JP5818943B2 - Indoor building materials - Google Patents

Description

  The present invention relates to indoor building materials.

  Titanium oxide is known as a photocatalytic material used for applications such as antifouling and deodorization. Photocatalytic materials are used in various fields such as outdoor and indoor building materials, and home appliances such as lighting devices, refrigerators, air conditioners, and toilets. However, since titanium oxide is excited in the ultraviolet region, sufficient photocatalytic performance cannot be obtained indoors where there is little ultraviolet light. Therefore, research and development of visible light responsive photocatalysts that exhibit photocatalytic performance even under visible light are being promoted.

  With respect to titanium oxide used as an ultraviolet light-responsive photocatalyst, methods for doping nitrogen or sulfur or supporting a metal or the like are being studied in order to improve the performance as a visible light-responsive photocatalyst. In these photocatalysts, the photocatalytic activity is proportional to the amount of light when the illuminance of ordinary indoor lighting (several lx to 3000 lx) is used. Then, there is a problem that performance is insufficient.

  The photocatalytic action absorbs light and excites a pair of electrons and holes for one photon. The excited electrons and holes activate the hydroxyl and oxygen on the surface by oxidation and reduction, and the activated oxygen generated by the activation It is considered that the seed has an action of oxidizing and decomposing organic gas and the like. For this reason, the amount of catalytic action of the photocatalyst decreases in a region where the amount of light is small (low illumination region).

  Generally, the illuminance for performance evaluation of a visible light responsive photocatalyst is 6000 lx or more. Titanium oxide that exhibits activity against visible light under such high illuminance has also been obtained, but as the illuminance decreases, the photocatalytic activity rapidly decreases, so in a practical environment as a visible light responsive photocatalyst. The performance cannot be fully demonstrated. A wide area catalyst membrane is effective for deodorizing indoors and removing harmful gases such as formaldehyde, but the ceiling, walls, and floors with large areas are practical unless they have low illumination and are effective in low illumination. There is little nature.

  Tungsten oxide is known as a visible light responsive photocatalyst. Patent Document 1 describes a photocatalytic material in which tungsten oxide is sputter-deposited on a substrate, and tungsten oxide having a triclinic crystal structure is mainly used. Sputter deposition exposes the substrate to a high temperature and may not be applicable depending on the heat-resistant temperature of the substrate. Sputter film formation is complicated in process management and the like, and not only the cost increases depending on the shape and size of the base material, but film formation over a wide range of building materials and the like is difficult. Furthermore, although the visible light responsive photocatalyst layer formed of sputtered tungsten oxide is excellent in hydrophilicity, it has a problem that the decomposition performance of harmful gases such as acetaldehyde is not sufficient. Moreover, since the hydrophilicity data under irradiation of visible light is not shown, it is estimated that sufficient photocatalytic performance is not obtained under visible light.

The use of tungsten oxide powder as a photocatalyst has also been studied. If it is a powder, it can be mixed with an organic binder such as a resin and applied to a base material, so that it is not necessary to expose the base material to a high temperature, and a coating film can be formed over a wide range like a building material. . As a method for producing tungsten oxide powder, a method is known in which ammonium paratungstate (APT) is heated in air to obtain tungsten trioxide powder (see Patent Document 2). Triclinic tungsten trioxide powder having a particle size of 0.01 μm (BET specific surface area = 82 m ² / g) has been obtained by heating APT in air.

The tungsten trioxide (WO ₃ ) powder produced by heating APT or the like in air needs to be fine particles in order to improve the photocatalytic performance. However, although it can be miniaturized to some extent by applying the crushing treatment, it is difficult to reduce the particle size to 100 nm or less, for example. Further, when the pulverization treatment is applied to make fine powder, the crystal structure of the tungsten trioxide (WO ₃ ) fine powder is changed by the stress of the pulverization treatment. It is thought that the photocatalytic performance is deteriorated because defects that cause recombination of electrons and holes are caused by the stress of crushing treatment. On the other hand, in the production method described in Patent Document 2, kneading for 20 hours or more is necessary to stabilize the BET specific surface area, and there is a problem that the production efficiency of the tungsten trioxide powder is low.

  As a method for efficiently obtaining fine powder, for example, Patent Document 3 describes thermal plasma treatment. By applying the thermal plasma treatment, fine powder having a particle diameter of 1 to 200 nm is obtained. Although fine powder can be obtained efficiently by thermal plasma treatment, sufficient photocatalytic properties are not necessarily obtained even if the tungsten oxide fine powder produced by applying the method described in Patent Document 3 is used as it is as a photocatalyst. I can't get it. This is probably because the optical characteristics and crystal structure of tungsten oxide fine powder may not be optimal in the thermal plasma method.

Examples of tungsten oxide include WO ₃ (tungsten trioxide), WO ₂ (tungsten dioxide), WO, W ₂ O ₃ , W ₄ O ₅ , and W ₄ O ₁₁ . Among these, tungsten trioxide (WO ₃ ) is mainly used as a photocatalytic material because it has excellent photocatalytic performance and is stable in the air at room temperature. However, tungsten trioxide (WO ₃ ) has a problem that the photocatalytic performance is not stable because the crystal structure is complex and easily changes with a little stress. Even if the crystal structure is stable, if the surface area is small, sufficient photocatalytic performance cannot be obtained.

  By the way, the indoor environment is low in ultraviolet rays. Furthermore, the indoor illuminance is 3000 lx or less at the highest, and is several hundred lx or less except for on a desk or work place. For example, the indoor illuminance is set for each place and work content according to “illuminance standard” of JIS-Z-9110 (1979). According to this, the place where important lighting such as a store or a department store or an extremely fine work such as a factory is performed has a slightly high illuminance of 1500 to 3000 lx.

  However, the general manufacturing process of a normal office or factory, the place where the detailed work of the house is performed is 1500 lx or less, and the illuminance of the dining room in the living room or the dining room table is reduced to 500 to 150 lx. Yes. In ceilings, walls, floors, furniture, home appliances, and the like for which visible light responsive photocatalysts are expected to be applied, the illuminance at the place where they are arranged is remarkably low at around 50 lx. In particular, since the lighting is dark in the hallway and the washroom, the illuminance near the wall in such a place is less than 50 lx. No conventional photocatalyst exhibits practical photocatalytic performance under such low illuminance visible light.

JP 2001-152130 A JP 2002-293544 A JP 2006-102737 A

  An object of the present invention is to provide an indoor building material using visible light responsive photocatalyst powder capable of obtaining practical photocatalytic performance even in a low illumination environment such as a factory, a store, a public facility, or a house. is there.

  The indoor building material according to an aspect of the present invention includes a visible light responsive photocatalyst material containing a visible light responsive photocatalyst powder having a tungsten oxide powder or a tungsten oxide composite powder in a range of 1% by mass to 100% by mass. And a base material having the visible light responsive photocatalytic material on its surface, wherein the tungsten oxide constituting the tungsten oxide powder or the tungsten oxide composite material powder is a single tungsten trioxide. The visible light responsive photocatalyst powder has a crystal structure in which an oblique crystal and a triclinic crystal are mixed, or a crystal structure in which the monoclinic crystal, the triclinic crystal, and an orthorhombic crystal of tungsten trioxide are mixed. -R-1701-1 (2004) nitrogen oxide removal performance (decomposition ability) in accordance with the evaluation of the initial concentration of 10p in a state where a 0.2g sample was put in a flow-type apparatus. In the gas concentration measured by flowing m acetaldehyde gas at 140 mL / min, the gas concentration before light irradiation is A, the gas concentration when 15 minutes or more have passed after light irradiation and when the gas is stable is B, and the gas concentration A When the gas decomposition rate (%) is calculated from the gas concentration B based on [Formula: (A−B) / A × 100], a white fluorescent lamp is used, and an ultraviolet cut filter is used. Is characterized in that the gas decomposition rate when irradiated with visible light having an illuminance of 200 lx with only light of 380 nm or more is 5% or more.

  The visible light responsive photocatalyst powder according to the embodiment of the present invention exhibits practical photocatalytic performance even in a low illuminance environment. Therefore, by applying such a visible light responsive photocatalyst powder, it is possible to provide an indoor building material that exhibits practical photocatalytic performance by visible light in a daily indoor environment with low illuminance.

  Hereinafter, modes for carrying out the present invention will be described. The visible light responsive photocatalyst powder according to an embodiment of the present invention includes a tungsten oxide powder or a tungsten oxide composite powder. The visible light responsive photocatalyst powder exhibits a gas decomposition rate of 5% or more when irradiated with visible light having an illuminance of 200 lx with light having a wavelength of only 380 nm or more in the following gas decomposition test. Further, the visible light responsive photocatalyst powder has a gas decomposition rate of 2% or more when irradiated with visible light having a wavelength of only 380 nm or more and an illuminance of 100 lx, and visible light having a wavelength of 380 nm or more and a light having a wavelength of 380 nm or more. It is preferable that the gas decomposition rate when irradiated with is 1% or more.

  The above-described gas decomposition test for determining the gas decomposition rate is carried out using a flow-type apparatus according to the nitrogen oxide removal performance (decomposition ability) evaluation of JIS-R-1701-1 (2004). In a state where a 0.2 g sample is put in a flow type apparatus, an acetaldehyde gas with an initial concentration of 10 ppm is flowed to measure the gas concentration. In such a gas concentration, A is the gas concentration before light irradiation, and B is the gas concentration when 15 minutes or more have elapsed since the light irradiation and has stabilized. A value calculated based on [Expression: (A−B) / A × 100] from the gas concentration A and the gas concentration B is defined as a gas decomposition rate (%).

  In general, visible light refers to light having a wavelength of 380 to 830 nm. In order to evaluate better performance under visible light similar to the actual use environment, visible light having a wavelength of only 380 nm or more is used in the evaluation of this embodiment. Specifically, a white fluorescent lamp specified in JIS-Z-9112 is used as a light source, and an ultraviolet cut filter that cuts light having a wavelength of less than 380 nm is used, and visible light having a wavelength of only 380 nm or more is irradiated. It is preferable to perform evaluation. As the white fluorescent lamp, for example, FL20SS · W / 18 manufactured by Toshiba Lighting & Technology Corp. or its equivalent is used. As the ultraviolet cut filter, for example, Clarex N-169 (trade name) manufactured by Nitto Jushi Kogyo Co., Ltd. or its equivalent is used.

  In indoors where visible light responsive photocatalysts are mainly used, the excitation light is the light from the lighting lamp and the natural light from the window, but the place where the light intensity in the living space is low is only the light from the lighting lamp. There are many. Since the most commonly used indoor illumination light source is a white fluorescent lamp, the performance measurement of the visible light responsive photocatalyst powder of this embodiment is performed using a white fluorescent lamp. As a result, a value closest to the practical performance can be obtained.

  As described above, the visible light responsive photocatalyst powder of this embodiment has a good gas decomposition rate under irradiation with visible light having an illuminance of 200 lx, further under irradiation with visible light having an illuminance of 100 lx, and under irradiation with visible light having an illuminance of 50 lx. Therefore, it is possible to obtain photocatalytic performance in an indoor environment with low illuminance. That is, good photocatalytic performance can be obtained on the basis of a gas decomposition rate of 5% or more, even under illuminance of about 200 lx, such as when the apartment is in a living room or in a bathroom, etc. It becomes possible to provide a visible light responsive photocatalyst powder. Furthermore, 2% or more (100 lx irradiation) or 1% or more (50 lx irradiation) even under extremely low illuminance of about 100 lx to 50 lx such as a place where indoor ceilings, walls, floors, furniture, home appliances, etc. are placed. Practical photocatalytic performance can be obtained based on the gas decomposition rate.

  It goes without saying that the visible light responsive photocatalyst powder of this embodiment exhibits high photocatalytic performance under a remarkably high illuminance such as 6000 lx, which is widely used for its evaluation. Furthermore, it exhibits excellent photocatalytic performance even in an indoor environment with a daily brightness of about 600 lx, such as when reading, in an environment with an illuminance of about 1000 lx, such as in an office or a place where detailed work is performed. . Thus, according to the visible light responsive photocatalyst powder of the embodiment, it is possible to exhibit photocatalytic performance under various illuminances.

  The gas decomposition rate when the visible light responsive photocatalyst powder is irradiated with visible light having an illuminance of 200 lx is preferably 15% or more. The gas decomposition rate when irradiated with visible light with an illuminance of 100 lx is more preferably 10% or more, and the gas decomposition rate when irradiated with visible light with an illuminance of 50 lx is more preferably 5% or more. According to the visible light responsive photocatalyst powder satisfying such conditions, it is possible to obtain excellent photocatalytic performance in indoor environments such as when the apartment is in a living room or in a bathroom. Also, good photocatalytic performance can be obtained even under extremely low illuminance such as a place where indoor ceilings, walls, floors, furniture, home appliances, and the like are placed. Furthermore, in this embodiment, the photocatalytic performance can be obtained even with a small amount of light such as 10 lx, and it becomes possible to provide a visible light responsive photocatalytic powder having unprecedented characteristics.

  The visible light responsive photocatalyst powder having the gas decomposition rate as described above has a particle size of a tungsten oxide powder or a tungsten oxide composite powder (hereinafter referred to as a tungsten oxide-based powder as a general term for these powders) constituting the visible light responsive photocatalyst powder. Specific surface area), crystal structure, crystallinity, powder color, and the like. Here, the tungsten oxide composite powder means that at least one metal element selected from, for example, Ti, Fe, Cu, Zr, Ag, Pt, Pd, Mn, Al, and Ce is added to tungsten oxide as a main component. It is contained in the range of mass% or less. When the content of the metal element exceeds 50% by mass, the remarkable effect of tungsten oxide may not be sufficiently exhibited. The content of the metal element is more preferably 10% by mass or less.

  In the tungsten oxide composite powder constituting the visible light responsive photocatalyst powder, the metal element can be present in various forms. The tungsten oxide composite powder can contain a metal element in the form of a simple metal element, a compound containing the metal element, a composite compound with tungsten oxide, or the like. The metal element contained in the tungsten oxide composite powder itself may form a compound with other elements. A typical form of the metal element is an oxide. The metal element is mixed with the tungsten oxide powder in the form of a simple substance, a compound, a complex compound or the like. The metal element may be supported on tungsten oxide.

  As a specific example of the tungsten oxide composite material powder, a powder containing a copper oxide powder in a range of 1% by mass to 5% by mass can be given. Metal oxide powders other than copper oxide powder (titanium oxide powder, iron oxide powder, etc.) are also preferably contained in the tungsten oxide composite powder in the range of 1% by mass to 5% by mass. The tungsten oxide composite material may contain a tungsten compound other than the oxide, for example, tungsten carbide. Tungsten carbide is mixed with tungsten oxide powder in the range of 1 to 5% by mass as its powder.

  A method of combining tungsten oxide and a metal element (specifically, at least one element selected from Ti, Fe, Cu, Zr, Ag, Pt, Pd, Mn, Al and Ce) It is not particularly limited, and various composite methods such as a mixing method in which powders are mixed with each other, an impregnation method, and a supporting method can be applied. A typical composite method is described below. Examples of the method of combining copper with tungsten oxide include a method of mixing tungsten oxide powder, copper oxide powder, copper nitrate powder, copper sulfate powder and the like. It is also effective to add tungsten oxide powder to an aqueous solution of copper nitrate or copper sulfate or an ethanol solution, mix the powder, and then dry it at a temperature of 70 to 80 ° C. and then fire it at a temperature of 500 to 550 ° C.

  As a method of combining copper with tungsten oxide, for example, a method (impregnation method) in which tungsten oxide powder is dispersed in an aqueous copper chloride solution or an aqueous copper sulfate solution and this dispersion is dried can be applied. The impregnation method is not limited to the copper composite method, but uses an iron composite method using an iron chloride aqueous solution, an iron composite method using a silver chloride aqueous solution, a platinum composite method using a chloroplatinic acid aqueous solution, and a palladium chloride aqueous solution. It can also be applied to the compounding method of palladium. Further, an oxide sol such as a titanium oxide sol or an alumina sol may be used to combine tungsten oxide and a metal element (oxide). In addition to these, various composite methods can be applied.

In the visible light responsive photocatalyst powder of this embodiment, the tungsten oxide-based powder constituting the same preferably has a BET specific surface area in the range of 4.1 to 820 m ² / g. The tungsten oxide powder preferably has an average particle size in the range of 1 to 200 nm. Here, the average particle diameter is determined based on the average particle diameter (D50) of n = 50 or more particles from image analysis of photographs such as SEM and TEM. The average particle diameter (D50) may coincide with the average particle diameter converted from the specific surface area.

The performance of the photocatalyst powder increases as the specific surface area increases and the particle size decreases. Therefore, when the BET specific surface area of the tungsten oxide powder is less than 4.1 m ² / g or the average particle diameter exceeds 200 nm, sufficient photocatalytic performance cannot be obtained. On the other hand, when the BET specific surface area of the tungsten oxide powder exceeds 820 m ² / g or the average particle diameter is less than 1 nm, the particles become too small, and the handleability as a powder is inferior, so the practicality is lowered. . The tungsten oxide-based powder more preferably has a BET specific surface area in the range of 8.2 to 410 m ² / g, and more preferably has an average particle size in the range of 2 to 100 nm.

Preferably the BET specific surface area of the tungsten oxide based powder is in the range of 11~300m ² / g, more preferably in the range of 16~150m ² / g. The average particle size is preferably in the range of 2.7 to 75 nm, more preferably in the range of 5.5 to 51 nm. When the tungsten oxide powder is applied to a visible light responsive photocatalyst paint or the like, if the particle size is too small, the dispersibility of the particles is lowered and it becomes difficult to form a paint. In order to improve such a point, it is preferable to use a tungsten oxide powder having an average particle size of 5.5 nm or more.

  The tungsten oxide constituting the tungsten oxide powder or the tungsten oxide composite powder is at least one crystal structure selected from monoclinic and triclinic tungsten trioxide, or at least selected from the monoclinic and triclinic crystals. It is preferable to have a crystal structure in which orthorhombic crystals are mixed into one kind. The tungsten oxide powder having such a crystal structure can exhibit excellent photocatalytic performance stably. Although it is difficult to identify the abundance ratio of each crystal phase of tungsten trioxide, the crystal structure described above is satisfied when the following conditions (1) to (4) are satisfied when measured by the X-ray diffraction method. It can be estimated that it has.

  (1) In the X-ray diffraction chart, 2θ ranges from 22.5 to 25 °, the first peak (diffraction peak having the highest intensity among all peaks), the second peak (diffraction peak having the second highest intensity), And a third peak (diffraction peak with the third highest intensity).

  (2) In the X-ray diffraction chart, a peak where 2θ is in the range of 22.8 to 23.4 ° is A, a peak where 2θ is in the range of 23.4 to 23.8 ° is B, and 2θ is 24. When the peak existing in the range of 0.02 to 24.25 ° is C and the peak existing in the range of 24.5 to 24.25 to 24.5 ° is D, the intensity ratio of peak A to peak D (A / D ) And peak D to peak B intensity ratio (B / D) is in the range of 0.7 to 2.0, respectively, and peak C to peak C intensity ratio (C / D) is 0.5 to 2. The range is 5.

  (3) In the X-ray diffraction chart, when the peak existing in the range of 33.85 to 34.05 ° is E and the peak existing in the range of 24.0 to 34.05 to 34.25 ° is F, the peak F The intensity ratio (E / F) of peak E with respect to is in the range of 0.5 to 2.0.

  (4) In the X-ray diffraction chart, when the peak existing in the range of 49.1 to 49.7 ° is G and the peak existing in the range of 29.7 to 50.3 ° is H, the peak H The intensity ratio (G / H) of peak G with respect to is in the range of 0.2 to 2.0.

  The measurement and analysis of X-ray diffraction will be described. X-ray diffraction measurement is performed using a Cu target and Ni filter, and only the smoothing process and background removal are performed so that the analysis is not affected by the difference in processing conditions, and the peak intensity is removed without performing Kα2 removal. Measurement shall be performed. Here, as to how to read the peak intensity within each 2θ range of the X-ray diffraction chart, when the mountain is clear, the peak is located at the high position of the mountain within the range, and the height is read. . When the mountain is not clear but there is a shoulder, the shoulder portion is regarded as a peak within the range, and the height of the shoulder portion is read. When the slope has no peaks or shoulders, the height in the middle of the range is read and regarded as the peak intensity within the range.

Furthermore, when the color of the tungsten oxide powder is represented by the L * a * b * color system (Elster / Aster / Baster color system), the tungsten oxide powder has an a * of −5 or less and a b * of Preferably, it has a color of 5 or more and L * of 70 or more. The L * a * b * color system is a method used to represent an object color, which was standardized by the International Commission on Illumination (CIE) in 1976, and specified in JIS Z-8729 in Japan. L * represents lightness, and a * and b * represent hue and saturation. Larger L * indicates brighter. a * and b * indicate the color direction, a * indicates the red direction, -a * indicates the green direction, b * indicates the yellow direction, and -b * indicates the blue direction. Further, saturation (c *) = ((a *) ² + (b *) ² ) ^1/2 is shown.

  The tungsten oxide powder preferably has a color where a * is −5 or less, b * is 5 or more, and L * is 70 or more. Further, a * is in the range of −25 to −8, and b * is 10 to 45. More preferably, the range, L *, has a color of 85 or greater. Such numerical values of the L * a * b * color system indicate that the tungsten oxide powder has a hue from yellow to around green and has high saturation and brightness. When the tungsten oxide powder has such optical characteristics, the photocatalytic performance by excitation with visible light can be improved. The color tone of the tungsten oxide powder is considered to change on the basis of composition variation due to oxygen deficiency or the like, light irradiation, etc., and good photocatalytic performance is obtained when it has the above-described hue, saturation, and brightness. When it has a hue near blue, it is considered that there are many oxygen vacancies and the like, and in such a hue, a decrease in photocatalytic performance is recognized.

  Gas decomposition rate when irradiated with visible light with an illuminance of 200 lx by using a tungsten oxide powder having the above-mentioned particle size (specific surface area), crystal structure, powder color, etc. and further improved crystallinity A visible light responsive photocatalyst powder having a gas decomposition rate of 2% or more when irradiated with visible light with an illuminance of 100 lx and a gas decomposition rate of 1% or more when irradiated with visible light with an illuminance of 50 lx is obtained. be able to. Here, the performance of the visible light responsive photocatalyst powder cannot be enhanced only by the specific surface area and particle size.

  In the case of titanium oxide, visible light responsiveness can be improved by doping nitrogen or sulfur to enhance the visible light absorption performance. Furthermore, by controlling the heat treatment temperature to improve crystallinity or by supporting a metal, it becomes possible to prevent recombination of electrons and holes and increase photocatalytic activity. However, there are some titanium oxides that exhibit high performance under extremely high illuminance at present, but the performance decreases as the illuminance decreases, and practical photocatalytic performance is reduced at daily low illuminances of about 150 to 500 lx. No indication has been obtained. Furthermore, there is no substance that shows activity with a slight light of about 10 lx.

  On the other hand, tungsten oxide powder having visible light absorption performance is applied to the visible light responsive photocatalyst powder, and the BET specific surface area, average particle diameter (D50), crystal structure, powder color, etc. of the tungsten oxide powder. As described above, and further improving the crystallinity of the tungsten oxide powder, it is possible to realize a gas decomposition rate of 5% or more under an illuminance of 200 lx. This is because increasing the specific surface area of the photocatalyst powder increases the amount of gas adsorption, thereby increasing the number of active sites, and also has the effect of reducing the probability of recombination due to improved crystallinity. .

Tungsten oxide has a band gap of 2.5 to 2.8 eV, and absorbs visible light because it is smaller than titanium oxide. Therefore, excellent visible light responsiveness can be realized. Furthermore, since the typical crystal structure of tungsten oxide is a ReO ₃ structure, a crystal plane having high reaction activity having oxygen in the outermost surface layer is easily exposed. For this reason, high hydrophilicity is exhibited by adsorbing water. Alternatively, by oxidizing the adsorbed water, OH radicals can be generated, whereby molecules and compounds can be oxidized. Therefore, photocatalytic performance superior to anatase and rutile crystals of titanium oxide can be exhibited. In addition, since the tungsten oxide powder of this embodiment has a negative zeta potential in an aqueous solution having a pH of 1 to 7, the tungsten oxide powder has excellent dispersibility, and thus can be applied thinly and uniformly to a substrate or the like.

  Examples of the photocatalytic performance include performance for decomposing organic gases such as acetaldehyde and formaldehyde, hydrophilicity, antibacterial / disinfecting performance, and the like. The visible light responsive photocatalyst powder of this embodiment is excellent in photocatalytic performance when irradiated with light of 430 to 500 nm. Examples of the excitation source that emits light having a wavelength of 430 to 500 nm include sunlight, a fluorescent lamp, a blue light emitting diode, and a blue laser. In particular, a blue light emitting diode or a blue laser is preferable because it can emit only light having a wavelength of 430 to 500 nm.

  The tungsten oxide-based powder constituting the visible light responsive photocatalyst powder may contain a metal element as a trace amount of impurities. The content of the metal element as the impurity element is preferably 2% by mass or less. Examples of the impurity metal element include elements generally contained in tungsten ore and contaminating elements mixed when producing a tungsten compound used as a raw material. For example, Fe, Mo, Mn, Cu, Ti, Al, Ca, Ni, Cr, Mg, etc. are mentioned. This is not the case when these elements are used as constituent elements of the composite material.

  The tungsten oxide powder constituting the visible light responsive photocatalyst powder of the above-described embodiment is produced, for example, as follows. The tungsten oxide powder is manufactured by applying a sublimation process. It is also effective to combine a heat treatment process with a sublimation process. According to the tungsten trioxide powder produced by applying a sublimation process or a combination of a sublimation process and a heat treatment process, the above-described crystal structure and BET specific surface area can be stably realized. Furthermore, when the powder is evaluated by SEM or TEM, the average particle size of the primary particles approximates the value converted from the BET specific surface area, and a powder with small particle size variation can be provided stably.

  First, the sublimation process will be described. The sublimation step is a step of obtaining tungsten trioxide powder by sublimating a metal tungsten powder, a tungsten compound powder, or a tungsten compound solution in an oxygen atmosphere. Sublimation is a phenomenon in which a state change from a solid phase to a gas phase or from a gas phase to a solid phase occurs without going through a liquid phase. By oxidizing metal tungsten powder, tungsten compound powder, or tungsten compound solution as a raw material while sublimating, a fine powder tungsten oxide powder can be obtained.

As the raw material for the sublimation process (tungsten raw material), any of metallic tungsten powder, tungsten compound powder, or tungsten compound solution may be used. Examples of the tungsten compound used as the raw material include tungsten trioxide (WO ₃ ), tungsten dioxide (WO ₂ ), tungsten oxides such as lower oxides, tungsten carbide, ammonium tungstate, calcium tungstate, tungstic acid, and the like. .

  By performing the sublimation process of the tungsten raw material as described above in an oxygen atmosphere, the metal tungsten powder and the tungsten compound powder are instantaneously changed from the solid phase to the vapor phase, and further oxidized by oxidizing the vaporized metal tungsten vapor. A tungsten powder is obtained. Even when a solution is used, it becomes a gas phase through tungsten oxide or a compound. Thus, tungsten oxide fine powder can be obtained by utilizing the oxidation reaction in the gas phase. Furthermore, the crystal structure of the tungsten oxide fine powder can be controlled.

  As a raw material for the sublimation process, impurities are hardly contained in the tungsten oxide powder obtained by sublimation in an oxygen atmosphere, and therefore at least one selected from metal tungsten powder, tungsten oxide powder, tungsten carbide powder, and ammonium tungstate powder. It is preferred to use seeds. Metal tungsten powder and tungsten oxide powder are particularly preferable as a raw material for the sublimation process because they do not contain harmful substances as by-products (substances other than tungsten oxide) formed in the sublimation process.

As a tungsten compound used as a raw material, a compound containing tungsten (W) and oxygen (O) as its constituent elements is preferable. When W and O are contained as the constituent components, it is easily sublimated instantaneously when an inductively coupled plasma treatment or the like described later is applied in the sublimation process. Examples of such tungsten compounds include WO ₃ , W ₂₀ O ₅₈ , W ₁₈ O ₄₉ , WO _{2 and the} like. Also effective are solutions or salts of tungstic acid, ammonium paratungstate, and ammonium metatungstate.

  The metal tungsten powder or tungsten compound powder as the tungsten raw material preferably has an average particle size in the range of 0.1 to 100 μm. The average particle size of the tungsten raw material is more preferably in the range of 0.3 μm to 10 μm, further preferably in the range of 0.3 μm to 3 μm, and desirably in the range of 0.3 μm to 1.5 μm. If a metal tungsten powder or a tungsten compound powder having an average particle diameter within the above range is used, sublimation is likely to occur.

  When the average particle size of the tungsten raw material is less than 0.1 μm, the raw material powder is too fine, so that it is necessary to adjust the raw material powder in advance, the handling property is lowered, and the cost is increased. It is not preferable. If the average particle size of the tungsten raw material exceeds 100 μm, a uniform sublimation reaction hardly occurs. Even if the average particle size is large, a uniform sublimation reaction can be caused by treatment with a large amount of energy, but this is not industrially preferable.

  Examples of the method for sublimating the tungsten raw material in the oxygen atmosphere in the sublimation process include at least one treatment selected from inductively coupled plasma treatment, arc discharge treatment, laser treatment, electron beam treatment, and gas burner treatment. Among these, in laser processing or electron beam processing, a sublimation process is performed by irradiating a laser or electron beam. Lasers and electron beams have a small irradiation spot diameter, so it takes time to process a large amount of raw materials at once, but there is an advantage that it is not necessary to strictly control the stability of the raw material particle size and supply amount. .

  Inductively coupled plasma treatment and arc discharge treatment require adjustment of the plasma and arc discharge generation region, but a large amount of raw material powder can be oxidized at a time in an oxygen atmosphere. In addition, the amount of raw material that can be processed at one time can be controlled. Although the gas burner treatment is relatively inexpensive, it is difficult to treat a large amount of raw material powder or raw material solution. For this reason, the gas burner treatment is inferior in terms of productivity. The gas burner treatment is not particularly limited as long as it has sufficient energy for sublimation. A propane gas burner or an acetylene gas burner is used.

  When inductively coupled plasma treatment is applied to the sublimation process, a method is generally used in which plasma is generated using argon gas or oxygen gas, and metal tungsten powder or tungsten compound powder is supplied into the plasma. As a method of supplying the tungsten raw material into the plasma, for example, a method of blowing a metal tungsten powder or a tungsten compound powder together with a carrier gas, a method of blowing a dispersion liquid in which a metal tungsten powder or a tungsten compound powder is dispersed in a predetermined liquid dispersion medium Etc.

  Examples of the carrier gas used when metal tungsten powder or tungsten compound powder is blown into plasma include air, oxygen, an inert gas containing oxygen, and the like. Of these, air is preferably used because of its low cost. When a reaction gas containing oxygen is introduced in addition to the carrier gas, or when the tungsten compound powder is tungsten trioxide, etc., when oxygen is sufficiently contained in the reaction field, a carrier gas such as argon or helium is not used. An active gas may be used. It is preferable to use oxygen, an inert gas containing oxygen, or the like as the reaction gas. In the case of using an inert gas containing oxygen, it is preferable to set the oxygen amount so that the oxygen amount necessary for the oxidation reaction can be sufficiently supplied.

  The crystal structure of the tungsten trioxide powder can be easily controlled by applying a method of blowing metal tungsten powder or tungsten compound powder together with the carrier gas and adjusting the gas flow rate, the pressure in the reaction vessel, and the like. Specifically, at least one selected from monoclinic crystal and triclinic crystal (monoclinic crystal, triclinic crystal, or mixed crystal of monoclinic crystal and triclinic crystal), or orthorhombic crystal mixed therewith. It is easy to obtain tungsten trioxide powder having a crystal structure. The crystal structure of the tungsten trioxide powder is more preferably a mixed crystal of monoclinic crystal and triclinic crystal, or a mixed crystal of monoclinic crystal, triclinic crystal and orthorhombic crystal.

  Examples of the dispersion medium used for preparing the dispersion liquid of the metal tungsten powder or the tungsten compound powder include a liquid dispersion medium having an oxygen atom in the molecule. Use of the dispersion facilitates handling of the raw material powder. As the liquid dispersion medium having an oxygen atom in the molecule, for example, a medium containing 20% by volume or more of at least one selected from water and alcohol is used. As the alcohol used as the liquid dispersion medium, for example, at least one selected from methanol, ethanol, 1-propanol and 2-propanol is preferable. Since water and alcohol are easily volatilized by the heat of plasma, the sublimation reaction and oxidation reaction of the raw material powder are not disturbed, and the oxygen reaction is easily promoted because the molecule contains oxygen.

  In the case of producing a dispersion by dispersing metallic tungsten powder or tungsten compound powder in a dispersion medium, the metallic tungsten powder or tungsten compound powder is preferably contained in the dispersion in a range of 10 to 95% by mass, more preferably It is the range of 40-80 mass%. By dispersing in the dispersion within such a range, the metal tungsten powder and the tungsten compound powder can be uniformly dispersed in the dispersion. If uniformly dispersed, the sublimation reaction of the raw material powder tends to occur uniformly. If the content in the dispersion is less than 10% by mass, the amount of the raw material powder is too small to produce efficiently. If it exceeds 95% by mass, the amount of the dispersion liquid is small, and the viscosity of the raw material powder increases, so that the container becomes easy to stick to the container, and the handleability is lowered.

  The crystal structure of the tungsten trioxide powder can be easily controlled by applying a method in which a metal tungsten powder or a tungsten compound powder is used as a dispersion and blown into the plasma. Specifically, it is easy to obtain a tungsten trioxide powder having a crystal structure in which at least one selected from monoclinic crystals and triclinic crystals, or an orthorhombic crystal mixed therewith. Furthermore, by using a tungsten compound solution as a raw material, the sublimation reaction can be performed uniformly, and the controllability of the crystal structure of the tungsten trioxide powder is improved. The method using the dispersion liquid as described above can also be applied to arc discharge treatment.

When the sublimation process is performed by irradiating with a laser or an electron beam, it is preferable to use as a raw material a metal tungsten or tungsten compound pelletized. Since the irradiation spot diameter of a laser or electron beam is small, supply becomes difficult when metal tungsten powder or tungsten compound powder is used, but it can be efficiently sublimated by using pellets of metal tungsten or tungsten compound. The laser is not particularly limited as long as it has sufficient energy to sublimate metallic tungsten or a tungsten compound, but a CO ₂ laser is preferable because of its high energy.

  When irradiating a laser beam or an electron beam onto the pellet, the entire surface of the pellet having a certain size can be effectively sublimated by moving at least one of the irradiation source of the laser beam and the electron beam or the pellet. This makes it easier to obtain a tungsten trioxide powder having a crystal structure in which orthorhombic crystals are mixed in at least one selected from monoclinic crystals and triclinic crystals. The above pellets can be applied to inductively coupled plasma processing and arc discharge processing.

  The tungsten oxide powder constituting the visible light responsive photocatalyst powder of this embodiment can be obtained only by the sublimation process as described above, but it is also effective to perform a heat treatment process on the tungsten oxide powder produced by the sublimation process. It is. In the heat treatment step, the tungsten trioxide powder obtained in the sublimation step is heat-treated at a predetermined temperature and time in an oxidizing atmosphere. Even when the tungsten trioxide fine powder cannot be sufficiently formed by controlling the conditions of the sublimation process or the like, the proportion of the tungsten trioxide fine powder in the tungsten oxide powder is 99% or more by the heat treatment, substantially 100%. %. Furthermore, the crystal structure of the tungsten trioxide fine powder can be adjusted to a predetermined structure in the heat treatment step.

  Examples of the oxidizing atmosphere used in the heat treatment step include air and oxygen-containing gas. An oxygen-containing gas means an inert gas containing oxygen. The heat treatment temperature is preferably in the range of 200 to 1000 ° C, more preferably 400 to 700 ° C. The heat treatment time is preferably 10 minutes to 5 hours, more preferably 30 minutes to 2 hours. By setting the temperature and time of the heat treatment step within the above ranges, it is easy to form tungsten trioxide from tungsten oxide other than tungsten trioxide. Further, in order to obtain a powder with good crystallinity with few defects, it is preferable to gradually raise or lower the temperature during the heat treatment. Rapid heating or rapid cooling during the heat treatment causes a decrease in crystallinity.

  When the heat treatment temperature is less than 200 ° C., there is a possibility that the oxidation effect for converting the powder that has not been changed to tungsten trioxide in the sublimation process into tungsten trioxide cannot be obtained sufficiently. When the heat treatment temperature exceeds 1000 ° C., the tungsten oxide fine particles grow rapidly, so that the specific surface area of the obtained tungsten oxide fine powder tends to decrease. Furthermore, by performing the heat treatment step at the temperature and time as described above, the crystal structure and crystallinity of the tungsten trioxide fine powder can be adjusted.

  The tungsten oxide powder may contain a transition metal element in order to improve photocatalytic performance and product characteristics such as gas decomposition performance or antibacterial properties. The content of the transition metal element is preferably 50% by mass or less. When content of a transition metal element exceeds 50 mass%, there exists a possibility that the characteristic as visible light responsive photocatalyst powder may fall. The content of the transition metal element is more preferably 10% by mass or less, and further preferably 2% by mass or less. The transition metal element is an element having an atomic number of 21 to 29, 39 to 47, 57 to 79, 89 to 109, and among these, at least one selected from Ti, Fe, Cu, Zr, Ag, and Pt is used. It is preferable. Transition metal elements are contained in the form of metal, oxide, composite oxide, compound, etc., and may be mixed or supported. Further, a compound with tungsten may be formed.

The visible light responsive photocatalyst powder of this embodiment may be used as it is as a visible light responsive photocatalyst, or a powder obtained by mixing, carrying, impregnating, etc., the visible light responsive photocatalyst powder with other materials. It is also possible to use (or a substance other than powder) as a visible light responsive photocatalyst. The visible light responsive photocatalyst material of this embodiment contains visible light responsive photocatalyst powder in the range of 1 to 100% by mass. The content of the visible light responsive photocatalyst powder is appropriately selected according to the desired characteristics, but if it is less than 1% by mass, sufficient photocatalytic performance cannot be obtained. The visible light responsive photocatalyst powder (tungsten oxide powder) may be mixed with particles such as SiO ₂ , ZrO ₂ , Al ₂ O ₃ , and TiO ₂ , or may be supported on these particles. Further, zeolite oxide or the like may be impregnated with tungsten oxide.

  In addition, the visible light responsive photocatalyst powder of this embodiment is used as a visible light responsive photocatalyst coating material by mixing with a solvent, an additive or the like. Instead of the visible light responsive photocatalyst powder, the above-mentioned visible light responsive photocatalyst material may be used as the main component of the visible light responsive photocatalyst paint. The content of the photocatalyst powder or the photocatalyst material in the visible light responsive photocatalyst coating material is in the range of 0.1 to 90% by mass. When the content of the photocatalyst powder or the photocatalyst material is less than 0.1% by mass, the photocatalytic performance cannot be sufficiently obtained, and when it exceeds 90% by mass, the properties as a paint are deteriorated.

  Examples of the solvent and additive blended in the visible light responsive photocatalyst coating material include water, alcohol, a dispersant, and a binder. The binder may be any of an inorganic binder, an organic binder, and an organic / inorganic composite binder. Examples of the inorganic binder include colloidal silica, alumina sol, zirconia sol, and the like. The organic-inorganic composite binder indicates an organic substance containing a metal element such as Si as a constituent component. As an organic component of the organic binder or the organic / inorganic composite binder, a silicone resin or the like is used.

  A visible light responsive photocatalyst product according to an embodiment of the present invention includes the above-described visible light responsive photocatalyst powder or photocatalyst material, or a coating layer of a photocatalyst paint. The photocatalyst product is, for example, a product obtained by adhering or impregnating a photocatalyst powder or a photocatalyst material on a base material, a product obtained by applying a photocatalyst paint to a base material, or the like. Also included are products containing zeolite, activated carbon, porous ceramics, etc. impregnated with photocatalyst powder.

  Specific examples of visible light responsive photocatalytic products include air conditioners, air purifiers, electric fans, refrigerators, microwave ovens, dishwashers / dryers, rice cookers, pots, IH heaters, washing machines, vacuum cleaners, lighting equipment (lamps, utensils) Main body, shade, etc.), sanitary ware, toilet bowl, wash basin, mirror, bathroom (wall, ceiling, floor, etc.), building materials (interior wall, ceiling material, floor, outer wall), interior goods (curtain, carpet, table, chair, Sofas, shelves, beds, bedding, etc.), glass, sashes, handrails, doors, knobs, clothes, filters used for home appliances, and the like. Examples of the substrate of the visible light responsive photocatalyst product include resins such as glass, plastic and acrylic, paper, fiber, metal, and wood. In particular, when a photocatalytic coating is applied to glass, highly transparent glass is obtained.

  The visible light responsive photocatalytic product according to this embodiment can be applied to parts used in a living space or an indoor space of an automobile. Since it is a highly sensitive photocatalyst, photocatalytic performance can be exhibited even in a place where it is difficult for light to hit indoors or in a place with low illuminance. In addition, since glass that hardly transmits ultraviolet rays is used in automobiles, the use of visible light responsive photocatalyst products is effective in decomposing organic gases in spaces where there is almost no ultraviolet rays, hydrophilicity, and antifouling. To do. Photocatalytic performance can be exhibited even when a light source with low illuminance is used, such as a light-emitting diode or miniature light bulb used as an interior of an automobile interior space. For this reason, visible light responsive photocatalyst products can be used even in places and uses where there has been concern about use due to problems with light sources, and the range of application is widened.

  Next, specific examples of the present invention and evaluation results thereof will be described. In the following examples, inductively coupled plasma processing is applied to the sublimation process, but the present invention is not limited to this.

Example 1
First, a tungsten trioxide powder having an average particle size of 0.5 μm was prepared as a raw material powder. This raw material powder was sprayed onto RF plasma together with a carrier gas (Ar), and oxygen was allowed to flow as a reaction gas at a flow rate of 80 L / min. In this manner, a tungsten oxide powder was produced through a sublimation process in which the raw material powder was subjected to an oxidation reaction while being sublimated. Table 1 shows the production conditions of the tungsten oxide powder.

  The BET specific surface area and average particle size (by image analysis of TEM photograph) of the obtained tungsten oxide powder were measured. The measurement of the BET specific surface area was performed using a specific surface area measuring device Macsorb1201 manufactured by Mountec. Pretreatment was performed in nitrogen at 200 ° C. for 20 minutes. For TEM observation, H-7100FA manufactured by Hitachi, Ltd. was used, and an enlarged photograph was subjected to image analysis to extract 50 or more particles, and a volume-based integrated diameter was obtained to calculate D50. Table 2 shows the measurement results of the BET specific surface area and the average particle diameter.

  Moreover, the X-ray diffraction of the tungsten oxide powder was implemented. X-ray diffraction was performed using a Rigaku X-ray diffractometer RINT-2000 using a Cu target, a Ni filter, and a graphite (002) monochromator. Measurement conditions were tube voltage: 40 kV, tube current: 40 mA, divergence slit: 1/2 °, scattering slit: automatic, light receiving slit: 0.15 mm, 2θ measurement range: 20 to 70 °, scanning speed: 0. 5 ° / min, sampling width: 0.004 °. In measuring the peak intensity, Kα2 removal was not performed, but only smoothing and background removal processes were performed. The smoothing was performed using Savizky-Golay (least square method), and filter points 11 were set. Background removal was performed with a linear fit and threshold value σ3.0 within the measurement range. Table 2 shows the identification results of the crystal structure of the tungsten oxide powder based on the X-ray diffraction results.

  Furthermore, the color of the tungsten oxide powder was measured based on the L * a * b * color system. Color measurement based on the L * a * b * color system was performed using a spectrocolorimeter CM-2500d manufactured by Konica Minolta. The measurement results of L * a * b * are shown in Table 2.

  Next, as a characteristic of the obtained tungsten oxide powder, the decomposition rate of acetaldehyde was measured. The decomposition rate of acetaldehyde gas was performed under the conditions shown below using a flow type apparatus similar to the evaluation of nitrogen oxide removal performance (decomposition ability) of JIS-R-1701-1 (2004). Table 3 shows gas decomposition rates when irradiated with visible light having an illuminance of 6000 lx, 2500 lx, 1000 lx, 600 lx, 200 lx, 100 lx, 50 lx, and 10 lx. The gas decomposition rate of the tungsten oxide powder of Example 1 at an illuminance of 200 lx was 21%. Further, the gas decomposition rate at an illuminance of 100 lx was 11%, and the gas decomposition rate at an illuminance of 50 lx was 7%. It was confirmed that the tungsten oxide powder of Example 1 showed a good gas decomposition rate up to an illuminance of 50 lx, and further exhibited a gas decomposition performance even under an extremely low illuminance of 10 lx.

  In the acetaldehyde gas decomposition test, the initial concentration of acetaldehyde was 10 ppm, the gas flow rate was 140 mL / min, and the sample amount was 0.2 g. The preparation of the sample was applied to a 5 × 10 cm glass plate and dried. In the case of a powder sample, it was spread with water and dried. Pretreatment was performed with black light for 12 hours. A white fluorescent lamp (FL20SS · W / 18 manufactured by Toshiba Lighting & Technology Co., Ltd.) was used as a light source, and light having a wavelength of less than 380 nm was cut using an ultraviolet cut filter (manufactured by Nitto Jushi Kogyo Co., Ltd., Clarex N-169). The illuminance was adjusted to a predetermined value. First, wait for the gas to disappear and stabilize without irradiating light. Light irradiation is started after stabilization. Light is irradiated under such conditions, and the gas concentration after 15 minutes is measured to determine the gas decomposition rate. However, if the gas concentration is not stable after 15 minutes, the concentration is continuously measured until it stabilizes. A multi-gas monitor 1412 manufactured by INOVA was used as the gas analyzer.

(Example 2)
A tungsten oxide powder is produced through the same sublimation process as in Example 1 except that argon is flowed at a flow rate of 80 L / min and oxygen is flowed as a reaction gas, and the pressure in the reaction vessel is adjusted to 35 kPa and the reduced pressure side. did. Furthermore, the tungsten oxide powder was heat-treated in air at 450 ° C. × 0.5 h. At this time, the temperature was raised to the heat treatment temperature in 0.5 h, and after the heat treatment, it was cooled to room temperature over 2 h. The tungsten oxide powder thus obtained was measured and evaluated in the same manner as in Example 1. Table 1 shows the preparation conditions of the tungsten oxide powder, Table 2 shows the measurement results of the powder characteristics, and Table 3 shows the measurement results of the gas decomposition rate. It was confirmed that the tungsten oxide powder according to Example 2 showed good gas decomposition performance even under low illumination. Furthermore, it was confirmed that the activity was exhibited even under an illuminance of 10 lx.

(Examples 3 to 5)
In Examples 3-5, the same sublimation process as Example 1 was implemented. In Example 3, a sublimation process was performed by flowing argon as a reaction gas at a flow rate of 40 L / min and air at a flow rate of 40 L / min, and a heat treatment process was performed under conditions of 500 ° C. × 1 h after the sublimation process. At this time, the temperature was raised to the heat treatment temperature in 0.5 h, and after the heat treatment, it was cooled to room temperature over 2 h. In Example 4, a sublimation process was performed by flowing argon as a reaction gas at a flow rate of 40 L / min and oxygen at a flow rate of 100 L / min, and a heat treatment process was performed under conditions of 600 ° C. × 0.5 h after the sublimation process. At this time, the temperature was raised to the heat treatment temperature in 0.5 h, and after the heat treatment, it was cooled to room temperature over 2 h. In Example 5, the sublimation process was performed by flowing argon as a reaction gas at a flow rate of 40 L / min and oxygen at a flow rate of 40 L / min, and the heat treatment process was performed under conditions of 800 ° C. × 0.5 h after the sublimation process. At this time, the temperature was raised to the heat treatment temperature in 0.5 h, and after the heat treatment, it was cooled to room temperature over 2 h.

  About the obtained tungsten oxide powder, the same measurement and evaluation as Example 1 were performed. Table 1 shows the preparation conditions of the tungsten oxide powder, Table 2 shows the measurement results of the powder characteristics, and Table 3 shows the measurement results of the gas decomposition rate. It was confirmed that any of the tungsten oxide powders according to Examples 3 to 5 showed good gas decomposition performance even under low illuminance. Further, it was confirmed that all of Examples 3 to 5 showed activity even under an illuminance of 10 lx.

(Example 6)
Except for flowing argon at a flow rate of 40 L / min and oxygen at a flow rate of 40 L / min as a reaction gas, after performing a sublimation process in the same manner as in Example 1, heat treatment was performed in air at 950 ° C. × 0.75 h. The process was carried out. About the obtained tungsten oxide powder, the same measurement and evaluation as Example 1 were performed. Table 1 shows the preparation conditions of the tungsten oxide powder, Table 2 shows the measurement results of the powder characteristics, and Table 3 shows the measurement results of the gas decomposition rate. The tungsten oxide powder according to Example 6 showed good gas decomposition performance under an illuminance of 200 to 50 lx, which was inferior to Examples 1 to 5. For this reason, when the illuminance was lowered to 10 lx, gas decomposition performance could not be obtained, but under 200 lx illuminance, the gas decomposition rate was 5%.

(Comparative Example 1)
The tungsten oxide powder produced through the same sublimation process as in Example 3 was subjected to heat treatment in the atmosphere at 1050 ° C. × 0.25 h. About the obtained tungsten oxide powder, the same measurement and evaluation as Example 1 were performed. Table 1 shows the preparation conditions of the tungsten oxide powder, Table 2 shows the measurement results of the powder characteristics, and Table 3 shows the measurement results of the gas decomposition rate. The tungsten oxide powder had a slightly small BET specific surface area of 4 m ² / g and an average particle size of 215 nm, so that the gas decomposition rate at 200 lx was low, and no gas decomposition performance was exhibited at 100 lx or 50 lx. This is presumably because grain growth occurred by heat treatment at a high temperature.

(Comparative Example 2)
Measurements and evaluations similar to those in Example 1 were performed using a tungsten oxide powder (manufactured by Rare Metallic) commercially available as a reagent. Table 2 shows the powder characteristics, and Table 3 shows the measurement results of the gas decomposition rate. From the X-ray diffraction results, the crystal system was estimated to be a monoclinic and triclinic mixed crystal, the BET specific surface area was 0.7 m ² / g, and the average particle size was 1210 nm. Since the tungsten oxide powder of Comparative Example 2 has a small specific surface area and a remarkably large particle size, a slight gas decomposition performance was observed at 6000 lx, but no gas decomposition performance was exhibited at 2500 lx or less.

(Comparative Example 3)
In titanium oxide, titanium oxide carrying Pt for improving visible light activity was prepared, and the same measurement and evaluation as in Example 1 were performed. Table 2 shows the powder characteristics other than the crystal system, and Table 3 shows the measurement results of the gas decomposition rate. The BET specific surface area was as large as 210 m ² / g, and the average particle size was as small as 7.2 nm. The gas decomposition rates at 6000 lx and 2500 lx were relatively high, but the gas decomposition rates at 1000 lx, 600 lx, and 200 lx were 29%, 18%, and 5%, which were only small values compared to the examples. For this reason, the gas decomposability rate at 100 lx was very small, and gas decomposition performance was not exhibited at 50 lx or less, and it was confirmed that the activity was low at low illuminance.

(Comparative Example 4)
In titanium oxide, titanium oxide carrying Fe in order to improve visible light activity was prepared, and the same measurement and evaluation as in Example 1 were performed. Table 2 shows the powder characteristics other than the crystal system, and Table 3 shows the measurement results of the gas decomposition rate. The BET specific surface area was as large as 170 m ² / g, and the average particle size was as small as 8 nm. The gas decomposition rates of 6000 lx and 2500 lx were relatively high, but the gas decomposition rates at 1000 lx and 600 lx were 26% and 16%, which were only small values compared to the examples. For this reason, the gas decomposability rate at 200 lx was slight, and it was confirmed that the gas decomposition performance was not exhibited at 100 lx or less, and the activity was low at low illuminance.

  As described above, the visible light responsive photocatalyst powder comprising the tungsten oxide powder according to each example exhibits high photocatalytic performance even under low illuminance of about 200 lx such as when a living room is laid or in a bathroom. It can be seen that the photocatalytic performance is exhibited even under extremely low illuminance of about 50 lx such as a place where walls, furniture, home appliances, etc. are placed. Furthermore, a material exhibiting a relatively high photocatalytic performance at 200 to 50 lx exhibits activity even with a slight amount of light such as 10 lx, and has unprecedented characteristics. Of course, such materials exhibit excellent photocatalytic performance not only at a remarkably high illuminance of 6000 lx, but also under illuminances of 2500 lx, 1000 lx and 600 lx. From this, it is possible to provide a visible light responsive photocatalyst that can be used anywhere as long as light is present.

(Example 7)
The tungsten oxide powder obtained in Example 3 was mixed with 1% by mass of copper oxide (CuO) powder. The tungsten oxide powder thus obtained was measured for gas decomposition rate in the same manner as in Example 1. The gas decomposition rates under irradiation of illuminance of 6000 lx, 2500 lx, 1000 lx, 600 lx, 200 lx, 100 lx, 50 lx show excellent values of 96%, 90%, 74%, 60%, 35%, 18, 13%, respectively. It was. Further, it was confirmed that the gas decomposition rate was 3% even under a low illuminance of 10 lx, and the photocatalytic performance was exhibited.

(Example 8)
A water-based paint was prepared by adding 5% by mass of the tungsten oxide powder prepared in Example 3 and 0.05% by mass of colloidal silica. This was applied to glass and dried to produce a glass having a photocatalyst coating layer. About such glass, the gas decomposition rate was measured like the powder. As a result, it was confirmed that the gas decomposition rate under irradiation with an illuminance of 200 lx showed a good value of 11%.

  Furthermore, when the above-mentioned paint was applied to the glass in the interior space of an automobile, the smell of tobacco was reduced and the glass became difficult to get dirty. Incidentally, when the glass coated with this paint was evaluated for hydrophilicity, the contact angle was 1 ° or less, and superhydrophilicity was exhibited. Moreover, when antibacterial property was evaluated using Staphylococcus aureus, Escherichia coli and mold, it was confirmed that all exhibited excellent antibacterial property. Furthermore, when the above-mentioned paint was applied to the bathroom and its surroundings, where mold was prone to grow, it was confirmed that mold was difficult to grow even in places where it was difficult to hit.

  The visible light responsive photocatalyst powders of the examples are excellent in the decomposition performance of organic gases such as acetaldehyde, and the photocatalyst coating layer has high transmittance, so that problems such as color unevenness are not likely to occur visually. Therefore, it is suitably used for building materials used in automobile interior spaces, factories, shops, public facilities, houses, etc., interior materials, and home appliances. Moreover, since the gas decomposition performance is exhibited even at low illuminance, the effect can be exhibited even with light from an LED, a miniature light bulb or the like.

(Examples 9 and 10)
The tungsten oxide powder obtained in Example 3 and Example 5 was mixed with 15% by mass of Pd powder. The tungsten oxide composite powder thus obtained was measured for gas decomposition rate in the same manner as in Example 1. The gas decomposition rates under irradiation with an illuminance of 50 lx were 23% and 6%, respectively, and were higher than before Pd mixing regardless of the particle size. However, since the color of the powder was black, transparency was lost when the paint was prepared.

(Example 11)
The tungsten oxide powder obtained in Example 3 was dispersed in an aqueous iron chloride solution. This dispersion was centrifuged, and the supernatant was removed and washed by adding water twice. Thereafter, the powder after removing the supernatant was dried at 110 ° C. for 12 hours to produce a tungsten oxide composite material powder containing 1% by mass of Fe. The gas decomposition rate of the tungsten oxide composite powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was as high as 18% under irradiation with visible light having an illuminance of 50 lx.

(Example 12)
In the same manner as in Example 11, a tungsten oxide composite powder containing 0.3% by mass of Cu was prepared using an aqueous copper chloride solution. The gas decomposition rate of the tungsten oxide composite powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was as high as 17% under irradiation with visible light having an illuminance of 50 lx.

(Example 13)
In the same manner as in Example 11, a tungsten oxide composite powder containing 0.5% by mass of Ag was prepared using an aqueous silver nitrate solution. The gas decomposition rate of the tungsten oxide composite powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was as high as 15% under irradiation with visible light having an illuminance of 50 lx.

(Examples 14 to 17)
In the same manner as in Example 11, tungsten oxide composite powders containing 2% by mass and 0.5% by mass of Pd were prepared using an aqueous palladium chloride solution, and the powders of Example 14 and Example 15 were obtained. . Further, a tungsten oxide composite powder was produced in the same manner as in Example 15 except that the tungsten oxide powder obtained in Example 1 and Example 5 was used, and the powders of Example 16 and Example 17 were obtained. The gas decomposition rate of these powders was measured in the same manner as in Example 1. As a result, under the irradiation of visible light with an illuminance of 50 lx, the gas decomposition rates showed values of 17%, 22%, 20% and 10%, respectively, which were higher than before adding Pd regardless of the particle diameter. . However, the Pd content of 2% by mass has a lower gas decomposition performance than the one containing 0.5% by mass of Pd because Pd is too much around the tungsten oxide particles.

(Example 18)
The tungsten oxide powder obtained in Example 3 was dispersed in an aqueous chloroplatinic acid solution, irradiated with visible light and charged with methanol, and supported by a photoprecipitation method. Centrifugation was performed, and the supernatant was removed and the water was washed twice. After that, the supernatant was removed at 110 ° C. for 12 hours to obtain a tungsten oxide composite powder containing 0.1% by mass of Pt. Produced. The gas decomposition rate of this powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was as high as 25% under irradiation with visible light having an illuminance of 50 lx.

(Examples 19 to 21)
The tungsten oxide powder obtained in Example 3 was mixed with titanium oxide powder ST-01 (trade name, manufactured by Ishihara Sangyo Co., Ltd.) at a ratio of 70% by mass, 40% by mass, and 10% by mass. Tungsten oxide composite powders of Example 20 and Example 21 were prepared. Mixing was performed using a mortar. The gas decomposition rate of these powders was measured in the same manner as in Example 1. As a result, under the irradiation of visible light with an illuminance of 50 lx, the gas decomposition rates were 6%, 15%, and 18%, respectively. The performance of the tungsten oxide composite powder of Example 19 was slightly degraded due to too little tungsten oxide, but the other values were higher than before mixing.

(Examples 22 and 23)
Except for using the tungsten oxide powder obtained in Example 1 and Example 5, 10% by mass of titanium oxide powder was mixed in the same manner as in Example 21 to prepare the powders of Example 22 and Example 23. The gas decomposition rate of these powders was measured in the same manner as in Example 1. As a result, under the irradiation of visible light with an illuminance of 50 lx, the gas decomposition rates showed values of 12% and 9%, respectively, and it was confirmed that the gas decomposition rate was improved compared to before mixing of the titanium oxide powder.

(Example 24)
The tungsten oxide powder obtained in Example 3 was dispersed in titanium oxide sol STS-01 (trade name, manufactured by Ishihara Sangyo Co., Ltd.) and then dried at 110 ° C. for 12 hours to contain 5% by mass of TiO _2. A tungsten oxide composite powder was prepared. The gas decomposition rate of this powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was as high as 19% under irradiation with visible light having an illuminance of 50 lx. It is considered that high performance was obtained because TiO ₂ was more uniformly dispersed than when mixed with TiO ₂ powder.

(Example 25)
In the same manner as in Example 7, a powder in which 20% by mass of CuO powder was mixed with the tungsten oxide powder obtained in Example 3 was produced. The gas decomposition rate of this powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate was 8% under irradiation with visible light having an illuminance of 50 lx. However, because the content of CuO is too large, the characteristics are lower than the powder mixed at a ratio of 1% by mass, and the color of the powder is black.

(Example 26)
The tungsten oxide powder obtained in Example 3 was mixed with 0.5% by mass of zirconium oxide (ZrO ₂ ) powder. The gas decomposition rate of this powder was measured in the same manner as in Example 1. As a result, the gas decomposition rate showed a high value of 14% under irradiation with visible light having an illuminance of 50 lx.

(Example 27)
The tungsten oxide powder obtained in Example 3 was dispersed in alumina sol, and this dispersion was dried at 110 ° C. for 12 hours to produce a powder containing 2% by mass of Al ₂ O ₃ . The gas decomposition rate of this powder was measured in the same manner as in Example 1. As a result, under irradiation with visible light having an illuminance of 50 lx, the gas decomposition rate was 12%, which was equivalent to or better than that before mixing.

(Examples 28 to 30)
The tungsten oxide powder obtained in Example 3 was mixed with tungsten carbide (WC) powder at a ratio of 10% by mass, 2% by mass, and 0.5% by mass, and Example 28, Example 29, and Example 30 were mixed. A powder was prepared. The gas decomposition rate of these powders was measured in the same manner as in Example 1. Under the irradiation of visible light with an illuminance of 50 lx, the gas decomposition rates were 7%, 13%, and 15%, respectively. In Example 28, the value was lower than that before mixing because of too much WC, but Example 29 and Example 30 showed values equal to or higher than those before mixing. However, the higher the content of WC, the blacker the powder color, so the transparency was lost when the paint was produced.

(Example 31)
Using the tungsten oxide powder obtained in Example 3 and water, a dispersion treatment was performed in a bead mill to prepare an aqueous dispersion having a concentration of 10% by mass. This was mixed with an aqueous cerium chloride solution to prepare a solution having a mass ratio of Ce and WO ₃ of 1: 999. After apply | coating this solution to a glass plate, it was made to dry at 110 degreeC for 0.5 hour, and the sample of Example 31 was obtained. For comparison, a similar sample was prepared using only the aqueous dispersion before mixing with cerium chloride. The gas decomposition rate of these samples was measured in the same manner as in Example 1. As a result, under the irradiation of visible light with an illuminance of 50 lx, the gas decomposition rate showed a value of 4%, which was the same value as before Ce addition.

(Example 32)
The sample manufactured in Example 31 was further heat-treated at 350 ° C. for 1 hour in the air. The gas decomposition rate of this sample was measured in the same manner as in Example 1. As a result, under irradiation with visible light with an illuminance of 50 lx, the gas decomposition rate was 7%, which was higher than that of the sample only dried at 110 ° C. (Example 31). By increasing the heating temperature, excess moisture, chlorides, and the like were reduced, and it is considered that the characteristics were improved.

(Example 33)
Similarly to Example 31, an aqueous dispersion of 10% by mass of tungsten oxide using the powder of Example 3 was prepared, and an aqueous nickel nitrate solution was mixed therewith so that the mass ratio of Ni and WO ₃ was 1: 999. A solution of was prepared. This solution was applied to a glass plate, dried at 110 ° C. for 0.5 hour, and further heated in air at 350 ° C. for 1 hour to obtain a sample of Example 33. The gas decomposition rate of this sample was measured in the same manner as in Example 1. As a result, under irradiation with visible light with an illuminance of 50 lx, the gas decomposition rate showed a value of 8%, which was higher than before Ni addition.

(Example 34)
Similarly to Example 33, an aqueous dispersion of 10% by mass of tungsten oxide using the powder of Example 3 was prepared, and an aqueous manganese chloride solution was mixed therewith so that the mass ratio of Mn to WO ₃ was 1: 999. A solution of was prepared. This solution was applied to a glass plate, dried at 110 ° C. for 0.5 hour, and further heated in air at 350 ° C. for 1 hour to prepare a sample. The gas decomposition rate of this sample was measured in the same manner as in Example 1. As a result, under irradiation with visible light having an illuminance of 50 lx, the gas decomposition rate was 7%, which was higher than before Mn addition. All of the samples of each of the above-described examples showed high hydrophilicity, and were confirmed to have antibacterial and antifungal properties.

Claims (10)

Visible light responsive photocatalyst material containing visible light responsive photocatalyst powder comprising tungsten oxide powder or tungsten oxide composite powder in the range of 1% by mass to 100% by mass, and the visible light responsive photocatalyst material on the surface An indoor building material comprising a base material that is present,
The tungsten oxide constituting the tungsten oxide powder or the tungsten oxide composite powder is a crystal structure in which monoclinic crystals and triclinic crystals of tungsten trioxide are mixed, or the monoclinic crystal, the triclinic crystal, and the tungsten trioxide. Has an orthorhombic crystal structure,
The visible light responsive photocatalyst powder has an initial concentration in a state where 0.2 g of a sample is put in a flow-type apparatus according to the nitrogen oxide removal performance (decomposition ability) evaluation of JIS-R-1701-1 (2004). In the gas concentration measured by flowing 10 ppm of acetaldehyde gas at 140 mL / min, the gas concentration before light irradiation is A, the gas concentration is 15 minutes after light irradiation, and the gas concentration when stable is B, and the gas concentration A When the gas decomposition rate (%) is calculated from the gas concentration B based on [Formula: (A−B) / A × 100], a white fluorescent lamp is used, and an ultraviolet cut filter is used. Is a building material for indoor use, wherein the gas decomposition rate is 5% or more when irradiated with visible light having an illuminance of 200 lx with light of only 380 nm or more. In the indoor building material of Claim 1,
The building material for indoor use, wherein the base material is made of glass, resin, paper, fiber, metal, or wood. In the indoor building material according to claim 1 or 2,
The substrate has an adhesion layer in which the visible light responsive photocatalytic material is adhered to the surface, or an application layer in which a coating material containing the visible light responsive photocatalytic material is applied on the surface. Building materials. In the indoor building material of any one of Claims 1 thru | or 3,
An indoor building material, wherein the gas decomposition rate when irradiated with visible light having a wavelength of 380 nm or more and illuminance of 100 lx is 2% or more. The indoor building material according to any one of claims 1 to 3,
A building material for indoor use, wherein the gas decomposition rate when irradiated with visible light having a wavelength of 380 nm or more and illuminance of 50 lx is 1% or more. In the indoor building material of any one of Claim 1 thru | or 5,
The building material for indoor use, wherein the tungsten oxide powder or the tungsten oxide composite material powder has a BET specific surface area of 4.1 m ² / g or more and 820 m ² / g or less. The indoor building material according to any one of claims 1 to 6,
The building material for indoor use, wherein the tungsten oxide powder or the tungsten oxide composite material powder has an average particle diameter (D50) in the range of 1 nm to 200 nm. In the indoor building material of any one of Claims 1 thru | or 7,
When the color of the tungsten oxide powder or the tungsten oxide composite material powder is expressed in the L * a * b * color system, the tungsten oxide powder or the tungsten oxide composite material powder has an a * of −5 or less and b * of An indoor building material characterized by having a color of 5 or more and L * of 70 or more. The indoor building material according to any one of claims 1 to 8,
The tungsten oxide composite powder contains at least one metal element selected from Ti, Fe, Cu, Zr, Ag, Pt, Pd, Mn, Al, and Ce in a range of 50% by mass or less. Indoor building materials. The indoor building material according to claim 9,
The building material for indoor use, wherein the tungsten oxide composite powder contains the metal element in an amount of 10% by mass or less.