Photocatalyst coated body and photocatalyst coating liquid

A photocatalyst paint object and photocatalyst coating liquid

Related application

0001Japan patent application No. 170065 [ 2010 to ] to which it applied for this application on July 29, 2010, A right of priority of the Japan patent application No. 063906 [ 2011 to ] for which it applied on March 23, 2011, and the Japan patent application No. 107363 [ 2011 to ] for which it applied on May 12, 2011 is claimed. Let the specification of these Japanese applications be a part of an indication of this application by quoting.

0002The present invention relates to the photocatalyst coating liquid for a photocatalyst paint object and its formation.

0003Photocatalysts, such as titanium oxide, are used widely in recent years. It becomes possible to disassemble various toxic substances, or to hydrophilicity-ize the member surface in which the surface coat containing photocatalyst particles was formed, and to flush the dirt adhering to the surface with water easily using the activity excited by the light energy of the photocatalyst.

0004The method of forming a layer using the binder component which has corrosion resistance to a photocatalyst as a method of forming in the substrate surface the layer containing photocatalyst particles, and sticking on the substrate surface is known (for example, JP,7-171408,A (patent documents 1)).

0005Various kinds of binder used in such a method are also proposed. Specifically, it is a fluoro-resin (for example, JP,7-171408,A (patent documents 1)), Silicone (for example, JP,2005-161204,A (patent documents 2)), There are a silica particle (for example, JP,2008-264747,A (patent documents 3)), a zirconium compound (for example, international publication 99th / No. 28393 (patent documents 4)), an aluminium compound (for example, JP,2009-39687,A (patent documents 5)), etc.

0006In the composition which forms such a photocatalyst layer in the substrate surface, there is a possibility that organic materials may decompose or deteriorate that substrates are organic materials by the photocatalyst activity of a photocatalyst. In order to cope with this problem, adhesion layers, such as silicon denaturation resin, are provided between a photocatalyst layer and a substrate, and the art which protects the substrate of a ground from degradation by photocatalyst operation is known (international publication 97th / No. 00134 (patent documents 6)). If it is in this prior art, it is supposed that the example of quantity with the amount of photocatalysts of greater than 20 % of the weight was indicated concretely, and decomposition or degradation of a substrate was prevented effectively.

0007The middle class containing silicone modification resin and an organic antifungal agent is provided between a photocatalyst layer and a substrate, and the proposal which prevents decomposition or degradation of a substrate is also made (JP,2008-272718,A (patent documents 7)).

0008There are various proposals about the art understood by NOx using a photocatalyst (for example, JP,1-218622,A (patent documents 8), JP,2001-162176,A (patent documents 9), JP,2008-264747,A (patent documents 3), etc.).

0009It is [ performing the removal efficiently and ] harmful NO that it is important in NOx removal._２It is controlling generation of the intermediate product of etc. When a photocatalyst performs NOx removal, the desire to the art which can control generation of a harmful intermediate product exists.

0010As a prior art which is indicating the combination of a photocatalyst and a zirconium compound, there is JP,2009-270040,A (patent documents 11) first. This gazette is indicating light catalytic titanium oxide and the photocatalyst coating liquid in which D50 contains the zirconia particle which is 1-20 nm, and carboxylic acid. Addition of a zirconia particle aims at improvement in the adhesion nature of a photocatalyst layer. To 100 weight sections of titanium oxide, although a zirconia particle is 25-100 weight sections, addition of a silica particle is not indicated in this gazette. Although there is an indication of evaluation of aldehyde degradation ability, there is no indication about NOx resolvability and weatherability.

0011International publication 97th / No. 00134 (patent documents 6) have the indication of the photocatalyst layer containing titanium oxide, silica, and the sol of a zirconium dioxide (for example, Example 27). In this gazette, zirconium tetra-butoxide is indicated as zirconium dioxide sol, and it is supposed that drying by heating of it will be carried out. It is thought that the particle diameter of the zirconia obtained on the drying by heating conditions which this gazette indicates is set to several micrometers.

0012JP,2009-39687,A (patent documents 5) has the indication of photocatalyst particles, silica, and the photocatalyst paint object containing acetic acid zirconium. In this gazette, the constituent containing acetic acid zirconium is hardened at room temperature, and it is thought that the zirconium compound therefore generated does not become a form of particles. Although evaluation of the aldehyde degradation nature of a photocatalyst paint object is made, there is no indication about NOx resolvability and weatherability. The amount of addition of silica is less than 30 mass parts.

0013International publication 98th / No. 015600 (patent documents 12) have the indication of the photocatalyst layer containing a photocatalyst, a zirconium compound and/or a tin compound, and a silica compound. In this gazette, it is supposed that the zirconia compound is aimed at alkali-proof grant. In order to obtain a zirconium compound, drying by heating of the zirconium tetra-butoxide is carried out as sol of a zirconium dioxide, and it seems that single Oblique crystal zirconia is obtained on the conditions of a statement, but it is thought that the particle diameter is several micrometers.

<p num="0014"><patcit num="1"><text>JP,7-171408,A</text></patcit><patcit num="2"><text>JP,2005-161204,A</text></patcit><patcit num="3"><text>JP,2008-264747,A</text></patcit><patcit num="4"><text>The international publication 99th/No. 28393 pamphlet</text></patcit><patcit num="5"><text>JP,2009-39687,A</text></patcit><patcit num="6"><text>The international publication 97th/No. 00134 pamphlet</text></patcit><patcit num="7"><text>JP,2008-272718,A</text></patcit><patcit num="8"><text>JP,1-218622,A</text></patcit><patcit num="9"><text>JP,2001-162176,A</text></patcit><patcit num="10"><text>JP,9-227156,A</text></patcit><patcit num="11"><text>JP,2009-270040,A</text></patcit><patcit num="12"><text>The international publication 98th/No. 015600 pamphlet</text></patcit></p>

0015These artificers contain photocatalyst particles and a silica particle by a specific ratio this time, At least one sort chosen from the group which an average crystallite diameter becomes from a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less, While having the various characteristics and an especially good photocatalytic degradation function by constituting a photocatalyst layer from specific composition which contains a noncrystalline zirconia particle more preferably, knowledge that control of degradation by the photocatalyst of organic group material can be improved dramatically was acquired. It is NO, the above-mentioned photocatalyst layer raising the amount of NOx removal, when removing NOx in the air._２Knowledge that generation of the intermediate product of etc can be controlled was acquired.

0016Therefore, the present invention sets offer of the photocatalyst coating liquid used for the various characteristics, the photocatalyst paint object which was especially excellent in a photocatalytic degradation function and weatherability, and its formation as the purpose.

0017The present invention is NO, raising the amount of NOx removal, when removing NOx in the air._２Offer of the photocatalyst coating liquid used for the photocatalyst paint object which can control generation of the intermediate product of etc, and its formation is set as the purpose.

0018And the photocatalyst paint object by the present invention is a photocatalyst paint object provided with a substrate and the photocatalyst layer provided on the substrate, and the above-mentioned photocatalyst layers are 20 mass parts or less of photocatalyst 1-mass part or more particles, 98 mass parts or less of silica particles of 30 mass parts or more, and 50 mass parts or less of 1-mass part or more zirconia particles, It contains so that the total quantity of the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle may be 100 mass parts, The above-mentioned zirconia particles are at least one sort chosen from the group which an average crystallite diameter becomes from a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less, more preferably a noncrystalline zirconia particle.

0019Photocatalyst coating liquid by the present invention, On the dry mass standard, 20 mass parts or less of photocatalyst particles of 1 mass part or more and 30 mass parts of silica particles are exceeded, and it is 98 mass parts or less, 50 mass parts or less of 1-mass part or more zirconia particles are included so that the total quantity of the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle may be 100 mass parts, The above-mentioned zirconia particles are at least one sort chosen from the group which an average crystallite diameter becomes from a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less including water and/or alcohol, more preferably a noncrystalline zirconia particle.

0020The photocatalyst paint object by the present invention can improve weatherability while having the various characteristics and an especially good photocatalytic degradation function. When especially a substrate is organic group material, degradation by the photocatalyst of organic group material is controlled dramatically, and can improve weatherability. The photocatalyst paint object by the present invention is NO, raising the amount of NOx removal, when removing NOx in the air._２Generation of the intermediate product of etc can be controlled. According to the desirable mode of the present invention, the photocatalyst paint object excellent also in hydrophilicity and the various desired tunic characteristics (transparency, film strength, etc.) is provided.

0021<u style="single">Photocatalyst paint object</u><br />The photocatalyst paint object by the present invention is a photocatalyst paint object provided with a substrate and the photocatalyst layer provided on the substrate, and the above-mentioned photocatalyst layers are 20 mass parts or less of photocatalyst 1-mass part or more particles, 98 mass parts or less of silica particles of 30 mass parts or more, and 50 mass parts or less of 1-mass part or more zirconia particles, It contains so that the total quantity of the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle may be 100 mass parts, and it is the above-mentioned zirconia particle, Average crystallite diameters are at least one sort chosen from the group which consists of a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less, more preferably a noncrystalline zirconia particle.

0022<u style="single">Substrate</u><br />In the present invention, if a substrate is the material which can form a photocatalyst layer on it, regardless of the charge of non-equipment, and organic materials, it may be various materials and the shape will not be limited, either. As a desirable example of the substrate seen from a viewpoint of material, what has a tunic of at least one layer is mentioned to metal, ceramics, glass, a plastic, rubber, a stone, cement, concrete, textiles, a textile, a tree, papers, those combination, those layered products, and those surfaces. As the desirable example of the substrate seen from a viewpoint of a use, The exterior of building materials, the building exterior, a window frame, a windowpane, a structure member, and a vehicle, and paint, The exterior of a mechanical apparatus or an article, a dustproof cover, paint, a traffic-control sign, various displays, The exterior of an ad pillar, the noise-proof wall for roads, the noise-proof wall for railroads, a bridge, and a guard rail, and paint, Exterior cases, such as a film for making it stick on the cover of tunnel interior, paint, an insulator, a solar cell cover, the collection heat cover of solar water heaters, a vinyl house, and the lighting for vehicles, the light for the outdoors, a stand, and the above-mentioned article surface, a sheet, and a seal, are mentioned.

0023That the advantage by the present invention is demonstrated advantageously is a substrate with which the surface contains an organic substance. As such a substrate, the layered product etc. which laminated the paint object which gave paint containing resin containing an organic matter and resin containing an organic matter to the surface, the film containing resin containing an organic matter, etc. on the surface are mentioned, for example. If an applicable substrate is said for a use, they will be metal laminate sheets, such as a metal paint board and a vinyl chloride steel plate, Building materials, such as a pottery-industry system decorative sheet and resin building materials, the building exterior, building interior, a window frame, a windowpane, The exterior of a structure member and a vehicle, paint and the exterior of a mechanical apparatus or an article, a dustproof cover, and paint, A traffic-control sign, various displays, an ad pillar, the noise-proof wall for roads, the noise-proof wall for railroads, a bridge, The exterior of a guard rail, paint, tunnel interior, paint, an insulator, a solar cell cover, The cover of the collection heat cover of solar water heaters, a vinyl house, and the lighting for vehicles, housing equipment, a toilet bowl, a bathtub, a washstand, a light, a lighting cover, kitchen utensils, tableware, a tableware syringe, a tableware drier, a sink, a cooking range, a kitchen hood, a ventilation fan, etc. are mentioned. In especially the present invention, when a metal paint board and a metal laminate sheet are used as a substrate, it is [ that it is hard to make a substrate deteriorate and corrode ] desirable.

0024If it is on a photocatalyst paint object conventionally, stopping the layer which consists the influence on the substrate by the photocatalyst activity of a photocatalyst layer of silicone series resin by providing between substrates has generally been performed. According to the present invention, a photocatalyst layer can also be directly provided in the substrate consisting of organic materials instead of such silicone series resin generally provided conventionally. As a result, the present invention becomes very advantageous in respect of if it uses [ the ] and a scope is expanded greatly.

0025<u style="single">The photocatalyst layer of a photocatalyst paint object</u><br />In the present invention, in addition to the shape of a perfect film, a photocatalyst layer also includes the state where it has become film-like partially, if photocatalyst particles exist in the substrate surface. It may disperse and exist in island shape on the substrate surface. According to the desirable mode of the present invention, this photocatalyst layer is obtained with the application of coating fluid.

0026The above-mentioned photocatalyst layer of the photocatalyst paint object by the present invention, 20 mass parts or less of photocatalyst particles of 1 mass part or more, and 98 mass parts or less of 30-mass part or more silica particles, 50 mass parts or less of 1-mass part or more zirconia particles are included so that the total quantity of the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle may be 100 mass parts, The above-mentioned zirconia particles are at least one sort chosen from the group which an average crystallite diameter becomes from a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less, more preferably a noncrystalline zirconia particle.

0027(a) Zirconia particle<br />The zirconia particle which constitutes a photocatalyst layer in the present invention can be a thing of crystalline material, a noncrystalline thing, or its mixture, and also in being crystalline material, the average crystallite diameter uses a thing of 10 nm or less. If an amorphous zirconia particle is used from the example for which weatherability is mentioned below although the reason is unknown, the result which was not able to be expected at all of coming to excel specifically is obtained. Therefore, it can be said that use of an amorphous zirconia particle is preferred as a zirconia particle. As a crystallized type in a crystalline material zirconia particle, although it can use single Oblique crystal, a tetragonal phase, a cubic, rhombohedral, etc. suitably, single Oblique crystal is preferred. The single Oblique crystal zirconia particle can realize a stable state chemically, without adding a stabilizer, especially since it is a stable phase in normal temperature. Therefore, it is advantageous at the point that the influence of a stabilizer can be reduced.

0028In the present invention, the amounts of zirconia particles in a photocatalyst layer are 1 mass part or more and 50 mass parts or less. A minimum is 5 mass parts or more preferably, and a maximum is 45 mass parts or less. From another viewpoint, desirable ranges are 5 mass parts or more and less than 50 mass parts, and are 5 mass parts or more and 45 mass parts or less more preferably. Good weatherability is obtained and good NOx resolvability is acquired because the amount of zirconia particles is in a mentioned range.

0029The average crystallite diameter in a crystalline material zirconia particle shall be 10 nm or less, preferably 8 nm or less. Here, an average crystallite diameter means the average crystallite diameter computed by Scherrer style after the pattern fitting processing except Buck Grant in an X diffraction using the biggest diffraction peak theta= 25 degrees - near 2 32 degree.

0030In the present invention, a noncrystalline zirconia particle means the zirconia particle which the peak of theta= 25 degrees - near 2 32 degree in an X diffraction cannot observe clearly after the pattern fitting processing except Buck Grant.

0031According to one mode of the present invention, average particle diameter exceeds 5 nm, as for a zirconia particle, it is preferred that it is 50 nm or less, and a more desirable minimum is 10 nm. Preferably it is 20 nm, and a more desirable maximum is 40 nm and is 30 nm still more preferably. From another viewpoint, the desirable range exceeds 10 nm, it is 40 nm or less, and, still more preferably they are 10 nm or more and 30 nm or less. Average particle diameter means here what is computed as number average value which measured the length of 100 arbitrary particles which go into the views of being 200,000 times many, with a scanning electron microscope. Although a real ball is the best as shape of particles, an approximate circle form and an elliptical form may be used, and the length of the particles in that case is abbreviated-computed as (a (major-axis + minor axis) / 2). While abrasion resistance improves [ that the diameter of a particle is in the above-mentioned range ], when forming an opening and the path improves a photocatalytic degradation function, it becomes easy to become moderate size.

0032(b) Photocatalyst particles<br />In the present invention, quantity of photocatalyst particles in a photocatalyst layer is 1 mass part or more and 20 mass parts or less. Preferably it is 1 mass part or more and 15 mass parts or less, and more preferably they are 1 mass part or more and 10 mass parts or less.

0033Especially if it is the particles which have photocatalyst activity, it will not be limited, but the photocatalyst particles used for the present invention are as the desirable example, Titanium oxide, for example, Anatase type titanium oxide, a rutile type titanium dioxide, the particles of a metal oxide like brookite type titanium oxide, a zinc oxide, tin oxide, titanic acid strontium, and tungstic oxide are mentioned -- more -- desirable -- titanium oxide particles -- most preferably they are Anatase type titanium oxide particles.

0034According to the desirable mode of the present invention, photocatalyst particles are 10 nm or more and 60 nm or less preferably [ having 10 nm or more the average particle diameter of 100 nm or less ], and more preferably. Average particle diameter means here what is computed as number average value which measured the length of 100 arbitrary particles which go into the views of being 200,000 times many, with a scanning electron microscope. Although a real ball is preferred as shape of particles, an approximate circle form and an elliptical form may be used, and the length of the particles in that case is abbreviated-computed as (a (major-axis + minor axis) / 2). When photocatalyst activity becomes high, and it forms an opening because the diameter of a particle is in this range and that path improves a photocatalytic degradation function, it becomes easy to become moderate size.

0035(c) Silica particle<br />In the present invention, content is 30 mass parts or more and 98 mass parts or less about a silica particle in a photocatalyst layer. A minimum is 35 mass parts preferably, and more preferably it is 40 mass parts, and most preferably is 70 mass parts, and a maximum is 94 mass parts preferably. From another viewpoint, desirable ranges are more than 30 mass % and below 94 mass %, and more than 40 mass % and below 94 mass % are more than 70 mass % and below 94 mass % most preferably. It is NO, raising [ good weatherability is obtained and ] the amount of NOx removal, when removing NOx in the air, because the content of a silica particle is in this range._２While being able to control generation of the intermediate product of etc, when it applies to organic group material, degradation can be controlled greatly.

0036Average particle diameter exceeds 5 nm, it is preferred that it is 50 nm or less, more preferably it exceeds 10 nm, and a silica particle used in the present invention is 40 nm or less. They are 10 nm or more and 30 nm or less preferably. This average particle diameter means what is computed as number average value which measured the length of 100 arbitrary particles which go into the views of being 200,000 times many, with a scanning electron microscope. Although a real ball is the best as shape of particles, an approximate circle form and an elliptical form may be used, and the length of the particles in that case is abbreviated-computed as (a (major-axis + minor axis) / 2). While abrasion resistance improves [ that the diameter of a particle is in this range ], when forming an opening and that path improves a photocatalytic degradation function, it becomes easy to become moderate size. It is NO, raising the amount of NOx removal by the size of a silica particle being controlled as mentioned above, when removing NOx in the air._２Generation of the intermediate product of etc can be controlled.

0037(d) Film thickness<br />As for the film thickness of the above-mentioned photocatalyst layer in a photocatalyst paint object, according to one mode of the present invention, it is preferred that it is 3 micrometers or less. The characteristic which was excellent in the film thickness of a photocatalyst layer being 3 micrometers or less also in transparency and film strength is acquired, and the effect which does not produce the poor appearance by a crack not progressing to the surface side is acquired more. As for the film thickness of a photocatalyst layer, 0.2 micrometer or more is preferred, and more preferably it is 0.5 micrometer or more. Good hydrophilicity is demonstrated because it is 0.2 micrometer or more. Weatherability improves more because the ultraviolet rays which reach the interface of a photocatalyst layer and a substrate fully decline. It is NO, raising the amount of NOx removal by considering it as the above-mentioned film thickness, when removing NOx in the air securing the transparency of a photocatalyst layer._２Generation of the intermediate product of etc can be controlled.

0038(d) Other ingredients (the amount of particle ingredients)<br />In the present invention, although what becomes substantial is preferred only from the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle as for the above-mentioned photocatalyst layer, existence of other ingredients including other particle ingredients is not eliminated.

0039According to one mode of the present invention, as for more than 85 mass %, below 100 mass % more preferably more than 90 mass %, and below 100 mass %, the amount of particle ingredients in the above-mentioned photocatalyst layer may be carried out. A particle ingredient contains here the particles which photocatalyst particles and an average crystallite diameter contain the crystalline material zirconia particle of 10 nm or less, and at least one sort of zirconia particles chosen from the group of a noncrystalline zirconia particle, and also are contained in photocatalyst layers, such as a silica particle and other inorganic oxide particles.

0040As other inorganic oxide particles, with photocatalyst particles, especially if it is the particles of the inorganic oxide which can form a layer, it will not be limited, The particles of compound oxides, such as particles; of single oxides, such as alumina, zirconia, Seria, and it rear The Bolonia, magnesia, calcia, a ferrite, amorphous Chita Near, and hafnia, barium titanate, and silicic acid calcium, etc. can be used.

0041In order to reveal high antibacterial properties, antivirotic, and mildew resistant performance according to the desirable mode of the present invention, The metallic compounds consisting of at least one sort of metal chosen from the group which consists of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, copper I oxide, the second copper of oxidization, silver, silver oxide, platinum, and gold, and/or its metal may be made to exist in a photocatalyst layer. A quantity [ very small quantity / and / quantity / the amount of addition ] required for revelation of the operation in which it is desirable not affecting formation of the gap between the particles by above-mentioned photocatalyst particles and inorganic oxide particles as for the existence therefore is little. Specifically, 0.001 to 10 mass %, more preferably the amount of addition about 0.05 - 5 mass % are preferred to a photocatalyst.

0042Below in 10 mass %, in the photocatalyst layer of the present invention, the binder component may contain [ more than 0 mass %, below 15 mass %, more preferably more than 0 mass % ] further. Here, as a binder, they are silicone emulsion and denaturation silicone emulsion, for example, At least one sort chosen from the group of hydrolysis / condensation thing of fluoro-resin emulsion, silicone resin, denaturation silicone resin, and Alkyl silicate, alkali silicate, a basic water solubility zirconium compound, and hydrolysis / condensation thing of metal Alkoxide can be used suitably.

0043In addition to photocatalyst particles, inorganic oxide particles, and the binder as an arbitrary ingredient, in the present invention, the ultraviolet-rays cover agent, the organic antifungal agent, etc. may be further added by the photocatalyst layer. Although not being added at all is preferred as for an ultraviolet-rays cover agent, an organic antifungal agent, etc., when added, the amount of addition is more than 0 mass % and below 15 mass %, when the whole photocatalyst layer is made into 100 mass %. Preferably below 5 mass % may contain [ more than 0 mass % and below 10 mass % / more than 0 mass % ] still more preferably. As for the existence, it is desirable not to affect formation of the gap between the particles by above-mentioned photocatalyst particles and inorganic oxide particles.

0044It is made for the percentage of void in a photocatalyst layer to be more than 15 volume % according to the desirable mode of the present invention. Since the opening of quantity sufficient by doing so is secured, while being able to permeate a silicone elution thing mostly in a hole, a lot of harmful gas contacts photocatalyst particles, and photocatalyst activity becomes is easy to be decomposed. It is made for the percentage of void in [ a viewpoint that sufficient abrasion resistance is securable to ] a photocatalyst layer to be below 50 volume % according to the desirable mode of the present invention.

0045Or more (preferably ten or more points) 5 measurement of the percentage of void per one sample is carried out using reflective part optical thin-film thickness meter:FE-3000 by Otsuka Electronics Co., Ltd., and it calculates the average value. A glass board is used for a substrate and the formation ingredient of a photocatalyst layer is TiO.₂And SiO₂The measurement procedure of the percentage of void of a of case is shown below.

0046Refractive-index determination of a procedure 1. glass board<br />1-1. Measure the reflectance in the wavelength of 230-800 nm of a glass board on condition of the following.<br />The measurement technique It is reflectance absolutely.<br />Lens Refrec.25X<br />Standard light reflector aluminum-S-13<br />Filter Nothing<br />Slit 0.2 mm x 2 mm<br />Sampling time 1000msec<br />The number of times of addition 9 times<br />Gain Normal

00471-2. Fresnel Amplitude Reflective Coefficient in Air / Glass Board Interface when Reflecting Light Which Made Reflectance in Wavelength of 230-800 Nm of Glass Board Phi= 0 Degree of Incidence Angles of Composition Medium = Air, Glass Board, and Light, and Entered from Air Side with Glass Board, and Distributed Type [Nm=C of N-Cauchy_m1+C_m2/lambda²+C_m3/lambda⁴(However, nm the refractive index of a glass board and lambda a wavelength, C)_m1C_m2C_m3It computes by Is a constant]. In the distributed type of n-Cauchy, it is a constant (C)._m1C_m2C_m3It is C about an initial value, respectively._m1= 1.5, C_m2= 0, C_m3= It is referred to as 0 and set 1 and the Extinction coefficient of air to 0 for the refractive index of air (basic theoretical [ of Mitsunobu Kohiyama and "optical thin film ] "p1-70, * (2003 and * Optronics)).

00481-3. C in case Survey Reflectance (1-1) is Compared with Calculation Reflectance (1-2) and Sum of Remaining Difference Becomes Minimum Square_m1C_m2C_m3Sought. In that case, the maximum of the sum of a Remaining difference is set to 0.02 the square.<br />C for which it asked by 1-4.1-3_m1C_m2C_m3It substitutes for the distributed type of n-Cauchy, and determines refractive index nm of a glass board.

0049Determination of the percentage of void of a procedure 2. photocatalyst layer<br />2-1. Measure the reflectance in the wavelength of 230-800 nm of a photocatalyst layer on condition of the following.<br />The measurement technique It is reflectance absolutely.<br />Lens Refrec.25X<br />Standard light reflector aluminum-S-13<br />Filter Nothing<br />Slit 0.2 mm x 2 mm<br />Sampling time 1000msec<br />The number of times of addition 9 times<br />Gain Normal

00502-2. Composition Medium = Light Which Reflected Light Which Considered it as Phi= 0 Degree of Incidence Angles of Air, Photocatalyst Layer = Monolayer Thin Film, Glass Board, and Light, and Entered from Air Side by Monolayer Thin Film, The Fresnel amplitude reflective coefficient in air / monolayer thin film interface when a light transmitted inside the monolayer thin film totals the light which carried out multiplex repetition reflection in respect of the upper and lower sides of a monolayer thin film (air / monolayer thin film interface, a monolayer thin film / glass board interface), and the approximate expression of Bruggeman<br />[C₁{(epsilon)₁- epsilon/(epsilon)₁+2epsilon}+C₂{(epsilon)₂- epsilon/(epsilon)₂+2epsilon}+C₃{(epsilon)₃- epsilon/(epsilon)₃+2epsilon}=0, C₁+C₂+C₃= 1 (however, epsilon the dielectric constant of a monolayer thin film, epsilon),₁Is SiO₂Dielectric constant of, epsilon₂Is TiO₂Dielectric constant of, epsilon₃The dielectric constant of Is air, C₁Is SiO₂Volume fraction of, C₂Is TiO₂Volume fraction of, C₃With volume fraction] of Is air, the reflectance in the wavelength of 230-800 nm of a photocatalyst layer is computed (Mitsunobu Kohiyama, basic theoretical [ of "optical thin film ] "p1-70 (2003 and * Optronics)). D. *E.*Aspnes, *Thin*Solid*Films, *89, *249 (1982).<br />C₁(SiO₂Volume fraction of, C₂(TiO₂Volume fraction of, C₃The initial value of (the volume fraction of air) sets up a value which the sum of a Remaining difference converges on the minimum the square, respectively. The refractive index of air is set to 1 and the Extinction coefficient of air is set to 0. SiO₂TiO₂Refractive index (n)₁n₂Extinction coefficient (k)₁k₂E.*D.*Palik*, * "Handbook*of*Optical*Constants*of*Solids" (1998),<br />It quotes from Academic*Press and *San*Diego.

00512-3. Film Thickness D and SiO₂TiO₂Volume fraction C of air₁C₂C₃C when survey reflectance (2-1) is compared with calculation reflectance (2-2), changing a of value and the sum of a Remaining difference becomes the minimum the square₁C₂C₃Ask for. C when the sum of a Remaining difference becomes less than 0.02 and the minimum the square₃It adopts as percentage of void. The other conditions are as follows.<br />Film thickness search method The optimizing method<br />Retrieving range (wavelength) 400-800 nm<br />Retrieving range (film thickness) 0-2000 nm<br />Film thickness step 10 nm<br />C for which it asked here_３It is considered as the percentage of void in the photocatalyst layer of the present invention.

0052<u style="single">Photocatalyst coating liquid</u><br />The photocatalyst coating liquid by the present invention is the dry mass standard, and is 20 mass parts or less of photocatalyst 1-mass part or more particles, 30 mass parts of silica particles are exceeded, and they are [ 98 mass parts or less and ] 50 mass parts or less of 1-mass part or more zirconia particles, It contains so that the total quantity of the above-mentioned photocatalyst particles, the above-mentioned silica particle, and the above-mentioned zirconia particle may be 100 mass parts, The above-mentioned zirconia particles are at least one sort chosen from the group which an average crystallite diameter becomes from a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less including water and/or alcohol, more preferably a noncrystalline zirconia particle.

0053At the rate of a mass ratio which described above each ingredient indicated in the photocatalyst layer also including the desirable range, in water and/or alcohol, it distributes or dissolves and the photocatalyst coating liquid by the present invention is manufactured. The photocatalyst particles which the coating fluid by the present invention contains, a crystalline material zirconia particle and a noncrystalline zirconia particle, and other ingredients may be substantially the same except being in the ingredient which constitutes an above-mentioned paint object, and the state of constituting a fluid constituent. What was mentioned as a desirable mode may be similarly added as a desirable thing in the coating fluid by the present invention about these ingredients.

0054In the photocatalyst coating liquid by the present invention, titanium oxide may be any, such as powder, the shape of sol, and the shape of solution. It is desirable especially preferred that it is a form of the organosol which colloid was made to distribute to hydrophilic solvents, such as water colloid; which made water carrier fluid or ethyl alcohol, isopropyl alcohol, or ethylene glycol, and a silica particle is colloidal silica. Water colloid; or ethyl alcohol in which the zirconia particle made water carrier fluid, That it is a form of the organosol which hydrophilic solvents, such as isopropyl alcohol or ethylene glycol, were made to distribute to colloid is the sol which a crystalline material zirconia particle and a noncrystalline zirconia particle of 10 nm or less distributed preferably desirable especially.

0055The photocatalyst coating liquid by the present invention may contain a surface-active agent as an arbitrary ingredient, Although the amount of addition may be determined suitably, 0 mass part or more and its less than 10 mass parts are common to photocatalyst coating liquid, preferably it is 0 mass part or more and 8 mass parts or less, and is 0 or more and 6 mass parts or less more preferably. By addition of a surface-active agent, smoothing of leveling, i.e., the Coating surface, and equalization can be attained. what a surface-active agent is an effective ingredient in order to improve the wettability of photocatalyst coating liquid, but is included for no [ substantially or ] surface-active agent if wettability is not made an issue of -- good -- better -- there is a case.

0056Although a surface-active agent takes into consideration the wettability at the time of applying on the dispersion stability of a photocatalyst or inorganic oxide particles, and the middle class and may be chosen suitably, A nonionic surface-active agent is preferred and more preferably an ether type nonionic surface-active agent, an ester type nonionic surface-active agent, a polyalkylene glycol nonionic surface-active agent, a fluorine system nonionic surface-active agent, and a silicon system nonionic surface-active agent are mentioned.

0057Although the solid content concentration in particular of the photocatalyst coating liquid of the present invention is not limited, it is preferred in the ease of applying to consider it as 1 - 10 mass %. Analysis of the composition ingredient in a photocatalyst coating constituent, It can evaluate by extra filtration separating coating fluid into a particle ingredient and Filtrate, analyzing each by infrared emission spectroscopy, a gel permeation chromatography, fluorescence X line segment photometric analysis, etc., and analyzing a spectrum.

0058<u style="single">A manufacturing method of a photocatalyst paint object</u><br />The photocatalyst paint object of the present invention can be manufactured by applying the photocatalyst coating liquid of the present invention on the substrate heated if needed. As for a coating method, brush coating, a roller, a spray, a roll coater, flow coater, a dip coat, sink coating, screen-stencil, etc. can use the method currently generally performed widely. After applying to the substrate of coating fluid, normal temperature dryness may be carried out or drying by heating may be carried out if needed. However, since there is a possibility that the opening between particles may decrease and it may become impossible to acquire sufficient photocatalyst activity when it heats until sintering progresses, or it does not affect opening formation, it is preferred to choose the temperature and time whose influence decreases. For example, drying temperature is above 5 and below 500 , and when resin is contained in at least one copy of a substrate, in consideration of the heat-resistant temperature of resin, etc., desirable drying temperature is above 10 and below 200 .

0059Since the photocatalyst paint object by the present invention does not necessarily have the necessity of making the middle class intervening between substrates, as above-mentioned, it is advantageous in respect of if the time and cost which the manufacture takes are reducible.

<p num="0060">Although the present invention is concretely explained based on the following examples, the present invention is not limited to these examples.</p><p num="0061">Example A1<br />First, the plate-like coloring organicity paint object of 50mmX100mm was prepared as a substrate. This coloring organicity paint object applies a red acrylics paint on the pottery-industry system siding substrate which carried out Sheeler processing, and it makes it fully dry and harden it.</p><p num="0062">Subsequently, photocatalyst coating liquid was prepared. This photocatalyst coating liquid is a Anatase type Chita Near particle water dispersing element (average particle diameter: 40 nm), It is the photocatalyst coating liquid which used water for the solvent, was mixed and adjusted water distributed colloidal silica (average particle diameter: 20 nm) and an amorphous zirconia particle water dispersing element (average particle diameter: 20 nm) to solid content concentration 5.5 mass %. It is here and is TiO._２The mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle was set to 2:93:5.</p><p num="0063">Carried out spray coating on the above-mentioned board coloring organicity paint object which heated the obtained photocatalyst coating liquid beforehand, the photocatalyst layer of 0.5 micrometer of film thickness was made to form by drying at normal temperature, and the photocatalyst paint object was acquired.</p><p num="0064">Example A2<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 2:88:10.</p><p num="0065">Example A3<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 3.5:91.5:5.</p><p num="0066">Example A4<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 3.5:86.5:10.</p><p num="0067">Example A5<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 3.5:94.5:2.</p><p num="0068">Example A6<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 3.5:92.5:4.</p><p num="0069">Example A7<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 5:90:5.</p><p num="0070">Example A8<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 5:85:10.</p><p num="0071">Example A9<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 10:80:10.</p><p num="0072">Example A10<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 10:70:20.</p><p num="0073">Example A11<br />A single Oblique crystal zirconia particle water dispersing element (average crystallite diameter of 5 nm) is used instead of an amorphous zirconia particle water dispersing element (average particle diameter: 20 nm), and it is TiO._２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 3.5:94.5:2.</p><p num="0074">Example A12<br />A single Oblique crystal zirconia particle water dispersing element (average crystallite diameter of 5 nm) is used instead of an amorphous zirconia particle water dispersing element (average particle diameter: 20 nm), and it is TiO._２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 3.5:92.5:4.</p><p num="0075">Example A13<br />The sample was produced on the same conditions as example A6 of an experiment except having used what applied the red acrylics paint on the aluminum substrate, and was fully dried and stiffened as a coloring organicity paint object.</p><p num="0076">Example A14<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 10:85:5.</p><p num="0077">Example A15<br />First, the plate-like coloring organicity paint object of 50mmX100mm was prepared as a substrate. This coloring organicity paint object applies acrylics silicone emulsion on the pottery-industry system siding substrate which carried out Sheeler processing, and it makes it fully dry and harden it.</p><p num="0078">Subsequently, photocatalyst coating liquid was prepared. This photocatalyst coating liquid is a Anatase type Chita Near particle water dispersing element (average particle diameter: 40 nm), It is the photocatalyst coating liquid which used water for the solvent, was mixed and adjusted water distributed colloidal silica (average particle diameter: 20 nm) and an amorphous zirconia particle water dispersing element (average particle diameter: 20 nm) to solid content concentration 5.5 mass %.<br />It is here and is TiO._２The mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle was set to 10:70:20.</p><p num="0079">Carried out spray coating on the above-mentioned board coloring organicity paint object which heated the obtained photocatalyst coating liquid beforehand, the photocatalyst layer of 0.5 micrometer of film thickness was made to form by drying at normal temperature, and the photocatalyst paint object was acquired.</p><p num="0080">Example A16<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A15 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of an amorphous zirconia particle to 10:45:45.</p><p num="0081">Comparative example A1<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 2:98:0.</p><p num="0082">Comparative example A2<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 3.5:96.5:0.</p><p num="0083">Comparative example A3<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 5:95:0.</p><p num="0084">Comparative example A4<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 10:90:0.</p><p num="0085">Comparative example A5<br />A single Oblique crystal zirconia particle water dispersing element (average crystallite diameter of 15 nm) is used instead of an amorphous zirconia particle water dispersing element (average particle diameter: 20 nm), and it is TiO._２The sample was produced on the same conditions as Example A1 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 3.5:92.5:4.</p><p num="0086">Comparative example A6<br />TiO of photocatalyst coating liquid_２The sample was produced on the same conditions as Example A15 except having set the mass ratio of Solid content, the solid content of colloidal silica, and the solid content of a zirconia particle to 10:90:0.</p><p num="0087">About each sample obtained in this way, various evaluation tests were done as follows.</p><p num="0088">Evaluation experiment A1: The long-term weathering test using sunshine Weather meter<br />It is JIS about a photocatalyst paint object.<br />It supplied to the sunshine Weather meter (the Suga Test Instruments make, S-300C) specified to B7753. taking out a specimen after progress for a predetermined period -- the Nippon Denshoku Colorimetric difference total -- in ZE2000, it is before and after a promotion examination, and measured color differences delta E and delta L.</p><p num="0089">It supplied to sunshine Weather meter (the Suga Test Instruments make, S-300C) on the conditions same about the same substrate as Example A1 which does not form a photocatalyst layer in a similar manner on the other hand. taking out a specimen after progress for a predetermined period -- the Nippon Denshoku Colorimetric difference total -- in ZE2000, it is before and after a promotion examination, and measured blank color difference deltaE (0) and deltaL (0).<br />Comparison between samples was performed by deltaE-deltaE (0) or deltaL-deltaL (0).<br />The result was as being shown in Table 1 and 2.</p><p num="0090"><tables num="1"><img file="WO2012014877A1_D0001.tif" /></tables></p><p num="0091"><tables num="2"><img file="WO2012014877A1_D0002.tif" /></tables></p><p num="0092">Evaluation experiment A2: Outdoor exposure examination<br />Outdoor exposure was performed at an angle of 20 degrees from the level towards the south face using the exposure mount specified to JIS K 5600-7-6 on the building roof in Chigasaki-shi, Kanagawa about Examples A5 and A6 and comparative examples A2 and A5. evaluation takes out a specimen in three months -- the Nippon Denshoku Colorimetric difference total -- in ZE2000, it is before and after a promotion examination, and carried out by measuring color difference deltaE.<br />The result was as being shown in Table 3.</p><p num="0093"><tables num="3"><img file="WO2012014877A1_D0003.tif" /></tables></p><p num="0094">Evaluation experiment A3: Photocatalytic degradation activity<br />Methylene blue resolution was evaluated about Examples A3, A5, A9, A10, and A14 and comparative examples A2 and A4. The methylene blue resolution by a photocatalyst is Selfie of a JISR1703-2"photocatalyst material.<br />Leaning performance-testing-method-part II: It carried out by the method of examining wet decomposition performance ". The decomposition active index (MB value) was as being shown in Table 4.</p><p num="0095">The TiO more nearly same than the result shown in Table 4_２In the case of quantity, it is ZrO._２It turned out that MB value becomes high in the added way.</p><p num="0096"><tables num="4"><img file="WO2012014877A1_D0004.tif" /></tables></p><p num="0097">Evaluation experiment A4: Outdoor exposure examination (Miyakojima)<br />Outdoor exposure was performed at an angle of 20 degrees from the level towards the south face using the exposure mount specified to JIS K 5600-7-6 in Okinawa Miyakojima about Examples A15 and A16 and comparative example A6. Evaluation took out the specimen six months afterward and computing the residual ratio of a photocatalyst layer by comparison of surface observation of five views by the electron microscope before and behind exposure estimated.<br />The result was as being shown in Table 5.</p><p num="0098"><tables num="5"><img file="WO2012014877A1_D0005.tif" /></tables></p><p num="0099">Example B1<br />First, photocatalyst coating liquid was prepared as follows. A Anatase type Chita Near water dispersing element (number mean particle size: 40 nm) and water distributed colloidal silica (number mean particle size: 20 nm), It mixed in the water as a solvent, the zirconia particle water dispersing element (single Oblique crystal, average crystallite diameter of 5 nm) was adjusted so that it might become solid content concentration 5.5 mass %, and photocatalyst coating liquid was obtained. It is here and is TiO._２Solid content, solid content of colloidal silica, and ZrO_２The mass ratio of Solid content was set to 10:81:9.</p><p num="0100">The crystallized type of each ingredient in this photocatalyst coating liquid was checked from the result of the powder X diffraction over each dry matter. The above-mentioned number mean particle size observed each dry matter with the scanning electron microscope, and computed it by measuring the length of 100 arbitrary particles included in the views of being 200,000 times many.</p><p num="0101">The average crystallite diameter in a zirconia particle water dispersing element is LaB as standard data from the peak in near 2 theta= 28 degree of the powder X diffraction over a dry matter._６It computed by Using Scherrer's formula.</p><p num="0102">The surface applied this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, it was dried at normal temperature, and the photocatalyst paint object was acquired. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0103">Example B-2<br />TiO of photocatalyst coating liquid_２Solid content, solid content of colloidal silica, and ZrO_２The sample was produced on the same conditions as Example B1 except having set the mass ratio of Solid content to 10:72:18. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0104">Example B3<br />TiO of photocatalyst coating liquid_２Solid content, solid content of colloidal silica, and ZrO_２The sample was produced on the same conditions as Example B1 except having set the mass ratio of Solid content to 10:45:45. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0105">Example B4<br />The sample was produced on the same conditions as Example B1 except having carried out the amorphous zirconia particle water dispersing element of the zirconia particle water dispersing element of photocatalyst coating liquid. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0106">Example B5<br />The sample was produced on the same conditions as Example B3 except having carried out the amorphous zirconia particle water dispersing element of the zirconia particle water dispersing element of photocatalyst coating liquid. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0107">Example B6<br />First, photocatalyst coating liquid was prepared. This photocatalyst coating liquid is a Anatase type Chita Near water dispersing element (number mean particle size: 40 nm), Carbonic acid zirconium ammonium solution was mixed with water distributed colloidal silica (number mean particle size: 20 nm) and a zirconia particle water dispersing element (single Oblique crystal, average crystallite diameter of 5 nm) in the water as a solvent, it adjusted so that it might become solid content concentration 5.5 mass %, and photocatalyst coating liquid was obtained. The solid content, solid content of colloidal silica, and ZrO which are TiO2 here_２The mass ratio of ZrO2 equivalent of Solid content and the solid content of carbonic acid zirconium ammonium was set to 10:72:9:9.</p><p num="0108">The crystallized type of each ingredient in this photocatalyst coating liquid was checked from the result of the powder X diffraction over that dry matter. About the above-mentioned number mean particle size, each dry matter was observed with the scanning electron microscope, and it computed by measuring the length of 100 arbitrary particles included in the views of being 200,000 times many.</p><p num="0109">The average crystallite diameter in a zirconia particle water dispersing element is LaB as standard data from the peak in near 2 theta= 28 degree of the powder X diffraction over a dry matter._６It computed by Using Scherrer's formula.</p><p num="0110">The surface applied this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, it was dried at normal temperature, and the photocatalyst paint object was acquired. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0111">Comparative example B1<br />First, photocatalyst coating liquid was prepared as follows. It mixed using the water as a solvent, a Anatase type Chita Near water dispersing element (number mean particle size: 40 nm) and water distributed colloidal silica (number mean particle size: 20 nm) were adjusted so that it might become solid content concentration 5.5 mass %, and photocatalyst coating liquid was obtained. It is here and is TiO._２The mass ratio of Solid content and the solid content of colloidal silica was set to 10:90.</p><p num="0112">The surface applied this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, it was dried at normal temperature, and the photocatalyst paint object was acquired. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 0.8 micrometer.</p><p num="0113">Comparative example B-2<br />First, photocatalyst coating liquid was prepared as follows. A Anatase type Chita Near water dispersing element (number mean particle size: 40 nm) and water distributed colloidal silica (number mean particle size: 20 nm), Carbonic acid zirconium ammonium solution was mixed with the amorphous zirconia particle water dispersing element in the water as a solvent, it adjusted so that it might become solid content concentration 5.5 mass %, and photocatalyst coating liquid was obtained. It is here and is TiO._２Solid content, solid content of colloidal silica, and ZrO_２ZrO of Solid content and the solid content of carbonic acid zirconium ammonium_２The mass ratio of the equivalent was set to 10:63:9:18.</p><p num="0114">The surface applied this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, it was dried at normal temperature, and the photocatalyst paint object was acquired. Film thickness of the photocatalyst layer in the acquired photocatalyst paint object<br />It was 8 micrometers.</p><p num="0115">Example B7<br />First, photocatalyst coating liquid was prepared as follows. Silica covering Anatase type Chita Near water dispersing element (number mean particle size: 10 nm), Isopropanol distributed colloidal silica (number mean particle size: 20 nm), It mixed to the mixed solvent (alcohol concentration &gt; 99 % of the weight) of alcohol and water, the zirconia particle water dispersing element (59% of single Oblique crystal with an average crystallite diameter of 8.6 nm and mix crystal of 41% of a cubic with an average crystallite diameter of 7.0 nm) was adjusted so that it might become solid content concentration 1.0 mass %, and photocatalyst coating liquid was obtained. It is here and is TiO._２Solid content, solid content of colloidal silica, and ZrO_２The mass ratio of Solid content was set to 10:81:9.</p><p num="0116">The crystallized type of each ingredient in this photocatalyst coating liquid was checked from the result of the powder X diffraction over each dry matter. The above-mentioned number mean particle size observed each dry matter with the scanning electron microscope, and computed it by measuring the length of 100 arbitrary particles included in the views of being 200,000 times many.</p><p num="0117">The average crystallite diameter in a zirconia particle MeOH dispersing element is LaB as standard data from the peak in theta= 27 degrees - near 2 32 degree the powder X diffraction over a dry matter._６It computed by Using Scherrer's formula.</p><p num="0118">The film thickness of the photocatalyst layer in the photocatalyst paint object acquired [ the surface applying this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, and drying, and ] repeatedly 10 times was 2.2 micrometers.</p><p num="0119">Example B8<br />TiO of photocatalyst coating liquid_２Solid content, solid content of colloidal silica, and ZrO_２The sample was produced on the same conditions as Example B7 except having set the mass ratio of Solid content to 10:72:18. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0120">Example B9<br />TiO of photocatalyst coating liquid_２Solid content, solid content of colloidal silica, and ZrO_２The sample was produced on the same conditions as Example B7 except having set the mass ratio of Solid content to 10:45:45. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0121">Example B10<br />As a zirconia particle methanol dispersing element in photocatalyst coating liquid, the sample was produced on the same conditions as Example B7 except having used 50% of single Oblique crystal with an average crystallite diameter of 5.6 nm, and the mix crystal of 50% of the cubic with an average crystallite diameter of 4.8 nm. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0122">Example B11<br />As a zirconia particle methanol dispersing element in photocatalyst coating liquid, the sample was produced on the same conditions as Example B8 except having used 50% of single Oblique crystal with an average crystallite diameter of 5.6 nm, and the mix crystal of 50% of the cubic with an average crystallite diameter of 4.8 nm. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0123">Example B12<br />As a zirconia particle methanol dispersing element in photocatalyst coating liquid, the sample was produced on the same conditions as Example B9 except having used 50% of single Oblique crystal with an average crystallite diameter of 5.6 nm, and the mix crystal of 50% of the cubic with an average crystallite diameter of 4.8 nm. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0124">Example B13<br />As a zirconia particle methanol dispersing element in photocatalyst coating liquid, the sample was produced on the same conditions as Example B7 except having used single Oblique crystal with an average crystallite diameter of 6.3 nm. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0125">Example B14<br />As a zirconia particle methanol dispersing element in photocatalyst coating liquid, the sample was produced on the same conditions as Example B8 except having used single Oblique crystal with an average crystallite diameter of 6.3 nm. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0126">Comparative example B3<br />First, photocatalyst coating liquid was prepared as follows. Silica covering Anatase type Chita Near water dispersing element (number mean particle size: 10 nm), It mixed to the mixed solvent (alcohol concentration &gt; 99 % of the weight) of alcohol and water, isopropanol distributed colloidal silica (number mean particle size: 20 nm) was adjusted so that it might become solid content concentration 1.0 mass %, and photocatalyst coating liquid was obtained. It is here and is TiO._２Solid content, solid content of colloidal silica, and ZrO_２The mass ratio of Solid content was set to 10:90.</p><p num="0127">The crystallized type of each ingredient in this photocatalyst coating liquid was checked from the result of the powder X diffraction over each dry matter. The above-mentioned number mean particle size observed each dry matter with the scanning electron microscope, and computed it by measuring the length of 100 arbitrary particles included in the views of being 200,000 times many.</p><p num="0128">It repeated 10 times the surface applying this photocatalyst coating liquid to the surface of the substrate by which acrylics silicone paint was carried out, and drying, and acquired the photocatalyst paint object. The film thickness of the photocatalyst layer in the acquired photocatalyst paint object was 2.2 micrometers.</p><p num="0129">Evaluation experiment B1:NOx removal examination<br />The NOx removal examination was done by the method as follows. The above-mentioned sample is first considered as a pretreatment, and it is 1mW/cm.^２It irradiated with 5 or more hr with of BLB light. Subsequently, after being immersed in distilled water for 2 hours, dryness was performed 30 minutes or more at 50 . After that, by the method given in JIS R 1701-1, the NOx removal examination was done and the amount of NOx removal (deltaNOx) (micromol) was computed.<br />Relative generation rate R of NO2 which is an intermediate product was calculated according to the following formula.<br />R(%)=[NO_２(Time of irradiation)-NO_２(After irradiation)]/[NO(after irradiation)-NO (irradiation)<br />Time]<br />The result was as being shown in Table 6 and 7.</p><p num="0130"><tables num="6"><img file="WO2012014877A1_D0006.tif" /></tables></p><p num="0131"><tables num="7"><img file="WO2012014877A1_D0007.tif" /></tables></p>