterior was applied to the colored organic coating body heated in advance by spraying 20 g / m 2 and dried at room temperature. In this way, a photocatalyst layer was formed to obtain a building exterior material.
（実施例２）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が４．６０：９５．４０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた点、および着色有機塗装体上への建築外装用コーティング液の塗布量を３０ｇ／ｍ２とした以外は、実施例１と同様の条件で試料を作製した。
(Example 2)
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 The point which used the coating liquid for building exteriors which mixed with water so that mass ratio with solid content of 2 might be 4.60: 95.40, and adjusted solid content concentration to 5.5 mass%, And the sample was produced on the conditions similar to Example 1 except the application quantity of the coating liquid for building exteriors on the coloring organic coating body having been 30 g / m < 2 >.
なお、空隙率測定のために、基材をガラス板とし、また塗布後の乾燥を９０℃で行った以外は、上と同様にして塗装体試料を得た。空隙率は２８体積％であった。 A coated body sample was obtained in the same manner as above except that the substrate was a glass plate and the coating was dried at 90 ° C. in order to measure the porosity. The porosity was 28% by volume.
（実施例３）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：１０ｎｍ、酸性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、酸性、アルミナ被覆）と、テトラエトキシシランの重縮合物（ＳｉＯ２換算濃度：４０質量％。溶媒：エタノール、水）とを、ＴｉＯ２の固形分とコロイダルシリカの固形分とテトラエトキシシランの重縮合物中のＳｉＯ２換算の乾燥質量との質量比が４．６０：９０．４０：５．００となるように溶媒に水とエタノールとを用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例２と同様の条件で試料を作製した。
(Example 3)
Anatase-type titania aqueous dispersion (average particle size: 10 nm, acidic), water-dispersed colloidal silica (average particle size: 14 nm, acidic, alumina coating), and tetraethoxysilane polycondensate as a coating solution for building exteriors (SiO 2 equivalent concentration: 40% by mass. Solvent: ethanol, water) The mass ratio of the solid content of TiO 2 , the solid content of colloidal silica, and the dry mass in terms of SiO 2 in the polycondensate of tetraethoxysilane. Except that the coating liquid for building exterior was adjusted to a solid content concentration of 5.5% by mass by mixing the solvent with water and ethanol so that the ratio was 4.60: 90.40: 5.00. A sample was prepared under the same conditions as in Example 2.
なお、空隙率測定のために、基材をガラス板とし、また塗布後の乾燥を９０℃で行った以外は、上と同様にして塗装体試料を得た。空隙率は２１体積％であった。 A coated body sample was obtained in the same manner as above except that the substrate was a glass plate and the coating was dried at 90 ° C. in order to measure the porosity. The porosity was 21% by volume.
（実施例４）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が４．９０：９５．１０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例３と同様の条件で試料を作製した。
Example 4
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 Except for using a coating liquid for building exterior that was mixed with water so that the mass ratio with respect to the solid content of 2 was 4.90: 95.10 and adjusted to a solid content concentration of 5.5% by mass. A sample was prepared under the same conditions as in Example 3.
（実施例５）
まず、基材として５０ｍｍＸ１００ｍｍの平板状の着色有機塗装体を用意した。この着色有機塗装体は、シーラー処理した窯業系サイディング基材上に白色顔料を添加したアクリル塗料（シリコンなし）を下地が隠ぺいされるまで塗布した後、常温で十分に乾燥および硬化させたものである。
(Example 5)
First, a plate-like colored organic coated body of 50 mm × 100 mm was prepared as a substrate. This colored organic coated body is made by applying an acrylic paint (without silicone) with white pigment on a sealer-treated ceramic-based siding base material until the base is concealed, and then thoroughly drying and curing at room temperature. is there.
次いで、建築外装用コーティング液を用意した。この建築外装用コーティング液は、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分の質量比が３．１０：９６．９０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液である。 Next, an architectural exterior coating solution was prepared. This building exterior coating liquid comprises anatase-type titania aqueous dispersion (average particle size: 42 nm, basic), water-dispersed colloidal silica (average particle size: 14 nm, basic), and a solid content of TiO 2. It is a coating liquid for exterior building, in which the mass ratio of the solid content of SiO 2 is 3.10: 96.90, and the solvent is mixed with water to adjust the solid content concentration to 5.5 mass%.
得られた建築外装用コーティング液をあらかじめ加熱した上記着色有機塗装体上に２０ｇ／ｍ２スプレー塗布し、常温で乾燥した。こうして、光触媒層を形成させて、建築用外装材を得た。 The obtained coating liquid for building exterior was applied to the colored organic coating body heated in advance by spraying 20 g / m 2 and dried at room temperature. In this way, a photocatalyst layer was formed to obtain a building exterior material.
（実施例６）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が４．６０：９５．４０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた点、および着色有機塗装体上への建築外装用コーティング液の塗布量を３０ｇ／ｍ２とした以外は、実施例５と同様の条件で試料を作製した。
(Example 6)
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 The point which used the coating liquid for building exteriors which mixed with water so that mass ratio with solid content of 2 might be 4.60: 95.40, and adjusted solid content concentration to 5.5 mass%, And the sample was produced on the conditions similar to Example 5 except the application quantity of the coating liquid for building exteriors on the coloring organic coating body having been 30 g / m < 2 >.
（実施例７）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：１０ｎｍ、酸性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、酸性、アルミナ被覆）と、テトラエトキシシランの重縮合物（ＳｉＯ２換算濃度：４０質量％。溶媒：エタノール、水）とを、ＴｉＯ２の固形分とコロイダルシリカの固形分とテトラエトキシシランの重縮合物中のＳｉＯ２換算の乾燥質量との質量比が４．６０：９０．４０：５．００となるように溶媒に水とエタノールとを用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例６と同様の条件で試料を作製した。
(Example 7)
Anatase-type titania aqueous dispersion (average particle size: 10 nm, acidic), water-dispersed colloidal silica (average particle size: 14 nm, acidic, alumina coating), and tetraethoxysilane polycondensate as a coating solution for building exteriors (SiO 2 equivalent concentration: 40% by mass. Solvent: ethanol, water) The mass ratio of the solid content of TiO 2 , the solid content of colloidal silica, and the dry mass in terms of SiO 2 in the polycondensate of tetraethoxysilane. Except that the coating liquid for building exterior was adjusted to a solid content concentration of 5.5% by mass by mixing the solvent with water and ethanol so that the ratio was 4.60: 90.40: 5.00. A sample was prepared under the same conditions as in Example 6.
（実施例８）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が４．９０：９５．１０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例６と同様の条件で試料を作製した。
(Example 8)
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 Except for using a coating liquid for building exterior that was mixed with water so that the mass ratio with respect to the solid content of 2 was 4.90: 95.10 and adjusted to a solid content concentration of 5.5% by mass. A sample was prepared under the same conditions as in Example 6.
（比較例１）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が０．６０：９９．４０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例２と同様の条件で試料を作製した。
(Comparative Example 1)
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 Except for using a coating liquid for building exterior that was mixed with water so that the mass ratio with the solid content of 2 was 0.60: 99.40 and adjusted to a solid content concentration of 5.5% by mass. A sample was prepared under the same conditions as in Example 2.
なお、空隙率測定のために、基材をガラス板とし、また塗布後の乾燥を９０℃で行った以外は、上と同様にして塗装体試料を得た。空隙率は１５体積％であった。 A coated body sample was obtained in the same manner as above except that the substrate was a glass plate and the coating was dried at 90 ° C. in order to measure the porosity. The porosity was 15% by volume.
（比較例２）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：１０ｎｍ、酸性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、酸性、アルミナ被覆）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が２．００：９８．００となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた点、および着色有機塗装体上への建築外装用コーティング液の塗布量を１５ｇ／ｍ２とした以外は、実施例１と同様の条件で試料を作製した。
(Comparative Example 2)
As an architectural exterior coating liquid, anatase-type titania aqueous dispersion (average particle size: 10 nm, acidic) and water-dispersed colloidal silica (average particle size: 14 nm, acidic, alumina-coated), solid content of TiO 2 that the solvent such that 98.00 mixing with water, was used having a solid fraction concentration of 5.5% by mass architectural exterior coating solution: mass ratio of the solid content of SiO 2 is 2.00 A sample was prepared under the same conditions as in Example 1 except that the coating amount of the coating solution for building exterior on the colored organic coated body was 15 g / m 2 .
（比較例３）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：１０ｎｍ、酸性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、酸性、アルミナ被覆）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が１０．００：９０．００となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、比較例２と同様の条件で試料を作製した。
(Comparative Example 3)
As an architectural exterior coating liquid, anatase-type titania aqueous dispersion (average particle size: 10 nm, acidic) and water-dispersed colloidal silica (average particle size: 14 nm, acidic, alumina-coated), solid content of TiO 2 Except for using a coating liquid for building exterior that is mixed with water so that the mass ratio of SiO 2 to the solid content is 10.00: 90.00 and adjusted to a solid content concentration of 5.5% by mass. Prepared a sample under the same conditions as in Comparative Example 2.
なお、空隙率測定のために、基材をガラス板とし、また塗布後の乾燥を９０℃で行った以外は、上と同様にして塗装体試料を得た。空隙率は３７体積％であった。 A coated body sample was obtained in the same manner as above except that the substrate was a glass plate and the coating was dried at 90 ° C. in order to measure the porosity. The porosity was 37% by volume.
（比較例４）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：４２ｎｍ、塩基性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）とを、ＴｉＯ２の固形分とＳｉＯ２の固形分との質量比が０．６０：９９．４０となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた以外は、実施例６と同様の条件で試料を作製した。
(Comparative Example 4)
As an architectural exterior coating solution, anatase-type titania aqueous dispersion (average particle size: 42 nm, basic) and water-dispersed colloidal silica (average particle size: 14 nm, basic), TiO 2 solid content and SiO 2 Except for using a coating liquid for building exterior that was mixed with water so that the mass ratio with the solid content of 2 was 0.60: 99.40 and adjusted to a solid content concentration of 5.5% by mass. A sample was prepared under the same conditions as in Example 6.
（比較例５）
建築外装用コーティング液として、アナターゼ型チタニア水分散体（平均粒径：１０ｎｍ、酸性）と、水分散型コロイダルシリカ（平均粒径：１４ｎｍ、酸性、アルミナ被覆）とを、ＴｉＯ２の固形分とコロイダルシリカの固形分との質量比が２．００：９８．００となるように溶媒に水を用いて混合し、固形分濃度５．５質量％に調整した建築外装用コーティング液を用いた点、および着色有機塗装体上への建築外装用コーティング液の塗布量を１５ｇ／ｍ２とした以外は、実施例５と同様の条件で試料を作製した。
(Comparative Example 5)
As an architectural exterior coating liquid, anatase-type titania aqueous dispersion (average particle size: 10 nm, acidic) and water-dispersed colloidal silica (average particle size: 14 nm, acidic, alumina-coated), solid content of TiO 2 The point which used the coating liquid for building exteriors which mixed water using water so that mass ratio with the solid content of colloidal silica might be set to 2.00: 98.00, and was adjusted to solid content concentration 5.5 mass% A sample was prepared under the same conditions as in Example 5, except that the coating amount of the architectural exterior coating liquid on the colored organic coated body was 15 g / m 2 .
（評価実験Ａ）
実施例１〜８、および比較例１〜５について、ＮＯｘ分解性試験を以下の通りの方法で行った。まず上記試料を前処理として１ｍＷ／ｃｍ２のＢＬＢ光（輝線スペクトルの波長が３５１ｎｍのものを使用）で５ｈｒ以上照射した。次いでＪＩＳ Ｒ １７０１−１に記載の反応容器内に塗装体サンプルを２枚セットした。２５℃、５０％ＲＨに調整した空気に約１０００ｐｐｂになるようにＮＯガスを混合し、遮光した反応容器内に流量１．５ｌ／ｍｉｎで２０分供給した。その後ガスを導入したままで１ｍＷ／ｃｍ２に調整したＢＬＢ光（輝線スペクトルの波長が３５１ｎｍのものを使用）を２０分間照射した。その後ガスを導入した状態で再度反応容器を遮光した。ＮＯｘ除去量は、ＢＬＢ光照射前後でのＮＯ、ＮＯ２濃度から下記の式に従って計算した。
ＮＯｘ除去量(ppb)＝［ＮＯ（照射後）−ＮＯ（照射時）］−［ＮＯ２（照射時）−ＮＯ２（照射後）］
(Evaluation Experiment A)
About Examples 1-8 and Comparative Examples 1-5, the NOx decomposability | decomposability test was done with the method as follows. First, as a pretreatment, the above sample was irradiated with 1 mW / cm 2 of BLB light (with a bright line spectrum having a wavelength of 351 nm) for 5 hours or more. Next, two coated body samples were set in the reaction vessel described in JIS R 1701-1. NO gas was mixed with air adjusted to 25 ° C. and 50% RH at about 1000 ppb, and the mixture was supplied into a light-shielded reaction vessel at a flow rate of 1.5 l / min for 20 minutes. Thereafter, BLB light adjusted to 1 mW / cm 2 was used for 20 minutes while the gas was introduced (using a wavelength of the emission line spectrum of 351 nm). Thereafter, the reaction vessel was shielded from light again with the gas introduced. The NOx removal amount was calculated according to the following formula from the NO and NO 2 concentrations before and after the BLB light irradiation.
NOx removal amount (ppb) = [NO (after irradiation) −NO (at irradiation)] − [NO 2 (at irradiation) −NO 2 (after irradiation)]
実施例１〜４および比較例１〜３の結果は表１に、また実施例５〜８および比較例４〜６の結果は表２に示されるとおりであった。 The results of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1, and the results of Examples 5 to 8 and Comparative Examples 4 to 6 are as shown in Table 2.
（評価実験Ｂ）
実施例１〜４、比較例３について、宮古島にてＪＩＳ Ｋ ５６００−７−６に規定される暴露架台を用い南面に向けて水平より２０°の角度で屋外暴露を行った。１２ヶ月後に外観を目視で確認した。
(Evaluation Experiment B)
About Examples 1-4 and the comparative example 3, outdoor exposure was performed at an angle of 20 degrees from the horizontal toward the south surface using the exposure stand prescribed | regulated to JISK5600-7-6 in Miyakojima. The appearance was visually confirmed after 12 months.
得られた結果は表２に示される通りであった。ここで、表中のＧはほとんど変化しなかったことを、ＮＧはわずかに白華が生じたことを示す。 The obtained results were as shown in Table 2. Here, “G” in the table shows almost no change, and “NG” shows a slight white bloom.
（評価実験Ｃ）
実施例５〜８、比較例４、５について、以下の通り基材からのブリードアウトによる親水阻害防止性の評価を行った。評価方法は、各試料を暗所にて１日間養生した後に、１ｍＷ／ｃｍ２に調整したＢＬＢ光（輝線スペクトルの波長が３５１ｎｍのものを使用）下に光触媒塗装面を上にして８日間放置後、試料表面の水との接触角を接触角計（協和界面科学製 ＣＡ−Ｘ１５０型）にて測定した。
(Evaluation Experiment C)
About Examples 5-8 and Comparative Examples 4 and 5, the hydrophilic inhibition prevention property by the bleed-out from a base material was evaluated as follows. In the evaluation method, each sample was cured in the dark for 1 day, and then left for 8 days with the photocatalyst coating surface facing up under BLB light adjusted to 1 mW / cm 2 (the wavelength of the emission spectrum was 351 nm). Then, the contact angle with the water of the sample surface was measured with the contact angle meter (Kyowa Interface Science CA-X150 type | mold).
結果は表２に示される通りであった。ここで、表中のＧは水との接触角が２０°未満、ＮＧは２０°以上を示す。 The results were as shown in Table 2. Here, G in the table indicates a contact angle with water of less than 20 °, and NG indicates 20 ° or more.
Claims (16)
前記光触媒層が、該光触媒層全体を１００質量％としたときに、
３質量％を超え５質量％未満の光触媒粒子と、
８５質量％を超え９７質量％未満の無機酸化物粒子と、
０質量％以上１０質量％未満のバインダーを含んでなる、建築用外装材。 A building exterior material comprising a base material and a photocatalyst layer provided on the base material,
When the photocatalyst layer is 100% by mass of the entire photocatalyst layer,
Photocatalyst particles of more than 3% by mass and less than 5% by mass;
Inorganic oxide particles greater than 85% by weight and less than 97% by weight;
A building exterior material comprising a binder of 0% by mass or more and less than 10% by mass.
The inorganic oxide particles have a number average particle diameter of more than 5 nm and not more than 100 nm calculated by measuring the length of any 100 particles entering a 200,000-fold field of view with a scanning electron microscope. The building exterior material according to any one of claims 1 to 7.
溶媒と、
３質量％を超え５質量％未満の光触媒粒子と、
８５質量％を超え９７質量％未満の無機酸化物粒子と、
０質量％以上１０質量％未満のバインダーを含んでなる
建築外装用コーティング液。 When the dry substance amount of the coating liquid for building exterior is 100% by mass,
A solvent,
Photocatalyst particles of more than 3% by mass and less than 5% by mass;
Inorganic oxide particles greater than 85% by weight and less than 97% by weight;
A coating liquid for building exterior comprising a binder of 0% by mass or more and less than 10% by mass.
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