WO2010107086A1 - Photocatalytic tile - Google Patents

Photocatalytic tile Download PDF

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Publication number
WO2010107086A1
WO2010107086A1 PCT/JP2010/054670 JP2010054670W WO2010107086A1 WO 2010107086 A1 WO2010107086 A1 WO 2010107086A1 JP 2010054670 W JP2010054670 W JP 2010054670W WO 2010107086 A1 WO2010107086 A1 WO 2010107086A1
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WO
WIPO (PCT)
Prior art keywords
tile
photocatalyst
photocatalytic
particles
oxide
Prior art date
Application number
PCT/JP2010/054670
Other languages
French (fr)
Japanese (ja)
Inventor
信 早川
秀紀 小林
Original Assignee
Toto株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009065531A external-priority patent/JP2012107376A/en
Priority claimed from JP2009065530A external-priority patent/JP2012107375A/en
Application filed by Toto株式会社 filed Critical Toto株式会社
Publication of WO2010107086A1 publication Critical patent/WO2010107086A1/en

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Classifications

    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/08—Flooring or floor layers composed of a number of similar elements only of stone or stone-like material, e.g. ceramics, concrete; of glass or with a top layer of stone or stone-like material, e.g. ceramics, concrete or glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00—Coverings or linings, e.g. for walls or ceilings
    • E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
    • E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
    • E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
    • E04F13/142—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass with an outer layer of ceramics or clays

Definitions

  • the present invention relates to a photocatalytic tile and a manufacturing method thereof.
  • photocatalysts such as titanium oxide have been used in many applications such as building exterior materials and interior materials.
  • solar energy can be used to provide a decomposition function for harmful substances such as NOx and SOx, to provide self-cleaning properties with rainwater, It becomes possible to give algae function.
  • photocatalyst is applied to the surface of the base material to add a function of decomposing toxic substances such as VOC (volatile organic compounds) using light energy, cigarette odors and odors. It is possible to impart a decomposition function of, and an antibacterial / antifungal function.
  • a technique for forming a photocatalytic layer on the tile surface is also known.
  • the tiles provided with a photocatalyst layer on the surface prevent algae in the pool, prevent hospital infections in the hospital, prevent the bathroom floor from being slimmed, and self-cleaning of the outer wall with rainwater (see the following prior patent document).
  • the object of the present invention is to provide a photocatalytic tile capable of sustaining a photocatalytic function and a method for producing the same even when exposed to severe wear conditions such as station concourses and airports.
  • the photocatalytic tile according to the first aspect of the present invention is characterized in that photocatalyst particles are impregnated and fixed in the vicinity of the surface of a porcelain or porcelain-free sintered tile firing base.
  • the photocatalyst tile according to the second aspect of the present invention is characterized in that a photocatalyst layer is further provided on the surface of the photocatalyst tile impregnated and fixed.
  • the photocatalyst tile according to this aspect is a photocatalyst tile including a porcelain or porcelain-free ceramic tile firing base and a photocatalyst layer fixed on the firing base, and the photocatalytic layer in the firing base.
  • the photocatalyst particles are impregnated and fixed in the vicinity of the surface on the side where is fixed.
  • a method for producing the photocatalyst tile wherein the water absorption rate of the surface is 3% or less after impregnating the photocatalyst particles on the surface of the tile generating feature. It is characterized by firing at a temperature.
  • a method for producing a photocatalytic tile according to the second aspect of the present invention wherein the method comprises impregnating the surface of the tile-generating feature with photocatalyst particles, and then absorbing the water on the surface. Baking is performed at a temperature at which the rate becomes 3% or less, and then a photocatalyst layer is formed on the surface side impregnated with the photocatalyst particles.
  • the photocatalyst tile according to the present invention is a photocatalyst tile characterized in that photocatalyst particles are impregnated and fixed in the vicinity of the surface of a porcelain or porcelain glazed tile firing base.
  • the photocatalytic tiles according to the present invention have good rub resistance, so that the photocatalytic function can last for a long time even when used in severe wear conditions such as station concourses and airports. To demonstrate.
  • the photocatalyst particles impregnated and fixed near the surface of the tile firing substrate are preferably photocatalytic metal oxide particles, such as titanium oxide, preferably rutile titanium oxide, tin oxide, zinc oxide, strontium titanate. Tungsten oxide and cerium oxide can be suitably used. Two or more of the above may be mixed and used.
  • the metal oxide particles may be doped with metals such as platinum, gold, silver, silver oxide, copper, cuprous oxide, cupric oxide, iron, and anions such as nitrogen and fluorine. You may use what gave antibacterial property, antifungal property, antiviral property, etc., or was excited by visible light.
  • the photocatalyst particles preferably have an average particle size of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less.
  • 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 photocatalytic tile according to the present invention preferably has a water absorption rate of 3% or less on the surface of the tile fired substrate on which the photocatalyst particles are impregnated and fixed.
  • the water absorption rate refers to a ratio of the volume of so-called naturally absorbed water to the volume of the entire tile, which is measured by a method of immersing in water at room temperature for 24 hours to absorb the material.
  • the portion where the photocatalyst particles are impregnated and fixed is preferably 1 mm or more from the surface, more preferably 2 mm or more, and further preferably 3 mm or more.
  • the amount of the photocatalyst particles impregnated and fixed in the photocatalyst tile according to the present invention is the photocatalyst with respect to the sum of the calcined green area and the photocatalyst particle area on the surface obtained by cutting the lower part near the surface of the tile fired body horizontally (that is, parallel to the surface). It is preferable that the ratio of the particle area is 1 area% or more and 50 area% or less. When the amount of the photocatalyst particles is within this range, the sintered body is sufficiently firmly bonded by the sintering reaction, and excellent wear resistance is exhibited, and the photocatalytic function after wear is advantageously exhibited, preferable.
  • the water absorption rate of the surface of the fired tile base impregnated with the photocatalyst particles is 0.1% or more, preferably 0.3% or more.
  • the water absorption rate refers to a ratio of the volume of so-called naturally absorbed water to the volume of the entire tile, which is measured by a method of immersing in water at room temperature for 24 hours to absorb the material.
  • vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper are provided in the vicinity of the surface of the tile firing substrate in order to express higher photocatalytic activity.
  • At least one metal selected from the group consisting of silver, platinum and gold and / or a metal compound comprising the metal may be added.
  • a photocatalyst tile characterized in that a photocatalyst layer is further provided on the surface of the photocatalyst tile impregnated and fixed.
  • the photocatalyst particles constituting the photocatalyst layer are preferably photocatalytic metal oxide particles, such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, tin oxide, zinc oxide, strontium titanate, Tungsten oxide and cerium oxide can be suitably used. Two or more of the above may be mixed and used.
  • the metal oxide particles may be doped with metals such as platinum, gold, silver, silver oxide, copper, cuprous oxide, cupric oxide, iron, and anions such as nitrogen and fluorine. Those having enhanced antibacterial performance, antifungal performance, antiviral performance, etc., or those excited by visible light may be used.
  • the photocatalyst particles constituting the photocatalyst layer preferably have an average particle diameter of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less.
  • the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles entering a 200,000-fold field of view with a scanning electron microscope.
  • a binder in addition to the photocatalyst particles, a binder may be added to the photocatalyst layer in order to enhance the wear of the photocatalyst layer.
  • a binder an amorphous oxide such as amorphous silica, amorphous titania or alkali silicate, or a hard binder such as silicone can be suitably used.
  • the photocatalyst layer has at least one selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold in order to develop higher photocatalytic activity.
  • a metal compound and / or a metal compound comprising the metal may be added.
  • the binder is added in a large amount of 20 to 99% by weight to the photocatalyst layer, it is preferable to add these metal compounds. As a result, excellent wear resistance is exhibited, and an advantage that the photocatalytic function after wear is maintained is obtained.
  • inorganic oxide particles may be added to the photocatalyst layer in order to develop a higher gas decomposition function.
  • inorganic oxide particles include silica, alumina, zirconia, ceria, yttria, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, hafnia, barium titanate, calcium silicate, aluminum borate, titanic acid. Potassium, zeolite, apatite, calcium phosphate and the like can be suitably used.
  • the inorganic oxide particles have an average particle size of more than 5 nm and not more than 50 nm, preferably not less than 10 and not more than 40 nm, in order to increase the contact probability between the photocatalyst and harmful gas and to make the film strong against wear and abrasion. Is preferable.
  • 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 particle shape, a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
  • the film thickness of the photocatalyst layer may be appropriately determined in consideration of its friction resistance, photocatalytic function, etc., but is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 5 ⁇ m or less.
  • the film thickness of the photocatalyst layer is within this range, it is possible to obtain an advantage that the transparency of the photocatalyst layer is ensured while the sustainability of a good photocatalyst function is exhibited.
  • the photocatalyst tile of the present invention has excellent abrasion resistance, and the photocatalytic function after wear is sustained, so that the floor tile applied to places exposed to severe wear conditions such as station concourses and airports, Furthermore, it can be suitably used as an exterior tile that is subjected to severe conditions regarding wear.
  • the photocatalytic tile according to the first aspect of the present invention is produced by impregnating photocatalyst particles on the surface of the tile-forming form and then firing at a temperature at which the water absorption rate of the surface is 3% or less. Can do.
  • impregnated formations made of porcelain or porcelain tile base material are impregnated with photocatalyst particles.
  • the depth of impregnation of the photocatalyst particles from the surface of the formed body is preferably 1 mm or more from the surface.
  • a wet method can be suitably used as the impregnation method for the photocatalyst particles.
  • the photocatalyst particle-containing liquid is applied by a method such as spraying, dip, or flow to a generated shape obtained by molding a porcelain or porcelain tile base material, the surface of the generated shape is dried.
  • the depth of impregnation of the photocatalyst particles from the surface of the formed body is a method of adjusting the viscosity of the photocatalyst-containing liquid, the factor governing the impregnation rate such as the application method of the photocatalyst-containing liquid, and the substrate drying temperature in advance. It can control by selecting suitably the factor which controls drying speeds, such as.
  • firing is performed at a temperature at which the water absorption rate of the obtained surface is 3% or less to obtain a fired body.
  • this temperature may be appropriately determined depending on the composition of the tile substrate, it is generally 1000 ° C or higher, preferably 1100 ° C or higher and 1500 ° C or lower, more preferably 1200 ° C or higher and 1400 ° C or lower. Therefore, when titanium oxide particles are used as the photocatalyst particles, even if the starting material is anatase or brookite, it often undergoes a phase transition to rutile.
  • a photocatalyst layer is then formed on the surface side impregnated with the photocatalyst particles of the fired body.
  • the photocatalyst formation method here is, for example, a dry method or a wet method known as a method for forming a photocatalyst layer described in WO96 / 29375 pamphlet, WO00 / 06300 pamphlet, JP-A-2003-93896, and the like. The law is available.
  • Example 1 A plurality of solid shaped products formed from a porcelain tile base material by a dry press method are dried at 100 ° C., and when the surface is 60 ° C., anatase-type titanium oxide having an average particle size of 70 nm and a silver compound are contained. The solution was spray coated and then dried again at 100 ° C. From the analysis of Ti and Ag in one cross section of the resulting shaped body, the penetration depth of the photocatalytic particles and Ag from the surface of the shaped body was estimated to be about 3 mm. Next, this formed shape was fired at a temperature of 1250 to 1300 ° C. to produce a fired body. The water absorption of this fired body was 0.2%.
  • Example 2 A plurality of solid generated shapes formed by porcelain tile base material by dry pressing are dried at 100 ° C. Thereafter, the substrate surface temperature was adjusted to 50 ° C. to 70 ° C., and a liquid containing anatase-type titanium oxide having an average particle diameter of 70 nm and a silver compound was spray-coated and then dried again at 100 ° C. From the analysis of Ti and Ag in one cross section of the resulting shaped body, the penetration depth of the photocatalytic particles and Ag from the surface of the shaped body was estimated to be about 3 mm. Next, this formed body was fired at a temperature of 1250 to 1350 ° C. to produce a fired body. The water absorption of this fired body was 0.2%.
  • a liquid mixture of anatase-type titanium oxide having an average particle size of 50 nm and alkali silicate was applied to the surface of the fired body by a flow coating method, and then dried and cured to form a photocatalyst layer having a thickness of 0.5 ⁇ m.
  • Comparative Example 1 A mixture of anatase-type titanium oxide having an average particle size of 50 nm and an alkali silicate was applied to the surface of the fired tile-free body by a flow coat method, and then dried and cured to obtain a film thickness of 0.5 ⁇ m. A photocatalytic layer was formed.

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Abstract

Disclosed is a photocatalytic tile capable of sustaining the photocatalytic action thereof even under severe wear conditions such as in a station concourse or in an airport. This photocatalytic tile is characterized in that photocatalytic particles have been fixed by impregnation in the vicinity of the surface of the baked body of a porcelain or stoneware unglazed tile. A photocatalytic tile, which is further provided with a photocatalytic layer on the surface having the photocatalytic particles fixed thereto by impregnation, also exhibits high wear resistance and good photocatalytic action.

Description

光触媒タイルPhotocatalytic tile
　本発明は、光触媒タイル、およびその製造方法に関する。 The present invention relates to a photocatalytic tile and a manufacturing method thereof.
　酸化チタンなどの光触媒が、近年、建築物の外装材、内装材など多くの用途において利用されている。外装用途については、基材表面に光触媒を塗装することにより、太陽光のエネルギーを利用してＮＯｘ、ＳＯｘ等の有害物質の分解機能を付与したり、雨水によるセルフクリーニング性を付与したり、防藻機能を付与したりすることが可能となる。また内装用途についても、基材表面に光触媒を塗装することにより、光エネルギーを利用してＶＯＣ（揮発性有機化合物volatile organic compounds）等の有害物質の分解機能を付与したり、たばこの臭いや悪臭の分解機能を付与したり、抗菌・防カビ機能を付与したりすることが可能となる。 In recent years, photocatalysts such as titanium oxide have been used in many applications such as building exterior materials and interior materials. For exterior applications, by applying a photocatalyst to the surface of the base material, solar energy can be used to provide a decomposition function for harmful substances such as NOx and SOx, to provide self-cleaning properties with rainwater, It becomes possible to give algae function. For interior use, photocatalyst is applied to the surface of the base material to add a function of decomposing toxic substances such as VOC (volatile organic compounds) using light energy, cigarette odors and odors. It is possible to impart a decomposition function of, and an antibacterial / antifungal function.
　タイル表面に光触媒層を形成する技術も知られている。その表面に光触媒層が設けられたタイルにより、プール内の防藻、病院内の院内感染防止、浴室床のぬめり防止、外壁の雨水によるセルフクリーニング等がなされている（下記先行特許文献参照）。 A technique for forming a photocatalytic layer on the tile surface is also known. The tiles provided with a photocatalyst layer on the surface prevent algae in the pool, prevent hospital infections in the hospital, prevent the bathroom floor from being slimmed, and self-cleaning of the outer wall with rainwater (see the following prior patent document).
特開昭６１－８３１０６号公報JP 61-83106 A 特開平５－２５３５４４号公報JP-A-5-253544 特開平７－１０２６７８号公報Japanese Patent Laid-Open No. 7-102678 ＷＯ９６／２９３７５号公報WO96 / 29375 特開平８－２６７６４６号公報JP-A-8-267646 特開２００１－２５８７８３号公報JP 2001-258783 A 特開２００１－４９８２９号公報JP 2001-49829 A ＷＯ００／６３００号公報WO00 / 6300
　駅のコンコースや空港などのような重歩行の場所（人が非常に多く通る場所）では、人が硬質な靴で歩き回る、重い台車が通る等のため、その表面には高い耐摩耗性が要求される。特に外装用途では、人が硬質な靴で歩き回るということに加え、その表面に強風で砂が吹き付けるなどの過酷な条件での使用も想定される。このような使用にタイルが耐え得るか否かを確認するために、ＰＥＩ試験、すなわち砂とセラミックスとを混合した水中下で鉄球をタイルに擦ることを繰り返し、目視で変化がないことを確認する試験等が広く行われている。 In heavy-walking places such as station concourses and airports (places where a lot of people pass), the surface has high wear resistance because people walk around with hard shoes, heavy carts, etc. Required. In particular, in exterior applications, in addition to people walking around with hard shoes, use under severe conditions such as blowing sand on the surface with strong wind is also assumed. In order to confirm whether the tile can withstand such use, repeated PEI test, that is, rubbing the iron ball against the tile in water mixed with sand and ceramics, and confirming that there is no visual change There are a wide range of tests to be performed.
　しかし、従来の光触媒タイルでは、光触媒層は一般に膜厚がサブミクロンオーダーかミクロンオーダーであるため、繰り返し回数が多くなると、上記評価では光触媒層が失われてしまう。従って、上述のような過酷な条件に耐え得る光触媒タイルの実現は難しいものと当業界では理解されていた。
　しかしながら、今般、本発明者らは、磁器質またはせっ器質の無釉タイル焼成素地の表面近傍に光触媒を含浸固定させることで、良好な耐摩耗性が得られるとの知見を得た。本発明はかかる知見に基づくものである。
　すなわち、本発明は、駅のコンコースや空港などのような過酷な摩耗条件に晒される場合であっても、光触媒機能を持続可能な光触媒タイルおよびその製造方法の提供をその目的としている。 However, in the conventional photocatalytic tile, since the film thickness of the photocatalyst layer is generally in the submicron order or micron order, if the number of repetitions increases, the photocatalyst layer is lost in the above evaluation. Accordingly, it has been understood in the art that it is difficult to realize a photocatalytic tile that can withstand the severe conditions described above.
However, the present inventors have recently found that good wear resistance can be obtained by impregnating and fixing a photocatalyst in the vicinity of the surface of a porcelain or porcelain-free solid tile firing base. The present invention is based on such knowledge.
That is, the object of the present invention is to provide a photocatalytic tile capable of sustaining a photocatalytic function and a method for producing the same even when exposed to severe wear conditions such as station concourses and airports.
　そして、本発明の第一の態様による光触媒タイルは、磁器質またはせっ器質の無釉タイル焼成素地の表面近傍に光触媒粒子が含浸固定されてなることを特徴とするものである。
　また、本発明の第二の態様による光触媒タイルは、上記の光触媒タイルの光触媒粒子が含浸固定された表面上に、さらに光触媒層が設けられてなることを特徴とするものである。言い換えれば、この態様による光触媒タイルは、磁器質またはせっ器質の無釉タイル焼成素地と、前記焼成素地上に固定された光触媒層とを備えた光触媒タイルであって、前記焼成素地における前記光触媒層が固定されている側の表面近傍には光触媒粒子が含浸固定されてなることを特徴とするものである。
　また、本発明の別の態様によれば、上記光触媒タイルの製造方法が提供され、その方法は、タイル生成形体表面に光触媒粒子を含浸させた後に、前記表面の吸水率が３％以下になる温度で焼成することを特徴とするものである。
　さらに本発明の別の態様によれば、上記本発明の第二の態様による光触媒タイルの製造方法が提供され、その方法は、タイル生成形体表面に光触媒粒子を含浸させた後に、前記表面の吸水率が３％以下になる温度で焼成し、その後に、前記光触媒粒子を含浸させた表面側に光触媒層を形成することを特徴とする。 The photocatalytic tile according to the first aspect of the present invention is characterized in that photocatalyst particles are impregnated and fixed in the vicinity of the surface of a porcelain or porcelain-free sintered tile firing base.
The photocatalyst tile according to the second aspect of the present invention is characterized in that a photocatalyst layer is further provided on the surface of the photocatalyst tile impregnated and fixed. In other words, the photocatalyst tile according to this aspect is a photocatalyst tile including a porcelain or porcelain-free ceramic tile firing base and a photocatalyst layer fixed on the firing base, and the photocatalytic layer in the firing base. The photocatalyst particles are impregnated and fixed in the vicinity of the surface on the side where is fixed.
According to another aspect of the present invention, there is provided a method for producing the photocatalyst tile, wherein the water absorption rate of the surface is 3% or less after impregnating the photocatalyst particles on the surface of the tile generating feature. It is characterized by firing at a temperature.
Furthermore, according to another aspect of the present invention, there is provided a method for producing a photocatalytic tile according to the second aspect of the present invention, wherein the method comprises impregnating the surface of the tile-generating feature with photocatalyst particles, and then absorbing the water on the surface. Baking is performed at a temperature at which the rate becomes 3% or less, and then a photocatalyst layer is formed on the surface side impregnated with the photocatalyst particles.
　光触媒タイル
　本発明による光触媒タイルは、磁器質またはせっ器質の無釉タイル焼成素地の表面近傍には光触媒粒子が含浸固定されていることを特徴とする光触媒タイルである。本発明による光触媒タイルは、良好な耐摩擦性を有し、その結果、駅のコンコースや空港などのような過酷な摩耗条件に晒される場合において使用されても、光触媒機能を長期にわたり持続して発揮する。 Photocatalyst tile The photocatalyst tile according to the present invention is a photocatalyst tile characterized in that photocatalyst particles are impregnated and fixed in the vicinity of the surface of a porcelain or porcelain glazed tile firing base. The photocatalytic tiles according to the present invention have good rub resistance, so that the photocatalytic function can last for a long time even when used in severe wear conditions such as station concourses and airports. To demonstrate.
　本発明において、タイル焼成素地の表面近傍に含浸固定される光触媒粒子としては、光触媒性金属酸化物粒子が好ましく、例えば、酸化チタン、好ましくはルチル型酸化チタン、酸化錫、酸化亜鉛、チタン酸ストロンチウム、酸化タングステン、酸化セリウムが好適に利用可能である。上記のうち２種以上を混合して利用してもよい。また、光触媒粒子として、上記金属酸化物粒子に白金、金、銀、酸化銀、銅、酸化第一銅、酸化第二銅、鉄等の金属や窒素、フッ素等の陰イオン等をドープして抗菌性、防黴性、抗ウィルス性等を付与し、あるいは可視光で励起するようにしたものを用いてもよい。 In the present invention, the photocatalyst particles impregnated and fixed near the surface of the tile firing substrate are preferably photocatalytic metal oxide particles, such as titanium oxide, preferably rutile titanium oxide, tin oxide, zinc oxide, strontium titanate. Tungsten oxide and cerium oxide can be suitably used. Two or more of the above may be mixed and used. In addition, as photocatalyst particles, the metal oxide particles may be doped with metals such as platinum, gold, silver, silver oxide, copper, cuprous oxide, cupric oxide, iron, and anions such as nitrogen and fluorine. You may use what gave antibacterial property, antifungal property, antiviral property, etc., or was excited by visible light.
　本発明において、光触媒粒子は１０ｎｍ以上１００ｎｍ未満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。 In the present invention, the photocatalyst particles preferably have an average particle size of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less. 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.
　本発明による光触媒タイルは、光触媒粒子が含浸固定されたタイル焼成素地表面の吸水率が３％以下であるのが好ましい。吸水率が３％以下であることで、優れた耐摩耗性が発揮されるとともに、ある程度の摩耗後も光触媒機能が持続されるとの利点が得られる。ここで、吸水率とは、２４時間常温の水に浸漬して材料に吸水させる方法により測定される、いわゆる自然吸水された水の体積の、タイル全体の体積に対する比をいう。 The photocatalytic tile according to the present invention preferably has a water absorption rate of 3% or less on the surface of the tile fired substrate on which the photocatalyst particles are impregnated and fixed. When the water absorption is 3% or less, an excellent wear resistance is exhibited, and an advantage that the photocatalytic function is maintained even after a certain amount of wear is obtained. Here, the water absorption rate refers to a ratio of the volume of so-called naturally absorbed water to the volume of the entire tile, which is measured by a method of immersing in water at room temperature for 24 hours to absorb the material.
　本発明による光触媒タイルにおいて、光触媒粒子が含浸固定されている部分は表面から１ｍｍ以上が好ましく、より好ましくは２ｍｍ以上、さらに好ましくは３ｍｍ以上である。これにより、ある程度摩耗が進んでも光触媒機能を充分に持続することが可能となる。 In the photocatalyst tile according to the present invention, the portion where the photocatalyst particles are impregnated and fixed is preferably 1 mm or more from the surface, more preferably 2 mm or more, and further preferably 3 mm or more. As a result, the photocatalytic function can be sufficiently maintained even if the wear proceeds to some extent.
　本発明による光触媒タイルにおける、含浸固定されている光触媒粒子の量は、タイル焼成体表面近傍下部を水平（すなわち、表面と並行）に切断した面において、焼成素地面積と光触媒粒子面積の和に対する光触媒粒子面積の比率が１面積％以上５０面積％以下であるのが好ましい。光触媒粒子の量がこの範囲にあることで、焼成素地が焼結反応により充分強固に結合し、優れた耐摩耗性が発揮されるとともに、摩耗後の光触媒機能が有利に発揮されることとなり、好ましい。 The amount of the photocatalyst particles impregnated and fixed in the photocatalyst tile according to the present invention is the photocatalyst with respect to the sum of the calcined green area and the photocatalyst particle area on the surface obtained by cutting the lower part near the surface of the tile fired body horizontally (that is, parallel to the surface). It is preferable that the ratio of the particle area is 1 area% or more and 50 area% or less. When the amount of the photocatalyst particles is within this range, the sintered body is sufficiently firmly bonded by the sintering reaction, and excellent wear resistance is exhibited, and the photocatalytic function after wear is advantageously exhibited, preferable.
　本発明による光触媒タイルにおいて、光触媒粒子が含浸固定されたタイル焼成素地表面の吸水率が０．１％以上、好ましくは０．３％以上とすることが好ましい。吸水率をこの範囲に置くことで、優れた耐摩耗性が発揮されるとともに、ガス分解機能が良好に発揮され、さらにある程度の摩耗後であっても、光触媒によるガス分解機能がより良好な状態で持続される点で有利である。ここで、吸水率とは、２４時間常温の水に浸漬して材料に吸水させる方法により測定される、いわゆる自然吸水された水の体積の、タイル全体の体積に対する比をいう。 In the photocatalyst tile according to the present invention, the water absorption rate of the surface of the fired tile base impregnated with the photocatalyst particles is 0.1% or more, preferably 0.3% or more. By setting the water absorption rate within this range, excellent wear resistance is exhibited, the gas decomposition function is demonstrated well, and even after some wear, the gas decomposition function by the photocatalyst is better It is advantageous in that it is sustained at Here, the water absorption rate refers to a ratio of the volume of so-called naturally absorbed water to the volume of the entire tile, which is measured by a method of immersing in water at room temperature for 24 hours to absorb the material.
　本発明の好ましい態様によれば、タイル焼成素地の表面近傍には、光触媒粒子以外に、さらに高い光触媒能を発現するために、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および／またはその金属からなる金属化合物を添加してもよい。これにより、本発明の光触媒タイルにあっては、優れた耐摩耗性とあわせて抗菌性が発揮されるとともに、摩耗後の光触媒機能がより良好な状態で持続される。 According to a preferred embodiment of the present invention, in addition to the photocatalyst particles, vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper are provided in the vicinity of the surface of the tile firing substrate in order to express higher photocatalytic activity. , At least one metal selected from the group consisting of silver, platinum and gold and / or a metal compound comprising the metal may be added. Thereby, in the photocatalyst tile of the present invention, antibacterial properties are exhibited together with excellent wear resistance, and the photocatalytic function after wear is maintained in a better state.
　本発明の第二態様によれば、上記の光触媒タイルの光触媒粒子が含浸固定された表面上に、さらに光触媒層が設けられてなることを特徴とする光触媒タイルが提供される。このように光触媒層をさらに設けることで、光触媒機能が増強された光触媒タイルが実現される。 According to the second aspect of the present invention, there is provided a photocatalyst tile characterized in that a photocatalyst layer is further provided on the surface of the photocatalyst tile impregnated and fixed. By further providing a photocatalyst layer in this manner, a photocatalytic tile having an enhanced photocatalytic function is realized.
　本発明において、光触媒層を構成する光触媒粒子としては、光触媒性金属酸化物粒子が好ましく、例えば、アナターゼ型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタン、酸化錫、酸化亜鉛、チタン酸ストロンチウム、酸化タングステン、酸化セリウムが好適に利用可能である。上記のうち２種以上を混合して利用してもよい。また、光触媒粒子として、上記金属酸化物粒子に白金、金、銀、酸化銀、銅、酸化第一銅、酸化第二銅、鉄等の金属や窒素、フッ素等の陰イオン等をドープして抗菌性能、防黴性能、抗ウィルス性能等を高めたもの、あるいは可視光で励起するようにしたものを用いてもよい。 In the present invention, the photocatalyst particles constituting the photocatalyst layer are preferably photocatalytic metal oxide particles, such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, tin oxide, zinc oxide, strontium titanate, Tungsten oxide and cerium oxide can be suitably used. Two or more of the above may be mixed and used. In addition, as photocatalyst particles, the metal oxide particles may be doped with metals such as platinum, gold, silver, silver oxide, copper, cuprous oxide, cupric oxide, iron, and anions such as nitrogen and fluorine. Those having enhanced antibacterial performance, antifungal performance, antiviral performance, etc., or those excited by visible light may be used.
　光触媒層を構成する光触媒粒子は１０ｎｍ以上１００ｎｍ未満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ものである。 The photocatalyst particles constituting the photocatalyst layer preferably have an average particle diameter of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles entering a 200,000-fold field of view with a scanning electron microscope.
　また、本発明において、光触媒層には、光触媒粒子以外に、光触媒層の摩耗性を高めるために、結着剤を添加してもよい。結着剤としては、無定形シリカ、無定形チタニア、アルカリシリケート等のアモルファス酸化物、シリコーン等の硬質な結着剤が好適に利用可能である。 In the present invention, in addition to the photocatalyst particles, a binder may be added to the photocatalyst layer in order to enhance the wear of the photocatalyst layer. As the binder, an amorphous oxide such as amorphous silica, amorphous titania or alkali silicate, or a hard binder such as silicone can be suitably used.
　本発明において、光触媒層には、さらに高い光触媒能を発現するために、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および／またはその金属からなる金属化合物を添加してもよい。特に、光触媒層に対して、結着剤を２０重量～９９重量％と多量に添加する場合には、これら金属化合物を添加することが好ましい。これにより優れた耐摩耗性が発揮されるとともに、摩耗後の光触媒機能が持続されるとの利点が得られる。 In the present invention, the photocatalyst layer has at least one selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold in order to develop higher photocatalytic activity. A metal compound and / or a metal compound comprising the metal may be added. In particular, when the binder is added in a large amount of 20 to 99% by weight to the photocatalyst layer, it is preferable to add these metal compounds. As a result, excellent wear resistance is exhibited, and an advantage that the photocatalytic function after wear is maintained is obtained.
　本発明の好ましい態様によれば、光触媒層には、さらに高いガス分解機能を発現するために、無機酸化物粒子を添加してもよい。無機酸化物粒子としては、例えば、シリカ、アルミナ、ジルコニア、セリア、イットリア、酸化錫、酸化鉄、酸化マンガン、酸化ニッケル、酸化コバルト、ハフニア、チタン酸バリウム、ケイ酸カルシウム、ホウ酸アルミニウム、チタン酸カリウム、ゼオライト、アパタイト、リン酸カルシウム等が好適に利用できる。 According to a preferred embodiment of the present invention, inorganic oxide particles may be added to the photocatalyst layer in order to develop a higher gas decomposition function. Examples of inorganic oxide particles include silica, alumina, zirconia, ceria, yttria, tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, hafnia, barium titanate, calcium silicate, aluminum borate, titanic acid. Potassium, zeolite, apatite, calcium phosphate and the like can be suitably used.
　上記無機酸化物粒子は、５ｎｍを超え５０ｎｍ以下、好ましくは１０以上４０ｎｍ以下、の平均粒径を有するのが、光触媒と有害ガスの接触確率を高めつつ摩耗磨耗に対して強固な膜にする上で好ましい。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 inorganic oxide particles have an average particle size of more than 5 nm and not more than 50 nm, preferably not less than 10 and not more than 40 nm, in order to increase the contact probability between the photocatalyst and harmful gas and to make the film strong against wear and abrasion. Is preferable. 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 particle shape, a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
　本発明において光触媒層の膜厚はその耐摩擦性、光触媒機能などを考慮して適宜決定されてよいが、好ましくは０．１μｍ以上１０μｍ以下、より好ましくは０．２μｍ以上５μｍ以下である。光触媒層の膜厚がこの範囲にあることで、良好な光触媒機能の持続性を発揮するとともに、光触媒層の透明性が確保されるとの利点が得られる。 In the present invention, the film thickness of the photocatalyst layer may be appropriately determined in consideration of its friction resistance, photocatalytic function, etc., but is preferably 0.1 μm or more and 10 μm or less, more preferably 0.2 μm or more and 5 μm or less. When the film thickness of the photocatalyst layer is within this range, it is possible to obtain an advantage that the transparency of the photocatalyst layer is ensured while the sustainability of a good photocatalyst function is exhibited.
　本発明の光触媒タイルは優れた耐摩耗性を有するとともに、摩耗後の光触媒機能が持続されるので、駅のコンコースや空港などのような過酷な摩耗条件に晒される場所に適用した床タイル、さらには摩耗について過酷な条件におかれる外装タイルとして好適に使用可能となる。 The photocatalyst tile of the present invention has excellent abrasion resistance, and the photocatalytic function after wear is sustained, so that the floor tile applied to places exposed to severe wear conditions such as station concourses and airports, Furthermore, it can be suitably used as an exterior tile that is subjected to severe conditions regarding wear.
　光触媒タイルの製造方法
　本発明による第一の態様による光触媒タイルは、タイル生成形体表面に光触媒粒子を含浸させた後に、前記表面の吸水率が３％以下になる温度で焼成することにより製造することができる。 Method for Producing Photocatalytic Tile The photocatalytic tile according to the first aspect of the present invention is produced by impregnating photocatalyst particles on the surface of the tile-forming form and then firing at a temperature at which the water absorption rate of the surface is 3% or less. Can do.
　具体的には、まず、磁器質またはせっ器質のタイル素地原料を成形した無釉の生成形体に、光触媒粒子を含浸させる。この光触媒粒子の生成形体表面からの含浸の深さは、表面から１ｍｍ以上が好ましい。 Specifically, first, impregnated formations made of porcelain or porcelain tile base material are impregnated with photocatalyst particles. The depth of impregnation of the photocatalyst particles from the surface of the formed body is preferably 1 mm or more from the surface.
　光触媒粒子の含浸方法は、湿式法が好適に利用できる。具体的には、磁器質またはせっ器質のタイル素地原料を成形した生成形体に、光触媒粒子含有液をスプレー、ディップ、フロー等の方法で適用した後に、生成形体表面を乾燥させる。ここで、光触媒粒子の生成形体表面からの含浸の深さは、光触媒含有液の粘性、光触媒含有液の適用方法等の含浸速度を支配する因子と、予め素地の乾燥温度を調整したりする方法等の乾燥速度を支配する因子とを適宜選択することで制御できる。 A wet method can be suitably used as the impregnation method for the photocatalyst particles. Specifically, after the photocatalyst particle-containing liquid is applied by a method such as spraying, dip, or flow to a generated shape obtained by molding a porcelain or porcelain tile base material, the surface of the generated shape is dried. Here, the depth of impregnation of the photocatalyst particles from the surface of the formed body is a method of adjusting the viscosity of the photocatalyst-containing liquid, the factor governing the impregnation rate such as the application method of the photocatalyst-containing liquid, and the substrate drying temperature in advance. It can control by selecting suitably the factor which controls drying speeds, such as.
　次いで、得られた前記表面の吸水率が３％以下になる温度で焼成し、焼成体を得る。この温度は、タイル素地の組成により適宜決定されてよいが、一般的には１０００℃以上、好ましくは１１００℃以上１５００℃以下、より好ましくは１２００℃以上１４００℃以下の温度であることが好ましい。従って、光触媒粒子として酸化チタン粒子を用いた場合は、出発原料がアナターゼやブルッカイトであっても、多くの場合、ルチルに相転移することになる。 Next, firing is performed at a temperature at which the water absorption rate of the obtained surface is 3% or less to obtain a fired body. Although this temperature may be appropriately determined depending on the composition of the tile substrate, it is generally 1000 ° C or higher, preferably 1100 ° C or higher and 1500 ° C or lower, more preferably 1200 ° C or higher and 1400 ° C or lower. Therefore, when titanium oxide particles are used as the photocatalyst particles, even if the starting material is anatase or brookite, it often undergoes a phase transition to rutile.
　さらに、本発明の第二の態様による光触媒タイルの場合には、次いで、上記焼成体の光触媒粒子を含浸させた表面側に光触媒層を形成する。ここにおける光触媒形成方法は、例えば、国際公開第９６／２９３７５号パンフレット、国際公開第００／０６３００号パンフレット、特開２００３－９３８９６等に記載された、光触媒層の形成方法として公知の乾式法または湿式法が利用できる。 Further, in the case of the photocatalyst tile according to the second aspect of the present invention, a photocatalyst layer is then formed on the surface side impregnated with the photocatalyst particles of the fired body. The photocatalyst formation method here is, for example, a dry method or a wet method known as a method for forming a photocatalyst layer described in WO96 / 29375 pamphlet, WO00 / 06300 pamphlet, JP-A-2003-93896, and the like. The law is available.
　湿式法を用いる場合は、スプレーコート、ディップコート、フローコート、印刷、ロールコート等の方法で光触媒粒子を含有するコーティング液を上記焼成体の光触媒粒子を含浸させた表面側に適用した後に、光触媒コーティング液を乾燥・硬化させる。 When using the wet method, after applying the coating liquid containing photocatalyst particles to the surface side impregnated with the photocatalyst particles of the fired body by a method such as spray coating, dip coating, flow coating, printing, roll coating, etc., the photocatalyst Dry and cure the coating solution.
　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.
＜塗装体試料の作製＞
　以下のようにして、実施例1および２ならびに比較例を作製した。
実施例１：
　磁器質のタイル素地原料を乾式プレス法により成形した無釉の複数の生成形体を１００℃で乾燥させ、表面が６０℃のときに、平均粒径７０ｎｍのアナターゼ型酸化チタンと銀化合物とを含む液をスプレー塗布させた後に再び１００℃で乾燥させた。こうして得た生成形体の１つの断面におけるＴｉおよびＡｇの分析から、生成形体表面からの光触媒粒子およびＡｇの浸透深さは約３ｍｍと推定された。
　次いで、この生成形体を１２５０～１３００℃の温度で焼成して焼成体を作製した。尚、この焼成体の吸水率は０．２％であった。 <Preparation of painted body sample>
Examples 1 and 2 and a comparative example were produced as follows.
Example 1:
A plurality of solid shaped products formed from a porcelain tile base material by a dry press method are dried at 100 ° C., and when the surface is 60 ° C., anatase-type titanium oxide having an average particle size of 70 nm and a silver compound are contained. The solution was spray coated and then dried again at 100 ° C. From the analysis of Ti and Ag in one cross section of the resulting shaped body, the penetration depth of the photocatalytic particles and Ag from the surface of the shaped body was estimated to be about 3 mm.
Next, this formed shape was fired at a temperature of 1250 to 1300 ° C. to produce a fired body. The water absorption of this fired body was 0.2%.
実施例２：
　磁器質のタイル素地原料を乾式プレス法により成形した無釉の複数の生成形体を１００℃で乾燥させる。その後、素地表面温度が５０℃～７０℃になるように調整して、平均粒径７０ｎｍのアナターゼ型酸化チタンと銀化合物とを含む液をスプレー塗布させた後に再び１００℃で乾燥させた。こうして得た生成形体の１つの断面におけるＴｉおよびＡｇの分析から、生成形体表面からの光触媒粒子およびＡｇの浸透深さは約３ｍｍと推定された。
　次いで、この生成形体を１２５０～１３５０℃の温度で焼成して焼成体を作製した。尚、この焼成体の吸水率は０．２％であった。
　この焼成体の表面に、フローコート法により、平均粒径５０ｎｍのアナターゼ型酸化チタンとアルカリシリケートとの混合液を塗布した後に乾燥・硬化させて、膜厚０．５μｍの光触媒層を形成した。 Example 2:
A plurality of solid generated shapes formed by porcelain tile base material by dry pressing are dried at 100 ° C. Thereafter, the substrate surface temperature was adjusted to 50 ° C. to 70 ° C., and a liquid containing anatase-type titanium oxide having an average particle diameter of 70 nm and a silver compound was spray-coated and then dried again at 100 ° C. From the analysis of Ti and Ag in one cross section of the resulting shaped body, the penetration depth of the photocatalytic particles and Ag from the surface of the shaped body was estimated to be about 3 mm.
Next, this formed body was fired at a temperature of 1250 to 1350 ° C. to produce a fired body. The water absorption of this fired body was 0.2%.
A liquid mixture of anatase-type titanium oxide having an average particle size of 50 nm and alkali silicate was applied to the surface of the fired body by a flow coating method, and then dried and cured to form a photocatalyst layer having a thickness of 0.5 μm.
比較例１：無釉タイル焼成体の表面に、フローコート法により、平均粒径５０ｎｍのアナターゼ型酸化チタンとアルカリシリケートとの混合液を塗布した後に乾燥・硬化させて、膜厚０．５μｍの光触媒層を形成した。 Comparative Example 1: A mixture of anatase-type titanium oxide having an average particle size of 50 nm and an alkali silicate was applied to the surface of the fired tile-free body by a flow coat method, and then dried and cured to obtain a film thickness of 0.5 μm. A photocatalytic layer was formed.
＜評価＞
　得られた試料について、砂とセラミックスとを混合した水中下で鉄球をタイルに擦る試験を実施例1および比較例については６０００回、実施例２については５０００回繰り返した。
　摩耗後の試料について１０Ｗ／ｍ2のＢＬＢによる光触媒酸化還元活性を調べた。光触媒酸化還元活性は、試料表面に硝酸銀を塗布し１０分経過後の色差Ｅを求め、光触媒を塗布しない試料に硝酸銀を塗布し１０分経過後の色差Ｅ０との差ΔＥで評価した。
　その結果、上記実施例１および２ではΔＥがそれぞれ２．６および１．５となり光触媒酸化還元活性が確認できたが、比較例１ではΔＥが０で光触媒光触媒酸化還元活性は得られなかった。 <Evaluation>
About the obtained sample, the test which rubs an iron ball on a tile in the water which mixed sand and ceramics was repeated 6000 times about Example 1 and the comparative example, and 5000 times about Example 2. FIG.
The photocatalytic redox activity with 10 W / m 2 BLB was examined for the worn sample. The photocatalytic oxidation-reduction activity was evaluated based on the difference ΔE from the color difference E0 after 10 minutes had elapsed after silver nitrate was applied to the sample surface and silver nitrate was applied to the sample without application of the photocatalyst.
As a result, in Examples 1 and 2 above, ΔE was 2.6 and 1.5, respectively, and the photocatalytic redox activity was confirmed, but in Comparative Example 1, ΔE was 0 and no photocatalytic photocatalytic redox activity was obtained.

Claims (7)

  1. 　磁器質またはせっ器質の無釉タイル焼成素地の表面近傍に光触媒粒子が含浸固定されてなることを特徴とする、光触媒タイル。 A photocatalyst tile, wherein photocatalyst particles are impregnated and fixed in the vicinity of the surface of a porcelain or porcelain ceramic tile firing base.
  2. 　前記焼成素地表面の吸水率が３％以下である、請求項１に記載の光触媒タイル。 The photocatalytic tile according to claim 1, wherein the water absorption rate of the surface of the fired substrate is 3% or less.
  3. 　前記焼成素地の、光触媒粒子が含浸固定された表面上に、さらに光触媒層が設けられてなる、請求項１または２に記載の光触媒タイル。 The photocatalyst tile according to claim 1 or 2, wherein a photocatalyst layer is further provided on the surface of the calcined substrate impregnated and fixed with photocatalyst particles.
  4. 　前記焼成素地表面の吸水率が０．１％以上である、請求項１～３のいずれか一項に記載の光触媒タイル。 The photocatalytic tile according to any one of claims 1 to 3, wherein a water absorption rate of the surface of the fired substrate is 0.1% or more.
  5. 　床タイルまたは外装タイルである、請求項１～４のいずれか一項に記載の光触媒タイル。 The photocatalytic tile according to any one of claims 1 to 4, which is a floor tile or an exterior tile.
  6. 　タイル生成形体表面に光触媒粒子を含浸させた後に、前記表面の吸水率が３％以下になる温度で焼成することを特徴とする、光触媒タイルの製造方法。 A method for producing a photocatalytic tile, comprising impregnating photocatalyst particles on a surface of a tile-generating form and firing at a temperature at which the water absorption rate of the surface is 3% or less.
  7. 　前記表面の吸水率が３％以下になる温度で焼成した後に、さらに前記光触媒粒子を含浸させた表面上に、光触媒層を形成する、請求項６に記載の光触媒タイルの製造方法。 The method for producing a photocatalytic tile according to claim 6, wherein a photocatalyst layer is formed on the surface impregnated with the photocatalyst particles after firing at a temperature at which the water absorption rate of the surface is 3% or less.
PCT/JP2010/054670 2009-03-18 2010-03-18 Photocatalytic tile WO2010107086A1 (en)

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JP2009-065531 2009-03-18
JP2009-065530 2009-03-18
JP2009065531A JP2012107376A (en) 2009-03-18 2009-03-18 Photocatalyst tile
JP2009065530A JP2012107375A (en) 2009-03-18 2009-03-18 Photocatalyst tile

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011136984A (en) * 2009-12-01 2011-07-14 Sumitomo Chemical Co Ltd Antiviral agent and antiviral agent functional product using the same
CN113402300A (en) * 2021-07-16 2021-09-17 重庆大学 Ag/BiVO with high sterilization activity4Photocatalytic ceramic tile and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161708A (en) * 1997-08-22 1999-03-05 Fujikon:Kk Concrete product removing nox in atmospheric air by using catalytic effect and manufacture thereof
JP2002160984A (en) * 2000-11-27 2002-06-04 Inax Corp Tile and its manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1161708A (en) * 1997-08-22 1999-03-05 Fujikon:Kk Concrete product removing nox in atmospheric air by using catalytic effect and manufacture thereof
JP2002160984A (en) * 2000-11-27 2002-06-04 Inax Corp Tile and its manufacturing method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011136984A (en) * 2009-12-01 2011-07-14 Sumitomo Chemical Co Ltd Antiviral agent and antiviral agent functional product using the same
CN113402300A (en) * 2021-07-16 2021-09-17 重庆大学 Ag/BiVO with high sterilization activity4Photocatalytic ceramic tile and preparation method thereof

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