WO2018167914A1 - Photocatalyst coating agent - Google Patents

Photocatalyst coating agent Download PDF

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Publication number
WO2018167914A1
WO2018167914A1 PCT/JP2017/010667 JP2017010667W WO2018167914A1 WO 2018167914 A1 WO2018167914 A1 WO 2018167914A1 JP 2017010667 W JP2017010667 W JP 2017010667W WO 2018167914 A1 WO2018167914 A1 WO 2018167914A1
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WO
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Prior art keywords
particle diameter
coating agent
primary particle
silica
inorganic binder
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PCT/JP2017/010667
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French (fr)
Japanese (ja)
Inventor
誠之 島田
勇二 藤田
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ヒロセ株式会社
誠之 島田
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Priority to PCT/JP2017/010667 priority Critical patent/WO2018167914A1/en
Publication of WO2018167914A1 publication Critical patent/WO2018167914A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—

Definitions

  • the present invention relates to a photocatalyst coating agent capable of imparting functions such as antifouling, deodorizing, antibacterial, etc. by applying it to articles such as interior materials and cloth, and the surface of wall materials, for example.
  • photocatalyst coating agent for example, there is one in which a photocatalyst such as titanium oxide is dispersed in an inorganic binder such as silica, and when this is applied to the substrate surface, a photocatalyst such as titanium oxide is formed by the inorganic binder.
  • a photocatalyst such as titanium oxide
  • an inorganic binder such as silica
  • Titanium oxide which is widely used as a photocatalyst, can be obtained at a low price. However, since it exhibits catalytic activity only for ultraviolet light, sufficient performance cannot be obtained in a room where ultraviolet light is extremely weak. For this reason, a photocatalyst coating agent using a visible light active photocatalyst that exhibits sufficient performance indoors is required.
  • the photocatalyst imparted with visible light activity in this way has a characteristic that the oxidizing power of the photocatalyst is lower than the oxidizing power of the photocatalyst having the original ultraviolet photocatalytic activity.
  • the photoexcited state in order for a metal oxide to exhibit photocatalytic activity, the photoexcited state must be able to be maintained for a certain period of time. However, if the particle size of the metal oxide constituting the photocatalyst is reduced, the photoexcited state must be maintained. However, since excited electrons and holes generated by photoexcitation recombine and return to the original ground state, sufficient photocatalytic activity cannot be obtained. For this reason, as described above, with respect to a visible light active photocatalyst that does not have high oxidizing power, the visible light catalytic activity is increased by increasing the particle diameter of the metal oxide constituting the photocatalyst as much as possible. is the current situation.
  • the particle size of the metal oxide composing the photocatalyst is increased, the surface area becomes smaller (the contact area with the substance to be decomposed), so that the substance to be decomposed can be efficiently decomposed in a short time.
  • the decomposition ability is reduced.
  • the visible light activity type photocatalyst increases the visible light catalytic activity by increasing the particle size of the metal oxide constituting the photocatalyst
  • the decomposition ability of the substance to be decomposed decreases.
  • the particle size of the metal oxide is reduced to increase the decomposition ability of the substance to be decomposed, the visible light catalytic activity is lowered.
  • an object of the present invention is to provide a photocatalyst coating agent capable of ensuring a sufficient visible photocatalytic activity even when the particle diameter of the metal oxide constituting the photocatalyst is small.
  • the invention according to claim 1 is a photocatalyst coating agent in which a metal oxide is dispersed in an inorganic binder, and the inorganic binder comprises silica having a primary particle diameter of 20 nm or less and 5 nm or more.
  • a photocatalyst coating agent, wherein the main material particles and auxiliary particles containing silica whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles are dispersed in water. It is to provide.
  • the invention according to claim 2 is the photocatalytic coating agent according to the invention according to claim 1, wherein the inorganic binder has a platinum group element whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles. It contains at least one kind of auxiliary material particles selected from the above.
  • the invention according to claim 3 is the photocatalyst coating agent according to the invention according to claim 2, wherein the inorganic binder has a primary particle diameter of 1/3 or less of the primary particle diameter of the main material particles. And containing at least one kind of auxiliary material particles selected from tin oxide.
  • the invention according to claim 4 is the photocatalyst coating agent according to claim 1, 2, or 3, wherein the metal oxide has a primary particle diameter of 5 nm or less.
  • the invention according to claim 5 is the photocatalyst coating agent according to claim 1, 2, 3 or 4, wherein the metal oxide is titanium oxide, oxygen-deficient titanium oxide or tungsten oxide. It is said.
  • the photocatalyst coating agent of the invention according to claim 1 includes a metal oxide, a primary material particle composed of silica having a primary particle diameter of 20 nm or less and 5 nm or more, and a primary particle diameter of the primary particle.
  • a metal oxide that cannot obtain visible photocatalytic activity due to a small particle size is visible.
  • metal oxides that can exhibit photocatalytic activity and have sufficient visible photocatalytic activity due to the large particle size the effect of further increasing the visible photocatalytic activity is obtained.
  • the photocatalyst coating agent of the invention according to claim 2 includes primary particles in addition to the auxiliary particles made of silica in which the inorganic binder has a primary particle size of 1/3 or less of the primary particle size of the main material particles.
  • the photocatalyst coating agent of the invention according to claim 1 since it contains at least one kind of auxiliary material particles selected from platinum group elements, the diameter of which is 1/3 or less of the primary particle size of the main material particles.
  • the inorganic binder is at least one selected from selenium, molybdenum, and tin oxide whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles. Since the kind of auxiliary particles are included, the effect of increasing the visible photocatalytic activity as compared with the photocatalyst coating agent of the invention according to claim 2 can be obtained.
  • the photocatalyst coating agent of the invention according to claim 4 wherein the primary particle diameter of the metal oxide is 5 nm or less has a high translucency (transparency) of the photocatalyst coating agent applied to the substrate, and the texture of the substrate is There is an effect that the substrate is not damaged and the substrate is hardly damaged.
  • Example 1 Amorphous theoretical average primary particle size as the metal oxide is dispersed oxygen deficiency mean and becomes titanium oxide non-crystal of oxygen deficiency is Ti 2 O 3 is 1.27nm (the amorphous Ti 2 O 3) in pure water
  • Auxiliary particles composed of fine particle silica (SiO 2 ) having a particle diameter of 2 nm and platinum having an average primary particle diameter of 2 nm are composed of 0.9 g of main silica, 0.09 g of auxiliary silica, and 0.01 g of platinum.
  • TiO 2 dispersion obtained by dispersing 1g of pure water 49cc of primary particles, prepared in Example 1 and the TiO 2 dispersion 50g 100 g of a specimen liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder.
  • Example 3 To produce an average particle size of 20nm of titanium dioxide (TiO 2) TiO 2 dispersion with [Degussa Co. Titanium oxide 20nm] 1 g was dispersed in pure water 49cc of primary particles, Example 1 and the TiO 2 dispersion 50g 100 g of the sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in the above.
  • Example 4 A WO 3 dispersion was prepared by dispersing 1 g of tungsten trioxide (WO 3 ) [fine particle tungsten oxide dispersion manufactured by Hirose Co., Ltd.] having an average primary particle diameter of 5 nm in 49 cc of pure water, and 50 g of this WO 3 dispersion and 100 g of a sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in Example 1.
  • WO 3 tungsten trioxide
  • a sample liquid photocatalyst coating agent
  • Example 5 To produce an average particle diameter of 30nm tungsten trioxide (WO 3) [Toshiba Corp. tungsten oxide] WO 3 dispersion prepared by dispersing 1g of pure water 49cc of primary particles, Example 1 and the WO 3 dispersion 50g 100 g of the sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in the above.
  • WO 3 tungsten trioxide
  • Example 1 and the WO 3 dispersion 50g 100 g of the sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in the above.
  • Example 6 An inorganic binder dispersed in 49 cc of pure water at a ratio of 0.9 g of the main material silica and 0.1 g of the auxiliary silica is used as the auxiliary particles of the inorganic binder using only fine particle silica having an average primary particle diameter of 2 nm.
  • a sample liquid (photocatalyst coating agent) was produced in the same manner as in Example 1 except for the points used.
  • Example 7 As auxiliary particles of the inorganic binder, fine particle silica having an average primary particle diameter of 2 nm and palladium having an average primary particle diameter of 2 nm are used, and 0.9 g of main silica, 0.1 g of auxiliary silica, palladium A sample liquid (photocatalyst coating agent) was produced in the same manner as in Example 1 except that an inorganic binder dispersed in pure water 48.99 cc at a ratio of 0.01 g was used.
  • Example 8 Main material silica using fine particle silica with an average primary particle diameter of 2 nm, palladium with an average primary particle diameter of 2 nm, and selenium with an average primary particle diameter of 2 nm as auxiliary particles of the inorganic binder
  • the sample was prepared in the same manner as in Example 1 except that a binder dispersed in pure water 48.89 cc at a ratio of 0.9 g, auxiliary silica 0.1 g, palladium 0.01 g, and selenium 0.1 g was produced.
  • a liquid (photocatalyst coating agent) was produced.
  • Comparative Example 1 In the same manner as in Example 1, except that mixed particle silica having a primary particle size of 20 to 30 nm and a particle size distribution D50 of 25 nm is used as the silica constituting the main particles of the inorganic binder. A sample solution was produced.
  • Example 2 A sample solution was produced in the same manner as in Example 1 except that fine silica particles having an average primary particle size of 2 nm were used as the silica constituting the main particles of the inorganic binder.
  • Example 3 A sample liquid was produced in the same manner as in Example 1 except that silica and platinum constituting the inorganic binder aid particles were used, wherein silica and platinum having an average primary particle size of 10 nm were used.
  • Example 4 A specimen liquid was produced in the same manner as in Example 1 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
  • Example 5 A specimen liquid was produced in the same manner as in Example 2 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
  • Example 6 A specimen liquid was produced in the same manner as in Example 3 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
  • Example 7 A sample liquid was produced in the same manner as in Example 4 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
  • Example 8 A sample liquid was produced in the same manner as in Example 5, except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
  • Example 9 A sample solution was prepared by dispersing 4 g of silica (SiO 2 ) [sicastar 100 nm 25% weight ratio manufactured by Corefront Co., Ltd.] as an inorganic binder in 46 g of the 2 wt% amorphous Ti 2 O 3 dispersion prepared in Example 1.
  • Test method for color confirmation test Two specimens are placed so that the specimen liquid application surface is top and horizontal, and one specimen top is irradiated with ultraviolet light at a height of 20 cm so that the specimen is directly under the light beam. While installing the black light 20W, a white LED for irradiating visible light was installed above the other specimen so that the specimen would be directly under the light and the illuminance would be 3500 Lx. Appropriate spacing is applied to the application surface of each specimen, and Rhodamine B having a concentration of 0.001% and methylene blue having a concentration of 0.001% are dropped one by one with a dropper, and then ultraviolet light is applied to one specimen. Each specimen was irradiated with visible light.
  • each sample solution was confirmed by visual confirmation of the color change of each dye at 5 minutes after the start of light irradiation, when the color change of the dye disappeared, and when the color change of the dye decreased ⁇ , and the case where the coloration of the pigment did not change was evaluated as x.
  • the amorphous Ti 2 O 3 dispersion or TiO 2 dispersion which is a dispersion of metal oxide, the main material particles composed of mixed particle silica having a primary particle diameter of 5 to 20 nm, and the primary particle diameter
  • the sample liquids of Examples 1 to 3 prepared by mixing auxiliary particles containing fine particle silica having a particle size of 1/3 or less of the primary particle diameter with water and an inorganic binder are sufficient ultraviolet photocatalysts. Not only has activity, but also has a high visible light catalytic activity for rhodamine B, and methylene blue could not be completely decomposed by irradiation within 5 minutes, but a little color was left. It was confirmed that the compound had visible light catalytic activity.
  • the WO 3 dispersion which is a dispersion of metal oxide, the main material particles composed of mixed particle silica having a primary particle size of 5 to 20 nm, and the primary particle size is the primary particle size of the main material particles.
  • the sample liquid of Comparative Example 1 using a mixed particle silica having a large primary particle size of 20 to 30 nm as the main material particles constituting the inorganic binder can form a film. Since it peels from the glass plate surface, the sample liquid of Comparative Example 1 did not have a basic function as a coating agent, and a color confirmation test by light irradiation could not be performed.
  • the specimen liquid of Comparative Example 2 in which the fine particle silica having a primary particle diameter of 2 nm which is too small is used as the main material particle constituting the inorganic binder is amorphous Ti 2 O 3 which is a metal oxide.
  • the inorganic binder and the inorganic binder agglomerated violently and could not be applied to the glass plate as the base material.
  • auxiliary particles constituting the inorganic binder 10 nm of silica or platinum whose primary particle diameter exceeds 1/3 of the primary particle diameter (5 to 20 nm) of the main material particle (mixed particle silica) is used.
  • the sample liquid of Comparative Example 3 can form a film on the surface of the glass plate, it has been found that it does not have both ultraviolet photocatalytic activity and visible photocatalytic activity and does not become a photocatalytic coating agent.
  • the sample liquid of Comparative Example 4 composed of an amorphous Ti 2 O 3 dispersion not using an inorganic binder of Example 1 can form a strong film on the glass plate surface, but exhibits both ultraviolet photocatalytic activity and visible photocatalytic activity. It was found that the sample liquid of Comparative Example 4 was not a photocatalyst coating agent.
  • the sample liquids of Comparative Examples 5 and 6 composed of a TiO 2 dispersion not using an inorganic binder of Example 1 cannot form a film on the surface of the glass plate and have a basic function as a coating agent. Although there was no color confirmation test by light irradiation, it was confirmed that it had ultraviolet photocatalytic activity but no visible photocatalytic activity.
  • the sample liquids of Comparative Examples 7 and 8 composed of a WO 3 dispersion that does not use the inorganic binder of Example 1 cannot form a film on the surface of the glass plate, and have a basic function as a coating agent. Although it was not, it was confirmed by a color-viewing confirmation test by light irradiation that it has no ultraviolet photocatalytic activity but has visible light catalytic activity.
  • Example whitening test After plasma treatment, the sample liquids of Examples 1 to 5 and Comparative Examples 4 to 8 were applied at 10 cc / m 2 with a spray gun to a 10 cm 2 polycarbonate plate made hydrophilic, and then dried at room temperature. The specimens were left outdoors for one day with the application surface on top in good weather. Since the whitening phenomenon occurs when the polycarbonate plate that is the base is damaged, damage to the base material that is the base is evaluated based on the presence or absence of whitening using this phenomenon, and the results are shown in Table 3.
  • the sample liquid of Comparative Example 4 which originally does not have both ultraviolet photocatalytic activity and visible photocatalytic activity has one or both of ultraviolet photocatalytic activity and visible photocatalytic activity.
  • main particles and primary particles composed of mixed particle silica having a primary particle diameter of 5 nm or less and a primary particle diameter of 5 to 20 nm of the metal oxide.
  • the sample liquid of Example 6 using only fine particle silica as the auxiliary binder particle of inorganic binder has both ultraviolet photocatalytic activity and visible photocatalytic activity, but takes time to decompose the dye.
  • the degradation rate of the dye was greatly increased (at least twice as much as that of the sample liquid of Example 6), and the auxiliary material particles made of selenium were further added. It was confirmed that the sample solution of Example 8 further increased the degradation rate of the dye.
  • the auxiliary particles added to greatly increase the decomposition rate of the dye are not limited to the above-mentioned palladium, but are selected from platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, platinum). It is sufficient to use at least one kind of noble metal, and the auxiliary particles to be added are not limited to the above-mentioned selenium, but use at least one kind selected from selenium, molybdenum and tin oxide. A similar effect can be obtained.
  • the present invention can be used as a coating agent that imparts functions such as antifouling, deodorizing, antibacterial, etc. by applying it to articles such as interior materials and cloth, and the surface of wall materials.

Abstract

[Problem] To provide a photocatalyst coating agent with which it is possible to ensure sufficient visible-light catalytic activity even when the particle diameter of metal oxides constituting the photocatalyst is low. [Solution] A photocatalyst coating agent in which the following are mixed: 50 g of a 2% by mass amorphous Ti2O3 dispersion liquid as a metal oxide, said dispersion liquid being obtained by dispersing, in pure water, a titanium oxide amorphous body (amorphous Ti2O3) of which the amorphous theoretical average primary particle diameter is 1.27 nm and in which the amount of oxygen deficiency is the oxygen deficiency average value of Ti2O3; and 50 g of an inorganic binder in which main particles including mixed-particle silica of which the primary particle diameter is 5-20 nm and in which the grain size distribution D50 has a peak at 8 nm, and auxiliary particles comprising microparticle silica in which the average particle diameter of primary particles is 2 nm and platinum in which the average particle diameter of primary particles is 2 nm, are dispersed in 49 cc of pure water such that the proportion of main silica is 0.9 g, that of auxiliary silica is 0.09 g, and that of platinum is 0.01 g.

Description

光触媒コーティング剤Photocatalyst coating agent
　この発明は、例えば、内装材や布等の物品や壁材の表面等に塗布することで、防汚、消臭、抗菌等の機能を付与することができる光触媒コーティング剤に関する。 The present invention relates to a photocatalyst coating agent capable of imparting functions such as antifouling, deodorizing, antibacterial, etc. by applying it to articles such as interior materials and cloth, and the surface of wall materials, for example.
　この種の光触媒コーティング剤としては、例えば、酸化チタン等の光触媒をシリカ系等の無機バインダーに分散させたものがあり、これを基材表面に塗布すると、無機バインダーにより、酸化チタン等の光触媒が基材表面に固定化され、光触媒に光が照射されることによって光触媒活性が発現し、防汚、消臭、抗菌等の種々の機能が発揮される。 As this type of photocatalyst coating agent, for example, there is one in which a photocatalyst such as titanium oxide is dispersed in an inorganic binder such as silica, and when this is applied to the substrate surface, a photocatalyst such as titanium oxide is formed by the inorganic binder. By immobilizing on the surface of the substrate and irradiating the photocatalyst with light, photocatalytic activity is exhibited, and various functions such as antifouling, deodorizing, and antibacterial are exhibited.
　光触媒として広く利用されている酸化チタンは、廉価に入手することができるが、紫外光にだけ触媒活性を示すため、紫外光が極めて弱い室内では十分な性能が得られない。このため、室内で十分な性能を発現する可視光活性型の光触媒を用いた光触媒コーティング剤が求められている。 Titanium oxide, which is widely used as a photocatalyst, can be obtained at a low price. However, since it exhibits catalytic activity only for ultraviolet light, sufficient performance cannot be obtained in a room where ultraviolet light is extremely weak. For this reason, a photocatalyst coating agent using a visible light active photocatalyst that exhibits sufficient performance indoors is required.
　紫外光活性を有する酸化チタン等の金属酸化物に可視光活性を付与するには、銅、硫黄、窒素等の不純物を助触媒として、主触媒である金属酸化物にドープする方法が一般的に知られているが、このようにして可視光活性が付与された光触媒の酸化力は、元々の紫外光触媒活性の光触媒の酸化力に比べて低下するという特性を有している。 In order to impart visible light activity to a metal oxide such as titanium oxide having ultraviolet light activity, a method in which impurities such as copper, sulfur and nitrogen are used as a co-catalyst and a metal oxide as a main catalyst is generally doped. As is known, the photocatalyst imparted with visible light activity in this way has a characteristic that the oxidizing power of the photocatalyst is lower than the oxidizing power of the photocatalyst having the original ultraviolet photocatalytic activity.
特開平１１－１６９７２７号公報Japanese Patent Laid-Open No. 11-169727
　ところで、金属酸化物が光触媒活性を発現するためには、光励起状態をある程度の時間維持できなければならないが、光触媒を構成している金属酸化物の粒子径を小さくすると、光励起状態を維持することができず、光励起により生成した励起電子と正孔とが再結合して元の基底状態に戻ってしまうので、十分な光触媒活性を得ることができない。このため、上述したように、そもそも酸化力が大きくない可視光活性型の光触媒については、光触媒を構成している金属酸化物の粒子径をなるべく大きくすることで、可視光触媒活性を高くしているのが現状である。 By the way, in order for a metal oxide to exhibit photocatalytic activity, the photoexcited state must be able to be maintained for a certain period of time. However, if the particle size of the metal oxide constituting the photocatalyst is reduced, the photoexcited state must be maintained. However, since excited electrons and holes generated by photoexcitation recombine and return to the original ground state, sufficient photocatalytic activity cannot be obtained. For this reason, as described above, with respect to a visible light active photocatalyst that does not have high oxidizing power, the visible light catalytic activity is increased by increasing the particle diameter of the metal oxide constituting the photocatalyst as much as possible. is the current situation.
　しかしながら、光触媒を構成している金属酸化物の粒子径を大きくすると、表面積が小さくなる（被分解物質との接触面積が小さくなる）ので、被分解物質を短時間で効率よく分解することができず、分解能力が低下するといった問題がある。 However, when the particle size of the metal oxide composing the photocatalyst is increased, the surface area becomes smaller (the contact area with the substance to be decomposed), so that the substance to be decomposed can be efficiently decomposed in a short time. However, there is a problem that the decomposition ability is reduced.
　つまり、可視光活性型の光触媒は、光触媒を構成している金属酸化物の粒子径を大きくして可視光触媒活性を高めると、被分解物質の分解能力が低下し、逆に、光触媒を構成している金属酸化物の粒子径を小さくして被分解物質の分解能力を高めると、可視光触媒活性が低下してしまうというジレンマに陥っている。 In other words, when the visible light activity type photocatalyst increases the visible light catalytic activity by increasing the particle size of the metal oxide constituting the photocatalyst, the decomposition ability of the substance to be decomposed decreases. When the particle size of the metal oxide is reduced to increase the decomposition ability of the substance to be decomposed, the visible light catalytic activity is lowered.
　そこで、この発明の課題は、光触媒を構成している金属酸化物の粒子径が小さくても、十分な可視光触媒活性を確保することができる光触媒コーティング剤を提供することにある。 Therefore, an object of the present invention is to provide a photocatalyst coating agent capable of ensuring a sufficient visible photocatalytic activity even when the particle diameter of the metal oxide constituting the photocatalyst is small.
　上記の課題を解決するため、請求項１に係る発明は、金属酸化物を無機バインダーに分散させた光触媒コーティング剤であって、前記無機バインダーは、一次粒子径が２０ｎｍ以下、５ｎｍ以上のシリカからなる主材粒子と、一次粒子径が前記主材粒子の一次粒子径の１／３以下であるシリカを含む助材粒子とを水に分散させたものであることを特徴とする光触媒コーティング剤を提供するものである。 In order to solve the above problems, the invention according to claim 1 is a photocatalyst coating agent in which a metal oxide is dispersed in an inorganic binder, and the inorganic binder comprises silica having a primary particle diameter of 20 nm or less and 5 nm or more. A photocatalyst coating agent, wherein the main material particles and auxiliary particles containing silica whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles are dispersed in water. It is to provide.
　また、請求項２に係る発明は、請求項１に係る発明の光触媒コーティング剤において、前記無機バインダーは、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、白金族元素から選択される少なくとも１種類の助材粒子を含んでいることを特徴としている。 The invention according to claim 2 is the photocatalytic coating agent according to the invention according to claim 1, wherein the inorganic binder has a platinum group element whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles. It contains at least one kind of auxiliary material particles selected from the above.
　また、請求項３に係る発明は、請求項２に係る発明の光触媒コーティング剤において、前記無機バインダーは、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、セレン、モリブデン、酸化スズから選択される少なくとも１種類の助材粒子を含んでいることを特徴としている。 The invention according to claim 3 is the photocatalyst coating agent according to the invention according to claim 2, wherein the inorganic binder has a primary particle diameter of 1/3 or less of the primary particle diameter of the main material particles. And containing at least one kind of auxiliary material particles selected from tin oxide.
　また、請求項４に係る発明は、請求項１、２または３に係る発明の光触媒コーティング剤において、前記金属酸化物は、その一次粒子径が５ｎｍ以下であることを特徴としている。 The invention according to claim 4 is the photocatalyst coating agent according to claim 1, 2, or 3, wherein the metal oxide has a primary particle diameter of 5 nm or less.
　また、請求項５に係る発明は、請求項１、２、３または４に係る発明の光触媒コーティング剤において、前記金属酸化物は、酸化チタン、酸素欠損型酸化チタンまたは酸化タングステンであることを特徴としている。 The invention according to claim 5 is the photocatalyst coating agent according to claim 1, 2, 3 or 4, wherein the metal oxide is titanium oxide, oxygen-deficient titanium oxide or tungsten oxide. It is said.
　以上のように、請求項１に係る発明の光触媒コーティング剤は、金属酸化物を、一次粒子径が２０ｎｍ以下、５ｎｍ以上のシリカからなる主材粒子と、一次粒子径が前記主材粒子の一次粒子径の１／３以下であるシリカを含む助材粒子とを水に分散させた無機バインダーに分散させることにより、粒子径が小さいために可視光触媒活性が得られない金属酸化物については、可視光触媒活性を発現させることができ、粒子径が大きいために十分な可視光触媒活性を有している金属酸化物については、その可視光触媒活性がさらに高くなるという効果が得られる。 As described above, the photocatalyst coating agent of the invention according to claim 1 includes a metal oxide, a primary material particle composed of silica having a primary particle diameter of 20 nm or less and 5 nm or more, and a primary particle diameter of the primary particle. By dispersing an auxiliary particle containing silica having a particle size of 1/3 or less in an inorganic binder dispersed in water, a metal oxide that cannot obtain visible photocatalytic activity due to a small particle size is visible. For metal oxides that can exhibit photocatalytic activity and have sufficient visible photocatalytic activity due to the large particle size, the effect of further increasing the visible photocatalytic activity is obtained.
　特に、請求項２に係る発明の光触媒コーティング剤は、前記無機バインダーが、一次粒子径が前記主材粒子の一次粒子径の１／３以下であるシリカからなる助材粒子に加えて、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、白金族元素から選択される少なくとも１種類の助材粒子を含んでいるので、請求項１に係る発明の光触媒コーティング剤に比べて可視光触媒活性が高くなるという効果が得られる。 In particular, the photocatalyst coating agent of the invention according to claim 2 includes primary particles in addition to the auxiliary particles made of silica in which the inorganic binder has a primary particle size of 1/3 or less of the primary particle size of the main material particles. Compared to the photocatalyst coating agent of the invention according to claim 1, since it contains at least one kind of auxiliary material particles selected from platinum group elements, the diameter of which is 1/3 or less of the primary particle size of the main material particles. Thus, the effect of increasing the visible light catalytic activity can be obtained.
　また、請求項３に係る発明の光触媒コーティング剤は、無機バインダーは、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、セレン、モリブデン、酸化スズから選択される少なくとも１種類の助材粒子を含んでいるので、請求項２に係る発明の光触媒コーティング剤に比べて可視光触媒活性が高くなるという効果が得られる。 In the photocatalyst coating agent of the invention according to claim 3, the inorganic binder is at least one selected from selenium, molybdenum, and tin oxide whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles. Since the kind of auxiliary particles are included, the effect of increasing the visible photocatalytic activity as compared with the photocatalyst coating agent of the invention according to claim 2 can be obtained.
　特に、金属酸化物の一次粒子径が５ｎｍ以下である請求項４に係る発明の光触媒コーティング剤は、基材に塗布した光触媒コーティング剤の透光率（透明性）が高く、基材の風合いを損ねないと共に、基材を痛めにくいという効果が得られる。 In particular, the photocatalyst coating agent of the invention according to claim 4 wherein the primary particle diameter of the metal oxide is 5 nm or less has a high translucency (transparency) of the photocatalyst coating agent applied to the substrate, and the texture of the substrate is There is an effect that the substrate is not damaged and the substrate is hardly damaged.
　以下、本発明の実施例について図面を参照して説明するが、本発明の光触媒コーティング剤はこれらの実施例に限定されるものではない。 Hereinafter, examples of the present invention will be described with reference to the drawings. However, the photocatalyst coating agent of the present invention is not limited to these examples.
　（実施例１）
　金属酸化物としてアモルファス理論平均一次粒子径が１．２７ｎｍである酸素欠損量がＴｉ２Ｏ３の酸素欠損平均値となる酸化チタン非結晶体（アモルファスＴｉ２Ｏ３）を純水に分散させた２重量％アモルファスＴｉ２Ｏ３分散液を製造すると共に、一次粒子径が５～２０ｎｍで粒度分布Ｄ５０が８ｎｍのピークを持つ混合粒子シリカ（ＳｉＯ２）を含む主材粒子と、一次粒子の平均粒子径が２ｎｍである微粒子シリカ（ＳｉＯ２）及び一次粒子の平均粒子径が２ｎｍである白金からなる助材粒子とを、主材シリカ０．９ｇ、助材シリカ０．０９ｇ、白金０．０１ｇの割合で純水４９ｃｃに分散させた無機バインダーを製造し、アモルファスＴｉ２Ｏ３分散液５０ｇと無機バインダー５０ｇとを混合して検体液（光触媒コーティング剤）１００ｇを製造した。 Example 1
Amorphous theoretical average primary particle size as the metal oxide is dispersed oxygen deficiency mean and becomes titanium oxide non-crystal of oxygen deficiency is Ti 2 O 3 is 1.27nm (the amorphous Ti 2 O 3) in pure water An average of primary particles containing mixed particle silica (SiO 2 ) having a peak with a primary particle size of 5 to 20 nm and a particle size distribution D50 of 8 nm, while producing a 2 wt% amorphous Ti 2 O 3 dispersion Auxiliary particles composed of fine particle silica (SiO 2 ) having a particle diameter of 2 nm and platinum having an average primary particle diameter of 2 nm are composed of 0.9 g of main silica, 0.09 g of auxiliary silica, and 0.01 g of platinum. to produce an inorganic binder dispersed in pure water 49cc at a ratio of amorphous Ti 2 O 3 dispersion 50g and inorganic binder 50g were mixed with sample liquid (photocatalyst quotes To produce a bridging agent) 100g.
　（実施例２）
　一次粒子の平均粒子径が５ｎｍの二酸化チタン（ＴｉＯ２）［アエロジル社製Ｐ２５］１ｇを純水４９ｃｃに分散させたＴｉＯ２分散液を製造し、このＴｉＯ２分散液５０ｇと実施例１で製造した無機バインダー５０ｇとを混合して検体液（光触媒コーティング剤）１００ｇを製造した。 (Example 2)
To produce an average particle size of 5nm of titanium dioxide (TiO 2) [Aerosil P25] TiO 2 dispersion obtained by dispersing 1g of pure water 49cc of primary particles, prepared in Example 1 and the TiO 2 dispersion 50g 100 g of a specimen liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder.
　（実施例３）
　一次粒子の平均粒子径が２０ｎｍの二酸化チタン（ＴｉＯ２）［Ｄｅｇｕｓｓａ社製酸化チタン２０ｎｍ]１ｇを純水４９ｃｃに分散させたＴｉＯ２分散液を製造し、このＴｉＯ２分散液５０ｇと実施例１で製造した無機バインダー５０ｇとを混合して検体液（光触媒コーティング剤）１００ｇを製造した。 (Example 3)
To produce an average particle size of 20nm of titanium dioxide (TiO 2) TiO 2 dispersion with [Degussa Co. Titanium oxide 20nm] 1 g was dispersed in pure water 49cc of primary particles, Example 1 and the TiO 2 dispersion 50g 100 g of the sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in the above.
　（実施例４）
　一次粒子の平均粒子径が５ｎｍの三酸化タングステン（ＷＯ３）［ヒロセ社製微粒子酸化タングステン分散液]１ｇを純水４９ｃｃに分散させたＷＯ３分散液を製造し、このＷＯ３分散液５０ｇと実施例１で製造した無機バインダー５０ｇとを混合して検体液（光触媒コーティング剤）１００ｇを製造した。 Example 4
A WO 3 dispersion was prepared by dispersing 1 g of tungsten trioxide (WO 3 ) [fine particle tungsten oxide dispersion manufactured by Hirose Co., Ltd.] having an average primary particle diameter of 5 nm in 49 cc of pure water, and 50 g of this WO 3 dispersion and 100 g of a sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in Example 1.
　（実施例５）
　一次粒子の平均粒子径が３０ｎｍの三酸化タングステン（ＷＯ３）［東芝社製酸化タングステン]１ｇを純水４９ｃｃに分散させたＷＯ３分散液を製造し、このＷＯ３分散液５０ｇと実施例１で製造した無機バインダー５０ｇとを混合して検体液（光触媒コーティング剤）１００ｇを製造した。 (Example 5)
To produce an average particle diameter of 30nm tungsten trioxide (WO 3) [Toshiba Corp. tungsten oxide] WO 3 dispersion prepared by dispersing 1g of pure water 49cc of primary particles, Example 1 and the WO 3 dispersion 50g 100 g of the sample liquid (photocatalyst coating agent) was produced by mixing 50 g of the inorganic binder produced in the above.
　（実施例６）
　無機バインダーの助材粒子として一次粒子の平均粒子径が２ｎｍである微粒子シリカのみを使用し、主材シリカ０．９ｇ、助材シリカ０．１ｇの割合で純水４９ｃｃに分散させた無機バインダーを使用した点を除いて、実施例１と同様の方法で検体液（光触媒コーティング剤）を製造した。 (Example 6)
An inorganic binder dispersed in 49 cc of pure water at a ratio of 0.9 g of the main material silica and 0.1 g of the auxiliary silica is used as the auxiliary particles of the inorganic binder using only fine particle silica having an average primary particle diameter of 2 nm. A sample liquid (photocatalyst coating agent) was produced in the same manner as in Example 1 except for the points used.
　（実施例７）
　無機バインダーの助材粒子として一次粒子の平均粒子径が２ｎｍである微粒子シリカ及び一次粒子の平均粒子径が２ｎｍであるパラジウムを使用し、主材シリカ０．９ｇ、助材シリカ０．１ｇ、パラジウム０．０１ｇの割合で純水４８．９９ｃｃに分散させた無機バインダーを使用した点を除いて、実施例１と同様の方法で検体液（光触媒コーティング剤）を製造した。 (Example 7)
As auxiliary particles of the inorganic binder, fine particle silica having an average primary particle diameter of 2 nm and palladium having an average primary particle diameter of 2 nm are used, and 0.9 g of main silica, 0.1 g of auxiliary silica, palladium A sample liquid (photocatalyst coating agent) was produced in the same manner as in Example 1 except that an inorganic binder dispersed in pure water 48.99 cc at a ratio of 0.01 g was used.
　（実施例８）
　無機バインダーの助材粒子として一次粒子の平均粒子径が２ｎｍである微粒子シリカ、一次粒子の平均粒子径が２ｎｍであるパラジウム及び一次粒子の平均粒子径が２ｎｍであるセレンを使用し、主材シリカ０．９ｇ、助材シリカ０．１ｇ、パラジウム０．０１ｇ、セレン０．１ｇの割合で純水４８．８９ｃｃに分散させたバインダーを製造した点を除いて、実施例１と同様の方法で検体液（光触媒コーティング剤）を製造した。 (Example 8)
Main material silica using fine particle silica with an average primary particle diameter of 2 nm, palladium with an average primary particle diameter of 2 nm, and selenium with an average primary particle diameter of 2 nm as auxiliary particles of the inorganic binder The sample was prepared in the same manner as in Example 1 except that a binder dispersed in pure water 48.89 cc at a ratio of 0.9 g, auxiliary silica 0.1 g, palladium 0.01 g, and selenium 0.1 g was produced. A liquid (photocatalyst coating agent) was produced.
　（比較例１）
　無機バインダーの主材粒子を構成しているシリカとして、一次粒子径が２０～３０ｎｍで粒度分布Ｄ５０が２５ｎｍのピークを持つ混合粒子シリカを使用した点を除いて、実施例１と同様の方法で検体液を製造した。 (Comparative Example 1)
In the same manner as in Example 1, except that mixed particle silica having a primary particle size of 20 to 30 nm and a particle size distribution D50 of 25 nm is used as the silica constituting the main particles of the inorganic binder. A sample solution was produced.
　（比較例２）
　無機バインダーの主材粒子を構成しているシリカとして、一次粒子の平均粒子径が２ｎｍである微粒子シリカを使用した点を除いて、実施例１と同様の方法で検体液を製造した。 (Comparative Example 2)
A sample solution was produced in the same manner as in Example 1 except that fine silica particles having an average primary particle size of 2 nm were used as the silica constituting the main particles of the inorganic binder.
　（比較例３）
　無機バインダーの助材粒子を構成しているシリカ及び白金として、一次粒子の平均粒子径が１０ｎｍのシリカ及び白金を使用した点を除いて、実施例１と同様の方法で検体液を製造した。 (Comparative Example 3)
A sample liquid was produced in the same manner as in Example 1 except that silica and platinum constituting the inorganic binder aid particles were used, wherein silica and platinum having an average primary particle size of 10 nm were used.
　（比較例４）
　無機バインダーに代えて、主材粒子や助材粒子を含まない５０ｃｃの純水を使用した点を除いて、実施例１と同様の方法で検体液を製造した。 (Comparative Example 4)
A specimen liquid was produced in the same manner as in Example 1 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
　（比較例５）
　無機バインダーに代えて、主材粒子や助材粒子を含まない５０ｃｃの純水を使用した点を除いて、実施例２と同様の方法で検体液を製造した。 (Comparative Example 5)
A specimen liquid was produced in the same manner as in Example 2 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
　（比較例６）
　無機バインダーに代えて、主材粒子や助材粒子を含まない５０ｃｃの純水を使用した点を除いて、実施例３と同様の方法で検体液を製造した。 (Comparative Example 6)
A specimen liquid was produced in the same manner as in Example 3 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
　（比較例７）
　無機バインダーに代えて、主材粒子や助材粒子を含まない５０ｃｃの純水を使用した点を除いて、実施例４と同様の方法で検体液を製造した。 (Comparative Example 7)
A sample liquid was produced in the same manner as in Example 4 except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
　（比較例８）
　無機バインダーに代えて、主材粒子や助材粒子を含まない５０ｃｃの純水を使用した点を除いて、実施例５と同様の方法で検体液を製造した。 (Comparative Example 8)
A sample liquid was produced in the same manner as in Example 5, except that 50 cc of pure water containing no main material particles or auxiliary material particles was used in place of the inorganic binder.
　（比較例９）
　実施例１で製造した２重量％アモルファスＴｉ２Ｏ３分散液４６ｇに、無機バインダーとしてシリカ（ＳｉＯ２）［コアフロント社製 ｓｉｃａｓｔａｒ １００ｎｍ２５％重量比］４ｇを分散させた検体液を製造した。 (Comparative Example 9)
A sample solution was prepared by dispersing 4 g of silica (SiO 2 ) [sicastar 100 nm 25% weight ratio manufactured by Corefront Co., Ltd.] as an inorganic binder in 46 g of the 2 wt% amorphous Ti 2 O 3 dispersion prepared in Example 1.
　（比較例１０）
　一次粒子の平均粒子径が５ｎｍの二酸化チタン（ＴｉＯ２）［アエロジル社製Ｐ２５］１ｇと無機バインダーとしてのシリカ（ＳｉＯ２）［コアフロント社製 ｓｉｃａｓｔａｒ １００ｎｍ２５％重量比］４ｇとを純水４５ｃｃに分散させた検体液を製造した。 (Comparative Example 10)
1 g of titanium dioxide (TiO 2 ) having an average primary particle size of 5 nm [P25] manufactured by Aerosil Co. and 4 g of silica (SiO 2 ) [sicastar 100 nm 25% weight ratio manufactured by Corefront Co., Ltd.] as an inorganic binder in 45 cc of pure water A dispersed sample solution was produced.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（光照射による色見確認試験）
　実施例１～５及び比較例１～１０の検体液をスプレーガンにて１０ｃｍ２の２枚のガラス板片面に１０ｃｃ／ｍ２でそれぞれ塗布した後、常温で乾燥させることにより２枚の検体を作成し、以下に示す試験方法に従って光照射による色見確認試験を行い、各検体液の光触媒活性を評価し、表２に示した。なお、比較例９及び比較例１０については、検体液をスプレーガンにて１０ｃｍ２の２枚のガラス板片面に１０ｃｃ／ｍ２でそれぞれ塗布した後、エチルシリケート（コルコート社製４８）１ｇを４９ｃｃのエチルアルコールに分散させた分散液をスプレーガンにて１０ｇ／ｍ２でさらに上塗布することで加水反応を起こして被膜が形成された状態で光照射による色見確認試験を行った。 (Color viewing confirmation test by light irradiation)
The sample liquids of Examples 1 to 5 and Comparative Examples 1 to 10 were each applied to one side of two 10 cm 2 glass plates with a spray gun at 10 cc / m 2 and then dried at room temperature to obtain two samples. The sample was prepared and subjected to a color confirmation test by light irradiation according to the test method shown below, and the photocatalytic activity of each sample solution was evaluated. For Comparative Example 9 and Comparative Example 10, the specimen solution was applied to one side of two 10 cm 2 glass plates with a spray gun at 10 cc / m 2 , and then 1 g of ethyl silicate (48 by Colcoat Co., Ltd.) was 49 cc. The color dispersion confirmation test by light irradiation was performed in a state where a dispersion was further applied at 10 g / m 2 with a spray gun to cause a hydrolysis reaction and a film was formed.
　（色見確認試験の試験方法）
　２枚の検体を検体液の塗布面が上部かつ水平になるように載置し、一方の検体上部には、検体がライト光直下となるように、２０ｃｍの高さ位置に紫外光を照射するブラックライト２０Ｗを設置すると共に、他方の検体上部には、検体がライト光直下となり、照度が３５００Ｌｘとなるように、可視光を照射する白色ＬＥＤを設置した。それぞれの検体の塗布面に適度な間隔を開けて、濃度が０．００１％のローダミンＢ及び濃度が０．００１％のメチレンブルーをスポイドで１箇所ずつ滴下した後、一方の検体に紫外光、他方の検体に可視光をそれぞれ照射した。各検体液の光触媒活性は、光照射開始後５分経過時点で目視によりそれぞれの色素の色見の変化を確認し、色素の色見が消失した場合を〇、色素の色見が減少した場合を△、色素の色見が変化しなかった場合を×で評価した。 (Test method for color confirmation test)
Two specimens are placed so that the specimen liquid application surface is top and horizontal, and one specimen top is irradiated with ultraviolet light at a height of 20 cm so that the specimen is directly under the light beam. While installing the black light 20W, a white LED for irradiating visible light was installed above the other specimen so that the specimen would be directly under the light and the illuminance would be 3500 Lx. Appropriate spacing is applied to the application surface of each specimen, and Rhodamine B having a concentration of 0.001% and methylene blue having a concentration of 0.001% are dropped one by one with a dropper, and then ultraviolet light is applied to one specimen. Each specimen was irradiated with visible light. The photocatalytic activity of each sample solution was confirmed by visual confirmation of the color change of each dye at 5 minutes after the start of light irradiation, when the color change of the dye disappeared, and when the color change of the dye decreased Δ, and the case where the coloration of the pigment did not change was evaluated as x.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、金属酸化物の分散液であるアモルファスＴｉ２Ｏ３分散液やＴｉＯ２分散液と、一次粒子径が５～２０ｎｍの混合粒子シリカからなる主材粒子と一次粒子径が主材粒子の一次粒子径の１／３以下である微粒子シリカを含む助材粒子とを水に分散させた無機バインダーとを混合してなる実施例１～３の検体液は、十分な紫外光触媒活性を有しているだけでなく、ローダミンＢに対して高い可視光触媒活性を有しており、メチレンブルーに対しては５分以内照射で完全に分解することができず少し色見が残ったが、可視光触媒活性を有していることは確認できた。 As shown in Table 2, the amorphous Ti 2 O 3 dispersion or TiO 2 dispersion, which is a dispersion of metal oxide, the main material particles composed of mixed particle silica having a primary particle diameter of 5 to 20 nm, and the primary particle diameter The sample liquids of Examples 1 to 3 prepared by mixing auxiliary particles containing fine particle silica having a particle size of 1/3 or less of the primary particle diameter with water and an inorganic binder are sufficient ultraviolet photocatalysts. Not only has activity, but also has a high visible light catalytic activity for rhodamine B, and methylene blue could not be completely decomposed by irradiation within 5 minutes, but a little color was left. It was confirmed that the compound had visible light catalytic activity.
　表２に示すように、金属酸化物の分散液であるＷＯ３分散液と、一次粒子径が５～２０ｎｍの混合粒子シリカからなる主材粒子と一次粒子径が主材粒子の一次粒子径の１／３以下である微粒子シリカを含む助材粒子とを水に分散させた無機バインダーとを混合してなる実施例４、５の検体液は、十分な紫外光触媒活性を有しているだけでなく、メチレンブルーに対して高い可視光触媒活性を有しており、ローダミンＢに対しては５分以内照射で完全に分解することができず少し色見が残ったが、可視光触媒活性を有していることは確認できた。 As shown in Table 2, the WO 3 dispersion which is a dispersion of metal oxide, the main material particles composed of mixed particle silica having a primary particle size of 5 to 20 nm, and the primary particle size is the primary particle size of the main material particles. The sample liquids of Examples 4 and 5 formed by mixing an inorganic binder in which auxiliary particles containing fine particle silica that is 1/3 or less are dispersed in water only have sufficient ultraviolet photocatalytic activity. It has a high visible photocatalytic activity for methylene blue and rhodamine B cannot be completely decomposed by irradiation within 5 minutes, but a little color remains, but has a visible photocatalytic activity. I was able to confirm.
　一方、無機バインダーを構成している主材粒子として、一次粒子径が２０～３０ｎｍという粒子径の大きい混合粒子シリカを使用している比較例１の検体液は、被膜を形成することができるもののガラス板表面から剥離してしまうので、比較例１の検体液はコーティング剤としての基本的な機能を有しておらず、光照射による色見確認試験も行うことができなかった。 On the other hand, the sample liquid of Comparative Example 1 using a mixed particle silica having a large primary particle size of 20 to 30 nm as the main material particles constituting the inorganic binder can form a film. Since it peels from the glass plate surface, the sample liquid of Comparative Example 1 did not have a basic function as a coating agent, and a color confirmation test by light irradiation could not be performed.
　また、無機バインダーを構成している主材粒子として、一次粒子径が２ｎｍという粒子径の小さすぎる微粒子シリカを使用している比較例２の検体液は、金属酸化物であるアモルファスＴｉ２Ｏ３と無機バインダーとが激しく凝集し、基材であるガラス板に塗布することができず、当然のことながら、光照射による色見確認試験は行うことができなかった。 In addition, the specimen liquid of Comparative Example 2 in which the fine particle silica having a primary particle diameter of 2 nm which is too small is used as the main material particle constituting the inorganic binder is amorphous Ti 2 O 3 which is a metal oxide. The inorganic binder and the inorganic binder agglomerated violently and could not be applied to the glass plate as the base material.
　また、無機バインダーを構成している助材粒子として、一次粒子径が主材粒子（混合粒子シリカ）の一次粒子径（５～２０ｎｍ）の１／３を上回る１０ｎｍのシリカや白金を使用している比較例３の検体液は、ガラス板表面に被膜を形成することができるものの紫外光触媒活性及び可視光触媒活性の双方を有しておらず、光触媒コーティング剤とはならないことが判明した。 Further, as auxiliary particles constituting the inorganic binder, 10 nm of silica or platinum whose primary particle diameter exceeds 1/3 of the primary particle diameter (5 to 20 nm) of the main material particle (mixed particle silica) is used. Although the sample liquid of Comparative Example 3 can form a film on the surface of the glass plate, it has been found that it does not have both ultraviolet photocatalytic activity and visible photocatalytic activity and does not become a photocatalytic coating agent.
　実施例１の無機バインダーを使用しないアモルファスＴｉ２Ｏ３分散液からなる比較例４の検体液は、ガラス板表面に強固な被膜を形成することはできるものの紫外光触媒活性及び可視光触媒活性の双方を有しておらず、比較例４の検体液は光触媒コーティング剤とはならないことが判明した。 The sample liquid of Comparative Example 4 composed of an amorphous Ti 2 O 3 dispersion not using an inorganic binder of Example 1 can form a strong film on the glass plate surface, but exhibits both ultraviolet photocatalytic activity and visible photocatalytic activity. It was found that the sample liquid of Comparative Example 4 was not a photocatalyst coating agent.
　実施例１の無機バインダーを使用しないＴｉＯ２分散液からなる比較例５、６の検体液は、ガラス板表面に被膜を形成することができず、コーティング剤としての基本的な機能を有していないが、光照射による色見確認試験により、紫外光触媒活性を有しているが、可視光触媒活性は有していないことが確認できた。 The sample liquids of Comparative Examples 5 and 6 composed of a TiO 2 dispersion not using an inorganic binder of Example 1 cannot form a film on the surface of the glass plate and have a basic function as a coating agent. Although there was no color confirmation test by light irradiation, it was confirmed that it had ultraviolet photocatalytic activity but no visible photocatalytic activity.
　実施例１の無機バインダーを使用しないＷＯ３分散液からなる比較例７、８の検体液は、ガラス板表面に被膜を形成することができず、コーティング剤としての基本的な機能を有していないが、光照射による色見確認試験により、紫外光触媒活性を有していないが、可視光触媒活性は有していることが確認できた。 The sample liquids of Comparative Examples 7 and 8 composed of a WO 3 dispersion that does not use the inorganic binder of Example 1 cannot form a film on the surface of the glass plate, and have a basic function as a coating agent. Although it was not, it was confirmed by a color-viewing confirmation test by light irradiation that it has no ultraviolet photocatalytic activity but has visible light catalytic activity.
　バインダーとして粒子径が１００ｎｍのシリカを分散させた比較例９、１０の検体液は、ガラス表面に塗布した後、さらにエチルシリケートを塗布することにより、ガラス板表面に被膜を形成することはできるものの紫外光触媒活性及び可視光触媒活性の双方を有しておらず、光触媒コーティング剤とはならないことが判明した。 Although the sample liquids of Comparative Examples 9 and 10 in which silica having a particle size of 100 nm is dispersed as a binder can be formed on the glass plate surface by further applying ethyl silicate after coating on the glass surface. It has been found that it does not have both ultraviolet photocatalytic activity and visible photocatalytic activity and does not become a photocatalytic coating agent.
　（基材の白化試験）
　プラズマ処理後、親水状態にした１０ｃｍ２のポリカーボネート板に、実施例１～５及び比較例４～８の検体液をスプレーガンにて１０ｃｃ／ｍ２で塗布した後、常温で乾燥させることにより検体を作成し、これらの検体を好天候下、塗布面を上部になるように設置した状態で１日屋外放置した。下地であるポリカーボネート板を傷めると白化現象が起こるので、この現象を利用して下地となる基材の損傷を白化の有無によって評価し、結果を表３に示した。 (Substrate whitening test)
After plasma treatment, the sample liquids of Examples 1 to 5 and Comparative Examples 4 to 8 were applied at 10 cc / m 2 with a spray gun to a 10 cm 2 polycarbonate plate made hydrophilic, and then dried at room temperature. The specimens were left outdoors for one day with the application surface on top in good weather. Since the whitening phenomenon occurs when the polycarbonate plate that is the base is damaged, damage to the base material that is the base is evaluated based on the presence or absence of whitening using this phenomenon, and the results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３から分かるように、そもそも紫外光触媒活性及び可視光触媒活性の双方を有していない比較例４の検体液を除いて、紫外光触媒活性及び可視光触媒活性のいずれか一方または双方を有している実施例１～５及び比較例５～８の検体液のうち、金属酸化物の一次粒子径が５ｎｍ以下で、かつ、一次粒子径が５～２０ｎｍの混合粒子シリカからなる主材粒子と一次粒子径が主材粒子の一次粒子径の１／３以下である微粒子シリカを含む助材粒子とを水に分散させた無機バインダーを使用している実施例１、２、４の検体液については、ポリカーボネート板が白化しておらず、下地となる基材の損傷を防止できることが確認できた。 As can be seen from Table 3, the sample liquid of Comparative Example 4 which originally does not have both ultraviolet photocatalytic activity and visible photocatalytic activity has one or both of ultraviolet photocatalytic activity and visible photocatalytic activity. Of the specimen liquids of Examples 1 to 5 and Comparative Examples 5 to 8, main particles and primary particles composed of mixed particle silica having a primary particle diameter of 5 nm or less and a primary particle diameter of 5 to 20 nm of the metal oxide. For the sample liquids of Examples 1, 2, and 4 using an inorganic binder in which auxiliary particles containing fine particle silica having a diameter of 1/3 or less of the primary particle diameter of the main material particles are dispersed in water, It was confirmed that the polycarbonate plate was not whitened, and damage to the base material serving as the base could be prevented.
　（光触媒活性の比較試験）
　実施例６～８の各検体液について上述した光照射による色見確認試験を行い、各検体について色素の色見が消失するまでに要する時間を測定し、その結果を表４に示した。 (Photocatalytic activity comparison test)
For each sample solution of Examples 6 to 8, the above-described color-viewing confirmation test by light irradiation was performed, and the time required for the color-viewing of the dye to disappear for each sample was measured. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４から分かるように、無機バインダーの助材粒子として微粒子シリカのみを使用した実施例６の検体液は、紫外光触媒活性及び可視光触媒活性の双方を有しているものの色素の分解に時間がかかるが、パラジウムからなる助材粒子を添加した実施例７の検体液は、色素の分解速度が大幅（実施例６の検体液の２倍以上）に増大し、さらにセレンからなる助材粒子を添加した実施例８の検体液は、さらに色素の分解速度が増大することが確認できた。 As can be seen from Table 4, the sample liquid of Example 6 using only fine particle silica as the auxiliary binder particle of inorganic binder has both ultraviolet photocatalytic activity and visible photocatalytic activity, but takes time to decompose the dye. However, in the sample liquid of Example 7 to which the auxiliary material particles made of palladium were added, the degradation rate of the dye was greatly increased (at least twice as much as that of the sample liquid of Example 6), and the auxiliary material particles made of selenium were further added. It was confirmed that the sample solution of Example 8 further increased the degradation rate of the dye.
　なお、色素の分解速度を大幅に増大させるために添加する助材粒子としては、上述したパラジウムに限定されるものではなく、白金族元素（ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金）から選択される少なくとも１種類の貴金属を使用すればよく、さらに添加する助材粒子としては、上述したセレンに限定されるものではなく、セレン、モリブデン、酸化スズから選択される少なくとも１種類を使用することで同様の効果を得ることができる。 The auxiliary particles added to greatly increase the decomposition rate of the dye are not limited to the above-mentioned palladium, but are selected from platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, platinum). It is sufficient to use at least one kind of noble metal, and the auxiliary particles to be added are not limited to the above-mentioned selenium, but use at least one kind selected from selenium, molybdenum and tin oxide. A similar effect can be obtained.
　本発明は、内装材や布等の物品や壁材の表面等に塗布することで、防汚、消臭、抗菌等の機能を付与するコーティング剤として利用することができる。 The present invention can be used as a coating agent that imparts functions such as antifouling, deodorizing, antibacterial, etc. by applying it to articles such as interior materials and cloth, and the surface of wall materials.

Claims (5)

  1. 　金属酸化物を無機バインダーに分散させた光触媒コーティング剤であって、
    　前記無機バインダーは、一次粒子径が２０ｎｍ以下、５ｎｍ以上のシリカからなる主材粒子と、一次粒子径が前記主材粒子の一次粒子径の１／３以下であるシリカを含む助材粒子とを水に分散させたものであることを特徴とする光触媒コーティング剤。     A photocatalytic coating agent in which a metal oxide is dispersed in an inorganic binder,
    The inorganic binder includes main material particles made of silica having a primary particle diameter of 20 nm or less and 5 nm or more, and auxiliary particles containing silica whose primary particle diameter is 1/3 or less of the primary particle diameter of the main material particles. A photocatalyst coating agent characterized by being dispersed in water.
  2. 　前記無機バインダーは、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、白金族元素から選択される少なくとも１種類の助材粒子を含んでいる請求項１に記載の光触媒コーティング剤。 2. The photocatalyst according to claim 1, wherein the inorganic binder contains at least one auxiliary material particle selected from platinum group elements having a primary particle size of 1/3 or less of the primary particle size of the main material particle. Coating agent.
  3. 　前記無機バインダーは、一次粒子径が前記主材粒子の一次粒子径の１／３以下である、セレン、モリブデン、酸化スズから選択される少なくとも１種類の助材粒子を含んでいる請求項２に記載の光触媒コーティング剤。 The inorganic binder includes at least one auxiliary particle selected from selenium, molybdenum, and tin oxide, the primary particle diameter of which is 1/3 or less of the primary particle diameter of the main material particle. The photocatalyst coating agent as described.
  4. 　前記金属酸化物は、その一次粒子径が５ｎｍ以下である請求項１、２または３に記載の光触媒コーティング剤。 The photocatalyst coating agent according to claim 1, 2 or 3, wherein the metal oxide has a primary particle diameter of 5 nm or less.
  5. 　前記金属酸化物は、酸化チタン、酸素欠損型酸化チタンまたは酸化タングステンである請求項１、２、３または４に記載の光触媒コーティング剤。 The photocatalytic coating agent according to claim 1, 2, 3, or 4, wherein the metal oxide is titanium oxide, oxygen-deficient titanium oxide, or tungsten oxide.
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Citations (8)

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Publication number Priority date Publication date Assignee Title
JP2000233928A (en) * 1999-02-15 2000-08-29 Kawasaki Heavy Ind Ltd Production of anatase titanium dioxide
JP2003012965A (en) * 2001-06-27 2003-01-15 Catalysts & Chem Ind Co Ltd Coating liquid for forming clear lowly reflective conductive film, substrate with clear lowly reflective conductive film, and display
WO2003006159A1 (en) * 2001-07-10 2003-01-23 Yoshiyuki Nagae Coating material, paint, and process for producing coating material
JP2004231927A (en) * 2002-12-02 2004-08-19 Yoshiyuki Nagae Pigment, coating material, and method for producing them
JP2005186005A (en) * 2003-12-26 2005-07-14 Dainippon Printing Co Ltd Production method for photocatalyst-containing layer substrate and pattern formed body
JP2009078264A (en) * 2007-09-03 2009-04-16 Tetsuto Nakajima Visible light-responsive photocatalyst and its manufacturing method
WO2011125949A1 (en) * 2010-04-05 2011-10-13 株式会社 ジャパンナノコート Coating liquid and substrate
JP2015530246A (en) * 2012-09-26 2015-10-15 スリーエム イノベイティブ プロパティズ カンパニー COATING COMPOSITION, PHOTOCATALYST ARTICLE, AND METHOD FOR PRODUCING THE SAME

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000233928A (en) * 1999-02-15 2000-08-29 Kawasaki Heavy Ind Ltd Production of anatase titanium dioxide
JP2003012965A (en) * 2001-06-27 2003-01-15 Catalysts & Chem Ind Co Ltd Coating liquid for forming clear lowly reflective conductive film, substrate with clear lowly reflective conductive film, and display
WO2003006159A1 (en) * 2001-07-10 2003-01-23 Yoshiyuki Nagae Coating material, paint, and process for producing coating material
JP2004231927A (en) * 2002-12-02 2004-08-19 Yoshiyuki Nagae Pigment, coating material, and method for producing them
JP2005186005A (en) * 2003-12-26 2005-07-14 Dainippon Printing Co Ltd Production method for photocatalyst-containing layer substrate and pattern formed body
JP2009078264A (en) * 2007-09-03 2009-04-16 Tetsuto Nakajima Visible light-responsive photocatalyst and its manufacturing method
WO2011125949A1 (en) * 2010-04-05 2011-10-13 株式会社 ジャパンナノコート Coating liquid and substrate
JP2015530246A (en) * 2012-09-26 2015-10-15 スリーエム イノベイティブ プロパティズ カンパニー COATING COMPOSITION, PHOTOCATALYST ARTICLE, AND METHOD FOR PRODUCING THE SAME

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