JP2006062935A - Glaze containing material having photocatalytic function and product having photocatalytic function which is formed using the same - Google Patents
Glaze containing material having photocatalytic function and product having photocatalytic function which is formed using the same Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 112
- 239000000463 material Substances 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 77
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 7
- 230000037303 wrinkles Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011941 photocatalyst Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 4
- 241000519995 Stachys sylvatica Species 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- -1 for example Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Glass Compositions (AREA)
- Catalysts (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
Description
本発明は、例えば陶器質基材などの表面に光触媒微粒子を焼結させて光触媒機能を発揮させる、光触媒機能を有する物質を含有した釉薬、およびそれを用いて形成した光触媒機能を有する製品に関するものである。 TECHNICAL FIELD The present invention relates to a glaze containing a substance having a photocatalytic function that exhibits photocatalytic function by sintering photocatalyst fine particles on the surface of a ceramic base material, for example, and a product having a photocatalytic function formed using the glaze It is.
従来より、酸化チタン（ＴｉＯ２）などの光触媒機能を有する物質を、基材に付着させることにより、防汚性、抗菌性、脱臭性、または有機化合物の分解促進性等を向上させる技術が種々提案されている。 Conventionally, various techniques for improving antifouling properties, antibacterial properties, deodorizing properties, or promoting the decomposition of organic compounds by attaching a substance having a photocatalytic function, such as titanium oxide (TiO 2 ), to a substrate are various. Proposed.
光触媒機能を有する物質は、釉薬中に添加されて焼成されると、その殆どがガラス状に熔融した釉薬層内に埋没してしまう。このため、光触媒機能を有する物質と汚染物質等とが接触することが少なく、十分な光触媒機能を発揮できる製品が作製できないという問題があった。 When a substance having a photocatalytic function is added to the glaze and baked, most of the substance is buried in the glaze layer melted into a glass. For this reason, there has been a problem that a product capable of exhibiting a sufficient photocatalytic function cannot be produced because a substance having a photocatalytic function is hardly in contact with contaminants.
そして、そのような問題を解決するものとして、予め釉薬層を形成しその上面に光触媒機能を有する物質を吹き付けて付着させる方法が提案されている（特開平５−２５３５４４号公報参照）。 In order to solve such a problem, there has been proposed a method in which a glaze layer is formed in advance and a substance having a photocatalytic function is sprayed and adhered on the upper surface thereof (see JP-A-5-253544).
しかし、この方法は釉薬層の塗布工程と光触媒微粉末の噴霧工程とを要し煩雑な手順を要するため、通常の釉薬のように一回の塗布のみで容易に光触媒機能を有する物質を基材に付着できる釉薬が嘱望されていた。 However, this method requires a complicated procedure because it requires a coating process of the glaze layer and a spraying process of the photocatalyst fine powder, so that a substance having a photocatalytic function can be easily formed by a single coating like a normal glaze. The glaze that can be attached to was envyed.
また、光触媒の効果は、汚染物質と光触媒機能を有する物質とが接触すればするほど顕著なものとなるが、これは光触媒機能を有する物質が露呈する総表面積が大きければ大きいほど、光触媒機能を発揮できることを意味する。この点、釉薬層の上面に光触媒機能を有する物質を吹き付ける方法では、光触媒機能を有する物質が付着できる部位は釉薬層の略平坦な表面のみとなり、十分に光触媒機能を発揮できる製品を作製できなかった。 The effect of the photocatalyst becomes more prominent as the contaminant and the substance having the photocatalytic function come into contact with each other. This is because the larger the total surface area exposed by the substance having the photocatalytic function is, the more the photocatalytic function becomes. It means that it can be demonstrated. In this regard, in the method of spraying a substance having a photocatalytic function on the upper surface of the glaze layer, the portion to which the substance having the photocatalytic function can adhere is only the substantially flat surface of the glaze layer, and a product that can sufficiently exhibit the photocatalytic function cannot be produced. It was.
さらに、光触媒機能を有する物質を吹き付ける方法では、光触媒機能を有する物質が釉薬層の表面に十分に固着していないため、雨水に晒される屋外環境下や洗浄などで光触媒機能を有する物質が落ちてしまい、経時的な実効性に問題があった。 Furthermore, in the method of spraying a substance having a photocatalytic function, since the substance having a photocatalytic function is not sufficiently fixed to the surface of the glaze layer, the substance having the photocatalytic function is dropped in an outdoor environment exposed to rainwater or washing. Therefore, there was a problem with the effectiveness over time.
他方、汚染物質と光触媒機能を有する物質とをより接触させるためには、釉薬層が吸着作用を奏することが望ましく、このような観点からＡｇ+イオンなど酸素や水に対し優れた吸着特性を示す物質を釉薬層内に含有させる技術（特開平１０−３３７４７７号公報参照）が提案されているが、そのような吸着特性に優れた物質を別段添加しなくても釉薬層が吸着性に優れたものとなればより好ましい。 On the other hand, it is desirable that the glaze layer has an adsorption action in order to bring the contaminants and the substance having a photocatalytic function into contact with each other. From such a viewpoint, it exhibits excellent adsorption characteristics for oxygen and water such as Ag + ions. A technique for incorporating a substance into the glaze layer (see Japanese Patent Application Laid-Open No. 10-337477) has been proposed, but the glaze layer has excellent adsorptivity without adding a substance having such excellent adsorption characteristics. If it becomes a thing, it is more preferable.
本願発明者は、上記のような現状に鑑み、光触媒機能を有する物質が存在する部位を立体的に構成でき付着部位を各段に増大させ、それにより光触媒機能を有する物質が露呈する総表面積を増大させて光触媒効果を向上させると共に、耐水性または耐候性に優れ、さらに、吸着特性に優れた物質を別段添加しなくても釉薬層が吸着性に優れたものとなる釉薬を想起し本発明を完成するに至った。
すなわち、本発明の課題は、基材に塗布して焼成するのみで光触媒機能を有する物質を基材表面に大量付着でき極めて高い光触媒機能を発揮させることができると共に、耐水性または耐候性に優れ、吸着特性に優れた物質を別段添加しなくても釉薬層が吸着性に優れたものとなる光触媒機能を有する物質を含有した釉薬、およびそれを用いて形成した光触媒機能を有する製品を提供することにある。 That is, the object of the present invention is to apply a large amount of a substance having a photocatalytic function to the surface of the substrate simply by applying it to the substrate and baking it, and exhibit an extremely high photocatalytic function, and is excellent in water resistance or weather resistance. , A glaze containing a substance having a photocatalytic function in which a glaze layer has excellent adsorptivity without adding a substance having excellent adsorption characteristics, and a product having a photocatalytic function formed using the glaze There is.
本発明は、光触媒機能を有する物質を含有し、マット釉に形成されたことを主要な特徴とするものである。 The main feature of the present invention is that it contains a substance having a photocatalytic function and is formed into a mat ridge.
請求項１に記載の発明によれば、基材に塗布して焼成するのみで光触媒機能を有する物質を基材表面に有効的に付着でき極めて高い光触媒機能を発揮できると共に、耐水性または耐候性にも優れ、吸着特性に優れた物質を別段添加しなくても釉薬層が吸着性に優れたものとなる。
請求項２に記載の発明によれば、光触媒機能を有する物質としてアナターゼ型酸化チタンを使用することにより、より光触媒機能の高い釉薬を作製できると共に、６００℃以上７００℃未満で焼成可能であることにより、アナターゼ型酸化チタンが光触媒機能を喪失するルチル型酸化チタンに変容することもなく、光触媒効果が高い釉薬層を形成できる。
請求項３に記載の発明によれば、光触媒機能を有する物質を多量に含有するため、より光触媒効果が高い釉薬層を形成できる。
請求項４に記載の発明によれば、釉薬を構成する組成物の粒子径を極小とすることにより、光触媒機能を有する物質の総表面積が増大すると共に、それらが付着する部位の総表面積も増大し、より光触媒効果が高い釉薬層を形成できる。
請求項５に記載の発明によれば、釉薬層がガラス状に熔融することなく、多孔性を有し組成物が絡まり合い縺れ合った状態となり、そのようなマット状の多孔質釉薬層の表面および内部には大量の光触媒機能を有する物質が露呈した状態で焼結しているため、汚染物質等との接触が多く、さらに吸着性にも優れており、より光触媒効果が高い釉薬層を形成できる。
請求項６に記載の発明によれば、光触媒機能を有する物質の総表面積が極めて大きく光触媒効果が高くなると共に、汚染物質の吸着特性に優れた光触媒機能を有する製品となる。
According to the first aspect of the present invention, a substance having a photocatalytic function can be effectively adhered to the surface of the substrate simply by being applied to the substrate and baked, and can exhibit an extremely high photocatalytic function, and also has water resistance or weather resistance. In addition, the glaze layer is excellent in adsorptivity without adding a substance having excellent adsorption characteristics.
According to the invention described in claim 2, by using anatase-type titanium oxide as a substance having a photocatalytic function, it is possible to produce a glaze with a higher photocatalytic function and to be able to be fired at 600 ° C. or higher and lower than 700 ° C. Thus, the glaze layer having a high photocatalytic effect can be formed without transforming the anatase type titanium oxide into the rutile type titanium oxide that loses the photocatalytic function.
According to invention of Claim 3, since the substance which has a photocatalytic function is contained in large quantities, the glaze layer with a higher photocatalytic effect can be formed.
According to invention of Claim 4, by making the particle diameter of the composition which comprises a glaze minimum, the total surface area of the substance which has a photocatalytic function increases, and the total surface area of the site | part to which they adhere also increases. Thus, a glaze layer having a higher photocatalytic effect can be formed.
According to the invention described in claim 5, the glaze layer does not melt into a glass shape, and has a porosity and the composition is entangled and entangled, and the surface of such a mat-like porous glaze layer In addition, a large amount of material having photocatalytic function is sintered in the inside, so there is much contact with pollutants, etc., and it has excellent adsorptivity, forming a glaze layer with higher photocatalytic effect it can.
According to the invention described in claim 6, the total surface area of the substance having the photocatalytic function is extremely large, the photocatalytic effect is increased, and the product having the photocatalytic function excellent in the adsorption property of the pollutant is obtained.
本発明の光触媒機能を有する物質を含有した釉薬は、光触媒機能を有する物質を含有し、マット釉に形成したことにより、基材に塗布して焼成するのみで光触媒効果が高い釉薬層を形成可能としたものである。以下、具体的に詳述する。 The glaze containing a substance having a photocatalytic function of the present invention contains a substance having a photocatalytic function, and can be formed into a matt wrinkle so that a glaze layer having a high photocatalytic effect can be formed simply by applying to a substrate and baking. It is what. The details will be described below.
図１は本発明の光触媒機能を有する物質を含有した釉薬を用いて作製した光触媒機能を有する製品の表面を撮影した電子顕微鏡写真であり、図２は本発明の光触媒機能を有する物質を含有した釉薬を用いて作製した光触媒機能を有する製品の表面に存在する酸化チタンをＸ線マイクロアナライザーにより白点で表示した画像であり、図３は本発明の光触媒機能を有する物質を含有した釉薬を用いて作製した光触媒機能を有する製品の断面を撮影した電子顕微鏡写真であり、図４は本発明の光触媒機能を有する物質を含有した釉薬を用いて作製した光触媒機能を有する製品の断面に存在する酸化チタンをＸ線マイクロアナライザーにより白点で表示した画像である。なお、図４中、帯状に白点が多く分布している部位が釉薬層である。 FIG. 1 is an electron micrograph of the surface of a product having a photocatalytic function produced using a glaze containing a substance having a photocatalytic function of the present invention, and FIG. 2 contains the substance having a photocatalytic function of the present invention. FIG. 3 is an image in which titanium oxide present on the surface of a product having a photocatalytic function produced using a glaze is displayed with a white dot by an X-ray microanalyzer, and FIG. 3 uses the glaze containing the substance having the photocatalytic function of the present invention. FIG. 4 is an electron micrograph of a cross-section of a product having a photocatalytic function produced in the above, and FIG. 4 is an oxidation present in the cross-section of a product having a photocatalytic function produced using a glaze containing a substance having a photocatalytic function of the present invention It is the image which displayed titanium by the white spot with the X-ray microanalyzer. In FIG. 4, a portion where many white spots are distributed in a band shape is the glaze layer.
マット釉とは、釉が熔けた状態から冷えて固まる間に表面がちじれて亀裂が生成されたり、一部の成分が結晶化したりして、微細の凹凸結晶や気泡が生じるように調合された釉薬（艶消し釉）で、結晶粒によって光が散乱して光沢がなく艶消し状の釉薬層を形成するものである。 Matte cocoons were formulated so that fine cracked crystals and bubbles are generated by cracking the surface and crystallizing some components while the cocoon is cooled and solidified from the melted state. It is a glaze (matte glazing), in which light is scattered by crystal grains to form a matte glaze layer with no gloss.
このマット釉としては種々のものがあり、例えば、亜鉛マット釉、カオリン質マット釉、タルクマット釉、塩基質マット釉、珪酸質マット釉などが挙げられる。 There are various types of mat mats, such as zinc mats, kaolin mats, talc mats, basic mats, siliceous mats, and the like.
本発明の釉薬は、光触媒機能を有する物質を混入してマット釉に形成したものであり、これにより、通常の釉薬と同様に基材に塗布して焼成するのみで光触媒機能を有する物質を基材表面に露呈した状態で大量焼結でき極めて高い光触媒機能を発揮できる。より具体的には、図１ないし図４に示すように、基材に形成された釉薬層は多孔質的な性状を有し、かつ微細な凹凸が表面または内部に形成され、光触媒機能を有する物質が露呈した状態でかつ溶融した他の組成物に保持された状態で焼結しているため、光触媒機能を有する物質の総表面積が極めて大きい。また、マット釉が吸着性に優れている上に、大量に露呈している光触媒機能を有する物質自体も吸着性に優れているため、別段、吸着性に優れた物質を混入しなくても汚染物質を吸着しやすく、光触媒機能に優れた釉薬層を形成できる。 The glaze of the present invention is formed into a mat wrinkle by mixing a substance having a photocatalytic function. By this, it is based on a substance having a photocatalytic function only by being applied to a substrate and fired in the same manner as a normal glaze. It can be sintered in a large amount in the exposed state on the material surface and can exhibit extremely high photocatalytic function. More specifically, as shown in FIGS. 1 to 4, the glaze layer formed on the base material has a porous property, and fine irregularities are formed on the surface or inside thereof, and has a photocatalytic function. Since the material is sintered while being exposed and held in another molten composition, the total surface area of the material having a photocatalytic function is extremely large. In addition, the matt mat has excellent adsorptivity, and the substance with a photocatalytic function that is exposed in large quantities is also excellent in adsorptivity. It is easy to adsorb substances and can form a glaze layer with excellent photocatalytic function.
光触媒機能を有する物質としては、現在確認されている中で最も顕著な光触媒機能を有していること、および高い吸着特性を有することから酸化チタンが好適に使用できるが、これに限定されるものではなく、他の光触媒機能を有する物質を使用してもよい。なお、光触媒機能を有する物質は一種類のみではなく、複数種を組み合わせて使用してもよい。 As a substance having a photocatalytic function, titanium oxide can be preferably used because it has the most remarkable photocatalytic function currently confirmed and has high adsorption characteristics, but is limited to this. Instead, a substance having another photocatalytic function may be used. Note that the substance having a photocatalytic function is not limited to one type, and a plurality of types may be used in combination.
また、酸化チタンとしては、アナターゼ型酸化チタン、ブルカッイト型酸化チタン、ルチル型酸化チタンなどどあるが、最も光触媒機能を発揮するアナターゼ型酸化チタンが好適である。さらに、本発明の光触媒機能を有する物質を含有した釉薬は、６００℃以上７００℃未満で低温焼成可能であることが好ましい。これは、６００℃未満であると、十分な焼成が行われず釉薬層が基材表面から剥離しやすくなるからであり、他方、７００℃以上であると、アナターゼ型酸化チタンが光触媒機能を喪失するルチル型酸化チタンに変容し始めるため、光触媒効果が高い釉薬層の形成を阻害するおそれがあるからである。 Examples of titanium oxide include anatase-type titanium oxide, brookite-type titanium oxide, and rutile-type titanium oxide. Anatase-type titanium oxide that exhibits the most photocatalytic function is preferable. Furthermore, it is preferable that the glaze containing the substance having a photocatalytic function of the present invention can be fired at a low temperature of 600 ° C. or higher and lower than 700 ° C. This is because if the temperature is lower than 600 ° C., sufficient baking is not performed and the glaze layer is easily peeled off from the surface of the base material. On the other hand, if the temperature is 700 ° C. or higher, anatase-type titanium oxide loses its photocatalytic function. This is because the transformation into rutile type titanium oxide starts, which may hinder the formation of a glaze layer having a high photocatalytic effect.
光触媒機能を有する物質は、釉薬中に、４５重量％以上６０重量％未満含有されていることが好ましい。このように、光触媒機能を有する物質を多量に含有することにより光触媒機能が高い釉薬層を形成できる。なお、光触媒機能を有する物質が４５重量％未満であると、その分、ガラス化する組成物が増大し、光触媒機能を有する物質の露呈が阻害されるため４５重量％以上であることが好ましく、他方、６０重量％以上となると、光触媒機能を有する物質が他の組成物と共に一体となって釉薬層を構成せず、粉体として残存するおそれがあることから６０重量％未満が好ましい。 The substance having a photocatalytic function is preferably contained in the glaze at 45% by weight or more and less than 60% by weight. Thus, a glaze layer with a high photocatalytic function can be formed by containing a large amount of a substance having a photocatalytic function. In addition, if the substance having a photocatalytic function is less than 45% by weight, the composition to be vitrified is increased correspondingly, and exposure of the substance having a photocatalytic function is hindered. On the other hand, when the amount is 60% by weight or more, the substance having a photocatalytic function is integrated with other compositions to form a glaze layer and may remain as a powder.
さらに、光触媒機能を有する物質を含有した釉薬は、粒子径が５μｍ以下の組成物を９０％以上含有していることが好ましく、このように、釉薬を構成する組成物の粒子径を極小とすることにより、光触媒機能を有する物質の総表面積が増大すると共に、それらが付着する部位の総表面積も増大し、より光触媒効果が高い釉薬層が形成される。なお、釉薬を構成する組成物（光触媒機能を有する物質を含む）は調合された後、粉砕機にて粉砕されて粒子径が調製されている。 Furthermore, the glaze containing a substance having a photocatalytic function preferably contains 90% or more of a composition having a particle size of 5 μm or less, and thus the particle size of the composition constituting the glaze is minimized. As a result, the total surface area of the substance having the photocatalytic function is increased, and the total surface area of the portion to which the substance is attached is also increased, so that a glaze layer having a higher photocatalytic effect is formed. In addition, the composition (including the substance having a photocatalytic function) constituting the glaze is prepared and then pulverized by a pulverizer to prepare a particle size.
つぎに、本発明の光触媒機能を有する製品について説明する。
本発明の光触媒機能を有する製品は、光触媒機能を有する物質を含有してマット釉薬に形成した光触媒機能を有する物質を含有した釉薬を、基材に施釉し焼成して形成したものである。
Next, the product having the photocatalytic function of the present invention will be described.
The product having a photocatalytic function of the present invention is formed by applying a glaze containing a substance having a photocatalytic function, which is formed on a mat glaze, containing a substance having a photocatalytic function, and then baking the base.
基材としては、陶磁器素地が好適であるが、これに限定されるものではなく、例えばガラス質素地や金属などを基材としたものも本発明の範疇に包含される。 As the base material, a ceramic base is suitable, but is not limited to this, and for example, a base made of a vitreous base or a metal is also included in the scope of the present invention.
陶磁器素地は様々な形態に成形することにより、その目的に応じた各種製品（例えば置物、タイル、煉瓦、植木鉢、壁材）が作製できる。具体的には、本発明の光触媒機能を有する製品は、陶磁器素地であれば、成形工程、乾燥工程、釉薬塗布工程、焼成工程を経て作製される。そして、本発明の光触媒機能を有する製品は、焼成されてマット状の多孔質釉薬層が基材表面に形成されており、このマット状の多孔質釉薬層の表面および内部には多量の光触媒機能を有する物質が露呈した状態で焼結している。そのため、光触媒機能を有する物質が釉薬層から落ちることがなく、耐水性または耐候性等に優れ経時変化も少ない。 By forming the ceramic body into various forms, various products (for example, figurines, tiles, bricks, flower pots, wall materials) according to the purpose can be produced. Specifically, if the product having the photocatalytic function of the present invention is a ceramic body, it is produced through a molding process, a drying process, a glaze application process, and a firing process. The product having the photocatalytic function of the present invention is baked to form a mat-like porous glaze layer on the surface of the substrate, and a large amount of photocatalytic function is formed on the surface and inside of the mat-like porous glaze layer. It is sintered in a state where the substance having s is exposed. Therefore, a substance having a photocatalytic function does not fall from the glaze layer, and is excellent in water resistance, weather resistance, etc., and hardly changes over time.
（具体的実施例）
本発明の光触媒機能を有する物質を含有した釉薬を、以下の表１に示した成分組成に調合した後、粉砕機にて粉砕して調製した。この実施例の釉薬における光触媒機能を有する物質はアナターゼ型酸化チタンであり、このアナターゼ型酸化チタンが釉薬全体の約５７重量％含有され、粒子径が５μｍ以下の組成物を９０％以上含有したものとなっている。
(Specific examples)
The glaze containing the substance having a photocatalytic function of the present invention was prepared by preparing the component composition shown in Table 1 below and then pulverizing with a pulverizer. The substance having a photocatalytic function in the glaze of this example is anatase-type titanium oxide, and the anatase-type titanium oxide is contained in about 57% by weight of the whole glaze and contains a composition having a particle size of 5 μm or less and 90% or more. It has become.
（光触媒評価試験）
光触媒評価試験として、光触媒製品技術協議会が運営するＳＩＴＰＡマーク表示認証システムに基づく光触媒性能評価試験法（ガスバッグＢ法）を行った。
(Photocatalyst evaluation test)
As a photocatalyst evaluation test, a photocatalyst performance evaluation test method (gas bag B method) based on the SITPA mark display authentication system operated by the Photocatalyst Product Technical Council was performed.
（試験試料の作製）
約１００ｍｍ×１００ｍｍ×６ｍｍの寸法に素焼きした陶器製板状片の一表面に、上記表１の組成を有した光触媒機能を有する物質を含有した釉薬（アナターゼ型酸化チタンを約５７重量％含有し、粒子径が５μｍ以下の組成物を９０重量％以上含有したマット釉）を塗布し、７００℃で焼成して光触媒機能を有する釉薬層を備えた試料を４枚作製した。これらを水洗いし１１０℃で２時間乾燥させ、冷却した後、紫外線照射（１．０ｍＷ/ｃｍ２）を８時間行って前処理をし試験試料とした。
(Preparation of test sample)
A glaze containing about 57% by weight of anatase-type titanium oxide containing a substance having a photocatalytic function having the composition shown in Table 1 on one surface of an unglazed ceramic plate-like piece having a size of about 100 mm × 100 mm × 6 mm. 4 samples having a glaze layer having a photocatalytic function were prepared by applying a mat candy containing 90% by weight or more of a composition having a particle size of 5 μm or less and firing at 700 ° C. These were washed with water, dried at 110 ° C. for 2 hours, cooled, and then pretreated by ultraviolet irradiation (1.0 mW / cm 2 ) for 8 hours to obtain test samples.
（試験方法）
ミニコック付き５ｌの容量を有したフッ素樹脂製テドラーバッグ内に、試験試料とアセトアルデヒドガスを入れ暗所にて６時間静置させて当初ガス濃度を測定した。
その後、暗所にて２０時間静置したものを暗条件試験区とし、他方、紫外線照射（１．０ｍＷ/ｃｍ２）を２０時間行ったものを明条件試験区として、アセトアルデヒドの濃度を検知管にて測定した。なお、暗条件試験区および明条件試験区についてそれぞれ２試験つづ行い、各試験区ごとにガス濃度の平均値を算出した。
(Test method)
A test sample and acetaldehyde gas were placed in a fluororesin tedlar bag having a capacity of 5 liters with a mini-cock and allowed to stand in the dark for 6 hours, and the initial gas concentration was measured.
Thereafter, the sample which was allowed to stand for 20 hours in a dark place was used as a dark condition test group, while the sample subjected to ultraviolet irradiation (1.0 mW / cm 2 ) for 20 hours was used as a light condition test group, and the concentration of acetaldehyde was detected. Measured with Two tests were conducted for each of the dark condition test group and the light condition test group, and the average value of the gas concentration was calculated for each test group.
（その他の試験条件）
試験試料までの紫外線照射距離は１０ｃｍ、紫外線照射装置は日立製２０ｗ型ブラックライトＦＬ２０Ｓ−ＢＬ−Ｂを２本使用、紫外線強度計はトップコン製ＵＶＲ−２を使用、試験温度は２５度、検知管はガステック製９２Ｍを使用した。
(Other test conditions)
The UV irradiation distance to the test sample is 10cm, the UV irradiation device uses two Hitachi 20w type black light FL20S-BL-B, the UV intensity meter uses Topcon UVR-2, the test temperature is 25 degrees, detection The tube used was 92M manufactured by Gastec.
（試験結果）
当初ガス濃度は４試験平均値で９９ｐｐｍ、暗条件試験区のガス濃度の２試験平均値は９８ｐｐｍ、明条件試験区のガス濃度の２試験平均値は１３ｐｐｍであった。
(Test results)
The initial gas concentration was 99 ppm as an average value for 4 tests, the 2 test average value for the gas concentration in the dark condition test zone was 98 ppm, and the 2 test average value for the gas concentration in the light condition test zone was 13 ppm.
これらの数値を以下の式（１）に算入してアセトアルデヒドの除去率（％）を算出した。
除去率（％）＝（暗条件試験区のガス濃度−明条件試験区のガス濃度）/暗条件試験区のガス濃度×１００…（１）
＝（９８−１３）/９８×１００≒８６．７３％
These numerical values were included in the following formula (1) to calculate the removal rate (%) of acetaldehyde.
Removal rate (%) = (gas concentration in dark condition test section−gas concentration in light condition test section) / gas concentration in dark condition test section × 100 (1)
= (98-13) /98×100≈86.73%
この数値８６．７３％は、明条件試験区における試験試料（本発明の光触媒機能を有する製品）がアセトアルデヒドを８６．７３％除去したことを意味するものであり、光触媒製品技術協議会の性能基準によれば、除去率７０％以上を示す製品は光触媒製品と認証していることから、本発明の光触媒機能を有する製品は光触媒製品として極めて高い水準の製品であることが確認された。 This numerical value of 86.73% means that the test sample (the product having the photocatalytic function of the present invention) in the light condition test section has removed 86.73% of acetaldehyde, and is a performance standard of the Photocatalyst Products Technical Council. According to the above, since a product exhibiting a removal rate of 70% or more is certified as a photocatalyst product, it was confirmed that the product having the photocatalytic function of the present invention is a very high level product as a photocatalyst product.
Claims (6)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011108472A1 (en) * | 2010-03-01 | 2011-09-09 | 株式会社 オハラ | Glass for glaze, glaze, and photocatalyst member |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011108472A1 (en) * | 2010-03-01 | 2011-09-09 | 株式会社 オハラ | Glass for glaze, glaze, and photocatalyst member |
| JP5820799B2 (en) * | 2010-03-01 | 2015-11-24 | 株式会社オハラ | Glaze glass, glaze, and photocatalyst member |
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