JP2005255809A - Pigment, coating, method for producing pigment and method for producing coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating capable of sufficiently performing a photocatalytic function, especially capable of sufficiently performing the photocatalytic function even by visible light and further a pigment being a base of the coating. <P>SOLUTION: The photocatalyst-covered particles are obtained by heating an aqueous solution containing titanium hydroxide, carbon and lithium chloride after irradiating ultrasonic wave under vacuum, then drying the mixture in the aqueous solution by a dryer to obtain titanium dioxide-covered particles and then calcining the titanium dioxide-covered particles under an inert gas atmosphere to convert the titanium dioxide to titanium suboxide. The coating is produced by preparing a dispersion by dispersing the produced photocatalyst-covered particles and mixing with the colloid of an off-shaped silicic acid, etc. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to pigments and paints and methods for producing them.

  Conventionally, there are various pigments and paints. In paints, a technique has been proposed in which a photocatalyst is contained in a paint and a coating film is formed on a building material or a structure to give the surface of the building material or the structure a photocatalytic function. Specifically, a photocatalyst function by irradiating light to the photocatalyst body, that is, a sterilization, deodorizing and purifying function by an organic substance decomposition action based on the oxidation-reduction action of the photocatalyst body was formed. It is a technology that can be demonstrated on the surface of building materials and structures.

Here, conventionally, a photocatalyst in which photocatalyst particles are coated with a porous powder and carbon is used for the porous powder, and a photocatalyst coating containing the photocatalyst are disclosed (see Patent Document 1). ).
JP 2000-317314 A

  However, a photocatalyst coating having a photocatalytic function superior to that of the photocatalyst described in Patent Document 1 and a photocatalyst coating (pigment) used for the photocatalyst coating has been desired. In particular, there has been a demand for a paint that exhibits a sufficient photocatalytic function even under visible light and a photocatalyst (pigment) used in the paint.

  Therefore, the present invention provides a coating material that can sufficiently perform a photocatalytic function, and in particular, a coating material that can perform a sufficient photocatalytic function even with visible light, and further a pigment that is the basis of the coating material. It is for the purpose.

  The present invention was created to solve the above-mentioned problems. First, the pigment is a photocatalyst-coated particle, which is a pigment particle, and a concave portion is formed on the surface by ultrasonic irradiation. It has the photocatalyst coating particle | grains which have the pigment particle which has it, and the photocatalyst particle coat | covered on the surface of this pigment particle, It is characterized by the above-mentioned.

  In the pigment of the first configuration, since the surface of the pigment particle is coated with the photocatalyst particle, the energy excited by the light absorbed by the pigment particle is transmitted to the photocatalyst particle covering the pigment particle, thereby causing the photocatalytic reaction. It tends to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In addition, since the concave portion by ultrasonic irradiation is provided on the surface of the pigment particle, the photocatalyst particle can be easily fitted into the concave portion, and the photocatalyst particle can be surely fixed on the surface of the pigment particle, thereby improving the photocatalytic function. Can be made.

  Secondly, in the first configuration, the pigment further includes lithium (may be a lithium particle) attached (may be supported) to the pigment particle and / or the photocatalyst particle. Features. Due to the presence of the lithium particles, it is possible to obtain electrical characteristics (for example, an electron transfer promoting function) by the lithium particles. For example, when this pigment is used as an electrode paint of a solar cell, the lithium particles can store electricity. Can be obtained.

  Thirdly, in the first or second configuration, the pigment particles are carbon material particles that are particles made of a carbon material. Thereby, since carbon material particles are generally black, a black pigment can be obtained. In addition, since the carbon material particles are generally black, they easily absorb light and can sufficiently exhibit a photocatalytic function.

  Fourth, the pigment is a photocatalyst-coated particle, the carbon material particle being a particle composed of a carbon material, the photocatalyst particle coated on the surface of the carbon material particle, the carbon material particle, And / or photocatalyst-coated particles having lithium (or lithium particles) attached (or supported) to the photocatalyst particles.

  In the pigment of the fourth configuration, since the surface of the carbon material particles is coated with photocatalyst particles, the energy excited by the light absorbed by the carbon material particles is transmitted to the photocatalyst particles covering the carbon material particles, Photocatalytic reaction tends to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. Moreover, since it has lithium particles, the presence of the lithium particles makes it possible to obtain electrical characteristics (for example, an electron transfer promoting function) by the lithium particles. For example, this pigment can be used as an electrode paint for solar cells. When used, the lithium particles can provide a power storage function.

  According to a fifth aspect of the present invention, in the fourth configuration, the surface of the carbon material particle is provided with a concave portion formed by ultrasonic irradiation. Therefore, the photocatalyst particles and the lithium particles can be easily fitted in the recesses, and the photocatalyst particles can be reliably fixed to the surface of the pigment particles, thereby improving the photocatalytic function.

  Sixthly, in the fourth or fifth configuration, the pigment is ultrasonically irradiated to an aqueous solution containing titanium hydroxide, a carbon material, and lithium chloride in a pressure state of atmospheric pressure or lower. Then, heating is performed, and then the precipitate is dried, and then fired in an inert gas atmosphere or in a vacuum state. In addition, in the sixth configuration, after the above pigment was ultrasonically heated in a pressure state of atmospheric pressure or lower in a dispersion in which a carbon material was dispersed in a titanium hydroxide aqueous solution, a lithium chloride aqueous solution was dropped, and then a precipitate was formed. It is good also as what was produced | generated by drying after that and baking by inert gas atmosphere.

  Seventhly, in any one of the third to sixth configurations, the carbon material particles are at least one of carbon particles, carbon particles, and activated carbon particles.

Eighth, in any one of the first to seventh configurations, the photocatalyst particles are titanium suboxide. Therefore, since the photocatalytic particles are titanium suboxide, a strong photocatalytic function can be obtained, and a photocatalytic reaction can be easily caused even when the irradiated light is in the visible light region. The titanium suboxide includes, for example, titanium suboxide having a composition of Ti ₂ O ₃ , and the titanium suboxide composition includes not only Ti ₂ O ₃ but also Ti _X O _Y.

  Ninth, in any one of the first to eighth configurations, the pigment further includes titanium suboxide particles formed by firing metal titanium particles in an inert gas atmosphere. And Thus, the pigment can further enhance the photocatalytic function by further including titanium suboxide particles.

  Tenthly, in any one of the first to ninth configurations, the photocatalyst particles are produced by heating a mixed solution of titanium hydroxide and an alkaline aqueous solution in a pressure state of atmospheric pressure or lower. It is characterized by being rutile type titanium dioxide. In the pigment of the tenth configuration, since the photocatalyst particles are rutile type titanium dioxide, a strong photocatalytic function can be obtained, and in particular, a photocatalytic reaction can be obtained even by visible light.

  The eleventh aspect of the present invention is a paint comprising the pigment of the above-described first, second, third, fourth, fifth, sixth, seventh, eighth, ninth or tenth, and a colloidal solution. To do.

  In the paint of this eleventh configuration, since the photocatalyst particles are coated on the surface of the pigment particles constituting the pigment, the energy excited by the light absorbed by the pigment particles is transmitted to the photocatalyst particles covering the pigment particles. , Photocatalytic reaction tends to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. Further, since the pigment particles are adsorbed on the surface of the colloidal particles constituting the colloidal solution, the pigment particles can be efficiently irradiated with light on the surface of the colloidal particles. , Can stably exhibit the photocatalytic function. Therefore, it is possible to sufficiently function the ability of the photocatalyst to decompose organic substances even on a thin coating film.

  In addition, this eleventh constitution is “having photocatalyst-coated particles constituting the pigment having the constitution of the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth or tenth, and colloidal particles. It is good also as a paint characterized by. In addition, the eleventh constitution is “a paint, comprising water, colloidal particles, and the pigment of the constitution of the first, the second, the third, the fourth, the fifth, the sixth, the seventh, the eighth, the ninth, or the tenth. The coating material is characterized in that the photocatalyst-coated particles are dispersed. "

  Twelfth, in the eleventh configuration, the colloidal solution is a solution having a silicic acid heteromorphic colloid.

  In a thirteenth aspect, in the eleventh or twelfth configuration, the paint further includes at least one of lithium silicate and titanium hydroxide.

  The 14th is a method for producing a pigment, which includes an aqueous solution containing titanium hydroxide, pigment particles and a chloride compound, or an aqueous solution containing titanium hydroxide and pigment particles and chloride ions. An ultrasonic irradiation process for irradiating an ultrasonic wave in a pressure state of atmospheric pressure or lower with respect to the target aqueous solution that is an aqueous solution obtained by mixing the aqueous solution, and heating the target aqueous solution irradiated with the ultrasonic wave in the ultrasonic irradiation process A heating step for changing at least a part of titanium hydroxide into titanium dioxide, and a baking step for changing the precipitate produced in the heating step into titanium suboxide by baking in an inert gas atmosphere. It is characterized by having.

In the manufacturing method of the fourteenth configuration, at least a part of titanium hydroxide is changed to titanium dioxide by the heating step, thereby generating photocatalyst-coated particles in which the surface of pigment particles is coated with titanium dioxide, By changing the titanium dioxide into titanium suboxide by the firing step, a pigment in which the surface of the pigment particles is coated with titanium suboxide is generated. Since the pigment produced in this manner has the photocatalyst particles coated on the surface of the pigment particles, the energy excited by the light absorbed by the pigment particles is transmitted to the photocatalyst particles that coat the pigment particles, thereby causing a photocatalytic reaction. It becomes easy. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In particular, since the pigment particles are coated with titanium suboxide, a strong photocatalytic function can be obtained with the titanium suboxide, and a photocatalytic reaction can easily occur even when the irradiated light is in the visible light region. . The titanium suboxide includes, for example, titanium suboxide having a composition of Ti ₂ O ₃ , and the titanium suboxide composition includes not only Ti ₂ O ₃ but also Ti _X O _Y. Furthermore, since the concave portion is provided on the surface of the pigment particle by irradiating with ultrasonic waves, the photocatalyst particle can be easily fitted into the concave portion, and the photocatalyst particle can be securely fixed to the surface of the pigment particle, The photocatalytic function can be improved. Further, since the ultrasonic heating is performed under a pressure state equal to or lower than the atmospheric pressure, the pigment particles are likely to be fitted into the concave portion. Moreover, since the target aqueous solution contains an aqueous solution containing a chloride compound or chlorine ions, the adhesion between titanium hydroxide and pigment particles can be improved. In the above heating step, it is preferable to heat the aqueous solution while stirring.

  Fifteenth, the method for producing a pigment, an ultrasonic irradiation step of irradiating the target aqueous solution, which is an aqueous solution having titanium hydroxide and pigment particles, with an ultrasonic pressure in a pressure state equal to or lower than atmospheric pressure; , Heating the target aqueous solution irradiated with ultrasonic waves in the ultrasonic irradiation step to change at least a part of titanium hydroxide into titanium dioxide, the aqueous solution heated in the heating step, and chlorine ions A mixing step of mixing an aqueous solution or a chlorinated compound containing, and a baking step of changing titanium dioxide into titanium suboxide by baking a precipitate in the aqueous solution produced in the mixing step in an inert gas atmosphere. It is characterized by having.

In the manufacturing method of the fifteenth configuration, at least a part of titanium hydroxide is changed to titanium dioxide by the heating step, thereby generating photocatalyst-coated particles in which the surface of the pigment particles is coated with titanium dioxide, By changing the titanium dioxide into titanium suboxide by the firing step, a pigment in which the surface of the pigment particles is coated with titanium suboxide is generated. Since the pigment produced in this manner has the photocatalyst particles coated on the surface of the pigment particles, the energy excited by the light absorbed by the pigment particles is transmitted to the photocatalyst particles that coat the pigment particles, thereby causing a photocatalytic reaction. It becomes easy. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In particular, since the pigment particles are coated with titanium suboxide, a strong photocatalytic function can be obtained with the titanium suboxide, and a photocatalytic reaction can easily occur even when the irradiated light is in the visible light region. . The titanium suboxide includes, for example, titanium suboxide having a composition of Ti ₂ O ₃ , and the titanium suboxide composition includes not only Ti ₂ O ₃ but also Ti _X O _Y. Furthermore, since the concave portion is provided on the surface of the pigment particle by irradiating with ultrasonic waves, the photocatalyst particle can be easily fitted into the concave portion, and the photocatalyst particle can be securely fixed to the surface of the pigment particle, The photocatalytic function can be improved. Further, since the ultrasonic heating is performed under a pressure state equal to or lower than the atmospheric pressure, the pigment particles are likely to be fitted into the concave portion. Moreover, since the aqueous solution or chloride compound containing a chlorine ion is mixed in a mixing process, the adhesiveness of titanium dioxide (and titanium hydroxide) and a pigment particle can be improved. In the above heating step, it is preferable to heat the aqueous solution while stirring. In the fifteenth configuration, the mixing step may be a “mixing step of mixing an aqueous solution or chloride compound containing chlorine ions into the aqueous solution heated in the heating step”.

  Sixteenth, in the fourteenth or fifteenth configuration, the chloride compound is lithium chloride, and the aqueous solution containing chlorine ions is a lithium chloride aqueous solution. Therefore, since the manufactured pigment contains lithium particles, it is possible to obtain the effects, for example, the electrical characteristics (for example, the function of promoting the movement of electrons) due to the lithium particles. That is, for example, when this pigment is used as an electrode coating material for a solar battery, a power storage function can be obtained from the lithium particles.

  Seventeenth, the method for producing a pigment, an ultrasonic irradiation step of irradiating the target aqueous solution, which is an aqueous solution having titanium hydroxide and pigment particles, with an ultrasonic pressure under a pressure state of atmospheric pressure; A heating step in which at least a part of titanium hydroxide is changed to titanium dioxide by heating the aqueous solution irradiated with ultrasonic waves in the ultrasonic irradiation step, and a precipitate in the aqueous solution produced in the heating step. And a firing step of changing to titanium suboxide by firing in an inert gas atmosphere.

In the manufacturing method of the seventeenth configuration, at least a part of titanium hydroxide is changed to titanium dioxide by the heating step, thereby generating photocatalyst-coated particles in which the surface of pigment particles is coated with titanium dioxide, By changing the titanium dioxide into titanium suboxide by the firing step, a pigment in which the surface of the pigment particles is coated with titanium suboxide is generated. Since the pigment produced in this manner has the photocatalyst particles coated on the surface of the pigment particles, the energy excited by the light absorbed by the pigment particles is transmitted to the photocatalyst particles that coat the pigment particles, thereby causing a photocatalytic reaction. It becomes easy. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In particular, since the pigment particles are coated with titanium suboxide, a strong photocatalytic function can be obtained with the titanium suboxide, and a photocatalytic reaction can easily occur even when the irradiated light is in the visible light region. . The titanium suboxide includes, for example, titanium suboxide having a composition of Ti ₂ O ₃ , and the titanium suboxide composition includes not only Ti ₂ O ₃ but also Ti _X O _Y. Furthermore, since the concave portion is provided on the surface of the pigment particle by irradiating with ultrasonic waves, the photocatalyst particle can be easily fitted into the concave portion, and the photocatalyst particle can be securely fixed to the surface of the pigment particle, The photocatalytic function can be improved. Further, since the ultrasonic heating is performed under a pressure state equal to or lower than the atmospheric pressure, the pigment particles are likely to be fitted into the concave portion. In the above heating step, it is preferable to heat the aqueous solution while stirring.

  Eighteenth, in any of the fourteenth to seventeenth configurations, the target aqueous solution further contains metallic titanium. Therefore, titanium suboxide particles can be generated by firing particles in which titanium hydroxide is coated on titanium metal.

  Nineteenth, in any of the fourteenth to eighteenth aspects, metallic titanium is added before the firing step. Therefore, titanium suboxide particles can be generated by firing titanium metal in the firing step.

  In the twentieth aspect, in any of the fourteenth to nineteenth aspects, a drying step for drying the precipitate to be fired is provided immediately before the firing step. In the firing step, the drying step is performed. The precipitate dried in the process is calcined in an inert gas atmosphere.

  The 21st is a method for producing a pigment, comprising: heating a solution in which pigment particles, titanium hydroxide, and an alkaline aqueous solution are mixed to change the titanium hydroxide into rutile titanium dioxide. It is characterized by having.

  In the pigment manufactured by the manufacturing method of the twenty-first configuration, since the rutile type titanium dioxide as the photocatalyst particle is coated on the surface of the pigment particle, the energy excited by the light absorbed by the pigment particle By being transmitted to the photocatalyst particles to be coated, a photocatalytic reaction is likely to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In particular, since the pigment particles are coated with rutile titanium dioxide, a strong photocatalytic function can be obtained with the rutile titanium dioxide, and a photocatalytic reaction is easily caused even when the irradiated light is in the visible light region. be able to.

  The 22nd is a method for producing a pigment, in which a titanium hydroxide gel is produced by mixing a titanium tetrachloride aqueous solution, pigment particles and ammonia, and reacting titanium tetrachloride with ammonia. A step, an ultrasonic irradiation step of irradiating the target solution, which is a solution obtained by adding an alkaline aqueous solution to the generated titanium hydroxide gel and pigment particles, in a pressure state below atmospheric pressure, and heating the target solution And a heating step for producing photocatalyst-coated particles in which the surface of the pigment particles is coated with rutile-type titanium dioxide.

  In the manufacturing method of the twenty-second configuration, the target solution is heated with an alkaline aqueous solution added to the titanium hydroxide gel, so that rutile titanium dioxide is generated. In the pigment manufactured by the manufacturing method of the twenty-second structure, since the rutile type titanium dioxide as the photocatalyst particle is coated on the surface of the pigment particle, the energy excited by the light absorbed by the pigment particle By being transmitted to the photocatalyst particles to be coated, a photocatalytic reaction is likely to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. In particular, since the pigment particles are coated with rutile titanium dioxide, a strong photocatalytic function can be obtained with the rutile titanium dioxide, and a photocatalytic reaction is easily caused even when the irradiated light is in the visible light region. be able to. In addition, since the concave portion is provided on the surface of the pigment particle by irradiating with ultrasonic waves, the photocatalyst particle can be easily fitted into the concave portion, and the photocatalyst particle can be securely fixed to the surface of the pigment particle, The photocatalytic function can be improved. Further, since the ultrasonic heating is performed under a pressure state equal to or lower than the atmospheric pressure, the pigment particles are likely to be fitted into the concave portion. In the above heating step, it is preferable to heat the aqueous solution while stirring.

  According to a twenty-third aspect, in the twenty-first or twenty-second configuration, the alkaline aqueous solution is ammonia water.

  According to a twenty-fourth aspect, in any one of the fourteenth to twentieth configurations, the pigment particles are carbon material particles that are particles made of a carbon material. This makes it possible to produce a black pigment.

  According to a twenty-fifth aspect, in any one of the twenty-first to twenty-third configurations, the pigment particles are carbon material particles that are particles composed of a carbon material. This makes it possible to produce a black pigment.

  According to a twenty-sixth aspect, in the twenty-fourth or twenty-fifth configuration, the carbon material particles are at least one of carbon particles, carbon particles, and activated carbon particles.

According to a twenty-seventh aspect, in the twenty-fourth configuration, in the baking step, baking is performed in a vacuum state instead of an inert gas. That is, even if it is not in an inert gas atmosphere, carbon dioxide is vaporized by heating, so that titanium dioxide can be changed to titanium suboxide. The titanium suboxide includes, for example, titanium suboxide having a composition of Ti ₂ O ₃ , and the titanium suboxide composition includes not only Ti ₂ O ₃ but also Ti _X O _Y.

  In the fourteenth to twenty-seventh configurations, when heating is performed in the heating step, it is preferable to perform heating in an oxygen deficient state.

  The 28th is a method for producing a paint, a pigment production process for producing a pigment by the method for producing a pigment having any one of the above 14th to 27th aspects, a colloidal solution in water, And a dispersion production process for producing a solution in which the pigment produced by the pigment production process is dispersed.

  In the paint produced by the paint production method of the 28th composition, the surface of the pigment particles constituting the pigment is coated with the photocatalyst particles, so that the energy excited by the light absorbed by the pigment particles By being transmitted to the photocatalyst particles to be coated, a photocatalytic reaction is likely to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region. Further, since the pigment particles are adsorbed on the surface of the colloidal particles constituting the colloidal solution, the pigment particles can be efficiently irradiated with light on the surface of the colloidal particles. , Can stably exhibit the photocatalytic function. Therefore, it is possible to sufficiently function the ability of the photocatalyst to decompose organic substances even on a thin coating film. In the twenty-eighth configuration, the dispersion manufacturing process may be referred to as “a mixed liquid manufacturing process for manufacturing a mixed liquid in which water, a colloidal solution, and a pigment manufactured by the pigment manufacturing process are mixed”. Good.

  According to a twenty-ninth aspect, in the twenty-eighth configuration, the colloidal solution is a solution having a silicic acid irregular shape colloid.

  In the thirtieth aspect, in the twenty-eighth or twenty-ninth configuration, at least one of lithium silicate and titanium hydroxide is mixed in the dispersion manufacturing step.

  According to the pigment, paint, and pigment produced by the pigment production method according to the present invention, and the paint produced by the paint production method, the surface of the pigment particle is coated with photocatalyst particles. The energy excited by the absorbed light is transmitted to the photocatalyst particles covering the pigment particles, so that the photocatalytic reaction is likely to occur. Therefore, it is possible to easily cause a photocatalytic reaction even when the irradiated light is in the visible light region.

  In addition, when a concave portion is formed on the surface of the pigment particle by ultrasonic irradiation, the photocatalyst particle is easy to fit in the concave portion, and the photocatalyst particle can be securely fixed on the surface of the pigment particle, thereby improving the photocatalytic function. Can be made.

  In addition, when the pigment particles contain lithium, the presence of the lithium can provide electrical characteristics (for example, an electron transfer promoting function) due to the lithium. For example, the pigment can be used as an electrode paint for solar cells. When used, this lithium can provide a power storage function.

  Further, when the photocatalyst particles are titanium suboxide, a strong photocatalytic function can be obtained, and a photocatalytic reaction can be easily caused even when the irradiated light is in the visible light region.

  In addition, when the pigment particles are carbon material particles that are particles composed of a carbon material, a black pigment can be obtained, light can be easily absorbed, and a sufficient photocatalytic function can be exhibited. .

  In the present invention, a paint capable of sufficiently fulfilling a photocatalytic function, in particular, a paint capable of fulfilling a sufficient photocatalytic function even with visible light, and further a pigment as a basis of the paint are provided. The objective was realized as follows.

  The coating material of Example 1 is mainly composed of photocatalyst-coated particles (which may be photocatalyst-coated pigment particles) in which the surface of carbon particles is coated with titanium suboxide particles. That is, the surface of black particles is coated with a photocatalytic substance. Further, in the photocatalyst-coated particles, lithium particles are attached to the surfaces of the carbon particles and the titanium suboxide particles. As will be described later, in the production process of the photocatalyst-coated particles, since heating is performed after irradiating ultrasonic waves, a plurality of (specifically, a large number of) recesses are formed on the surface of the carbon particles, and the titanium suboxide particles Some lithium and lithium particles are fitted in the recesses.

  In the coating material of this example, the photocatalyst-coated particles are dispersed in a mixed solution of a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid aqueous solution (colloidal solution). . Thereby, since the silicic acid irregular-shaped body colloid is exhibiting the shape where the colloidal particle | grains were connected to the net shape, the photocatalyst covering particle | grains and the lithium silicate particle are in the state which adhered to this silicic acid irregular-shaped body colloid.

  Further, the photocatalyst-coated particles are obtained by coating the surfaces of carbon particles (pigment particles, carbon material particles) with titanium suboxide particles (photocatalyst particles). Lithium particles adhere to the surface of the titanium suboxide particles. That is, titanium suboxide particles with lithium particles adhering to the surface or lithium particles adhering to the surface of the carbon particles, which cover the carbon particles. Note that the degree of adhesion of lithium particles to titanium suboxide particles is not necessarily the same for each titanium suboxide, and in fact, lithium particles cover the entire surface of titanium suboxide particles. It may be coated or partially attached to the surface of titanium suboxide, and the degree of adhesion of lithium particles to the titanium suboxide particles varies depending on the individual titanium suboxide. Yes.

The titanium suboxide in the photocatalyst-coated particles includes, for example, titanium suboxide having a composition of Ti ₂ O _3. The composition of titanium suboxide includes not only Ti ₂ O ₃ but also Ti _X O _Y. Is mentioned. This is the same in the following description of this embodiment.

  The average particle diameter of the photocatalyst-coated particles is, for example, about 20 μm, and the average particle diameter of carbon particles in the photocatalyst-coated particles is, for example, about 20 μm. The particle size is, for example, 5 to 10 nm.

  A method for producing the paint having the above-described configuration will be described. First, a titanium hydroxide aqueous solution and a surface-treated carbon-dispersed aqueous solution are mixed and dispersed to produce a mixed dispersion. A lithium chloride aqueous solution is dropped into the mixed dispersion, and the mixture is allowed to stand after stirring for a predetermined time. To do. That is, an aqueous solution having titanium hydroxide, carbon as pigment particles, and lithium chloride is produced. Thereafter, the mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. In heating, the mixed dispersion is heated while stirring. Thereafter, the mixed dispersion liquid is drained and the mixture in the mixed dispersion liquid is dried with a dryer to obtain titanium dioxide-coated particles.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere, whereby the titanium dioxide becomes titanium suboxide and the photocatalyst-coated particles are obtained.

  Then, the produced photocatalyst-coated particles are dispersed in water to produce a dispersion, and the dispersion is mixed with a mixed liquid obtained by mixing a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid. By doing so, a paint was obtained.

  The above manufacturing method will be described more specifically as follows. First, 1000 g of an aqueous titanium hydroxide solution (for example, 2% solid content) and 1030 g of an aqueous solution in which 30 g of carbon (for example, an average particle diameter of 20 μm and a specific gravity of 0.3) subjected to surface treatment with alcohol or nitric acid are dispersed. To produce a mixed dispersion. Here, the aqueous solution of titanium hydroxide is obtained by, for example, reacting ammonia with titanium tetrachloride to obtain a titanium hydroxide gel, and by adding hydrogen peroxide water to the titanium hydroxide gel, an amorphous titanium hydroxide sol is obtained. Although obtained, it is set as the aqueous solution of this titanium hydroxide sol.

  Then, an aqueous lithium chloride solution is dropped into the mixed dispersion and left to stand after stirring for a predetermined time. For example, a lithium chloride aqueous solution is dropped into the mixed dispersion (may be mixed with lithium chloride), and the mixture is allowed to stand after stirring for 3 to 10 minutes (preferably 5 minutes). The lithium chloride aqueous solution is dropped to improve the adhesion between titanium hydroxide and carbon particles. The mixed dispersion in which the lithium chloride aqueous solution is dropped corresponds to the “target aqueous solution”. That is, this mixed dispersion is obtained by mixing “an aqueous solution that is an aqueous solution containing titanium hydroxide, pigment particles and a chloride compound” or “an aqueous solution containing titanium hydroxide and pigment particles and an aqueous solution containing chloride ions. The target aqueous solution which is an aqueous solution. The aqueous lithium chloride solution corresponds to the “aqueous solution containing chlorine ions”, and the lithium chloride corresponds to the “chloride compound”.

  The mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. That is, with the mixed dispersion in the sealed container, the sealed container is evacuated, and the mixed dispersion is heated after irradiating ultrasonic waves from the outside of the sealed container.

  Specifically, an ultrasonic heating device P as shown in FIG. 1 is used. That is, the ultrasonic heating device P includes a base part 5, an ultrasonic vibrator 7 provided on the base part 5, a sealed container 10 provided on the base part 5, and an inside of the sealed container 10. The container 12, the heater 14 for heating the inside of the sealed container 10, and the stirrer 16 for stirring the liquid or the like in the container 12, so that the inside of the sealed container 10 can be evacuated and gas can be enclosed. It has become. The mixed dispersion liquid is placed in the container 12, and the temperature adjusting agent 30 is placed between the sealed container 10 and the container 12.

  And while putting the said mixed dispersion liquid in the container 12 and putting the temperature regulator 30 between the airtight containers 10 and 12, the inside of the airtight container 10 is evacuated, and then the ultrasonic vibrator 7 Irradiate ultrasonic waves (ultrasonic irradiation process). Then, a plurality (specifically, a large number) of recesses are formed on the surface of the carbon particles by ultrasonic waves.

Then, the mixed dispersion is heated by the heater 14 (heating step). In addition, the heating is performed while stirring the mixed dispersion with the stirrer 16. Then, titanium hydroxide becomes titanium dioxide (strictly, anatase type titanium dioxide) by this heating. In this case, the heating temperature is 70 ° C. to 90 ° C. (preferably 80 ° C.), and the heating time is 15 minutes to 25 minutes (preferably 20 minutes). The degree of vacuum is about 10 ⁻⁴ to 10 ⁻¹⁰ Torr. In addition, at least a part of the titanium dioxide particles are fitted into the recesses formed on the surface of the carbon particles. Moreover, since it heats in the pressure_reduction | reduced_pressure state called a vacuum state, a titanium dioxide particle is easy to be fitted in this recessed part. In the production of the photocatalyst-coated particles, the mixed dispersion is heated in a vacuum state, that is, in an oxygen deficient state, so that the carbon particles are prevented from burning.

  In the above process, the surface of the carbon particles is coated with titanium dioxide, but in actuality, it is not necessarily in a completely coated state. It adheres not only to the surface of carbon particles. In addition, since the recessed part was formed in the surface of the carbon particle by the ultrasonic wave as mentioned above, the lithium particle fits in this recessed part.

  Then, 50 g of titanium dioxide-coated particles could be obtained by draining the mixed water of the mixed dispersion and drying the mixture in the mixed dispersion, that is, the precipitate with a dryer. In this case, the drying temperature is 70 to 90 ° C. (preferably 80 ° C.), and the drying time is 6 to 10 hours (preferably 8 hours). In addition, titanium hydroxide becomes titanium dioxide even when the mixed dispersion is heated, but the titanium hydroxide is sufficiently changed to titanium dioxide by heating in this drying. In this way, the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are obtained by coating the surface of carbon particles with titanium dioxide, and more strictly, lithium particles are attached to the surface of carbon particles or the surface of titanium dioxide particles.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere (firing step), whereby the titanium dioxide becomes titanium suboxide and 50 g of the photocatalyst-coated particles can be obtained. Since the photocatalyst-coated particles are basically in a state in which titanium suboxide is coated around the black carbon particles, a black pigment can be obtained. The produced pigment can also be referred to as a photocatalyst-coated pigment. In this case, for example, nitrogen gas or argon gas is used as the inert gas. The firing temperature is 350 ° C. to 950 ° C., and the firing time is 20 to 110 minutes (preferably 90 minutes). In addition, titanium dioxide changes into titanium suboxide by firing titanium dioxide in an inert gas atmosphere to change titanium dioxide into titanium suboxide, and some of the carbon in the carbon particles is vaporized. By doing so, titanium dioxide changes to titanium suboxide. In other words, in the above example, firing is performed in an inert gas, but titanium dioxide is sub-oxidized due to partial vaporization of carbon in the carbon particles even when firing in a vacuum rather than in an inert gas. Change to titanium. At that position, the firing temperature may be any temperature at which carbon vaporizes. A pigment is produced according to the above-described pigment production process.

  The X-ray analysis of the photocatalyst-coated particles produced above confirmed that the substance covering the carbon particles was titanium suboxide, and the electron microscope showed that the titanium suboxide coated the carbon particle surfaces. It was confirmed that The produced photocatalyst-coated particles have an average particle size of 20 μm.

  In the above description, the mixed dispersion is heated with a heater in a vacuum state and then heated with a heater. However, the mixed dispersion may be heated while being irradiated with an ultrasonic wave in a vacuum state.

  In the above, the mixed dispersion liquid in which the titanium hydroxide aqueous solution and the carbon-dispersed aqueous solution are mixed and dispersed is heated after being irradiated with ultrasonic waves in a vacuum. It may be omitted, and the subsequent steps may be performed by dropping a lithium chloride aqueous solution into the mixed dispersion.

  Next, 50 g of the produced photocatalyst-coated particles are dispersed in 100 g of water to produce a dispersion. The dispersion is made up of 10 g of a lithium silicate aqueous solution (solid content 45%) and a titanium hydroxide aqueous solution (solid content 10%). 40 g and 100 g of silicic acid irregularly shaped body colloid (solid content 20%) were mixed (mixed liquid production step) to obtain 300 g of a coating material. This paint is a black paint because the photocatalyst-coated particles as the main component are black pigments. In addition, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are mixed as a binder, so that these binders increase the adhesive strength with the photocatalyst-coated particles, and the coating surface and coating material on which the coating material is applied. It is possible to form a thin film by increasing the adhesive strength.

  In addition, with respect to said manufacturing method, you may manufacture photocatalyst covering particle | grains with the following manufacturing methods. That is, first, a mixed dispersion is produced by mixing and dispersing a titanium hydroxide aqueous solution and a surface-treated carbon-dispersed aqueous solution. Thereafter, the mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. In heating, the mixed dispersion is heated while stirring. Thereafter, an aqueous lithium chloride solution is dropped into the mixed dispersion and left to stand after stirring for a predetermined time. Thereafter, the mixed dispersion is dehydrated by drying the mixture in the mixed dispersion by drying the mixture water. Titanium-coated particles are obtained.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere, whereby the titanium dioxide becomes titanium suboxide and the photocatalyst-coated particles are obtained.

  Then, the produced photocatalyst-coated particles are dispersed in water to produce a dispersion, and the dispersion is mixed with a mixed liquid obtained by mixing a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid. By doing so, a paint was obtained.

  The above manufacturing method will be described more specifically as follows. First, 1000 g of an aqueous titanium hydroxide solution (for example, 2% solid content) and 1030 g of an aqueous solution in which 30 g of carbon (for example, an average particle diameter of 20 μm and a specific gravity of 0.3) subjected to surface treatment with alcohol or nitric acid are dispersed. To produce a mixed dispersion. This mixed dispersion corresponds to the target aqueous solution. The titanium hydroxide aqueous solution can be obtained, for example, by allowing ammonia to act on titanium tetrachloride, and further adding hydrogen peroxide to the titanium hydroxide gel to obtain an amorphous titanium hydroxide sol. However, an aqueous solution of this titanium hydroxide sol is used.

  The mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. That is, with the mixed dispersion in the sealed container, the sealed container is evacuated, and the mixed dispersion is heated after irradiating ultrasonic waves from the outside of the sealed container.

  Specifically, an ultrasonic heating device P as shown in FIG. 1 is used. That is, while the mixed dispersion liquid is put into the container 12 and the temperature adjusting agent 30 is put between the sealed container 10 and the container 12, the inside of the sealed container 10 is evacuated. Irradiate ultrasonic waves (ultrasonic irradiation process). Then, a plurality (specifically, a large number) of recesses are formed on the surface of the carbon particles by ultrasonic waves.

Then, the mixed dispersion is heated by the heater 14 (heating step). In addition, the heating is performed while stirring the mixed dispersion with the stirrer 16. Then, titanium hydroxide becomes titanium dioxide (strictly, anatase type titanium dioxide) by this heating. In this case, the heating temperature is 70 ° C. to 90 ° C. (preferably 80 ° C.), and the heating time is 15 minutes to 25 minutes (preferably 20 minutes). The degree of vacuum is about 10 ⁻⁴ to 10 ⁻¹⁰ Torr. In addition, at least a part of the titanium dioxide particles are fitted into the recesses formed on the surface of the carbon particles. Moreover, since it heats in the pressure_reduction | reduced_pressure state called a vacuum state, a titanium dioxide particle is easy to be fitted in this recessed part. In the production of the photocatalyst-coated particles, the mixed dispersion is heated in a vacuum state, that is, in an oxygen deficient state, so that the carbon particles are prevented from burning.

  Thereafter, an aqueous lithium chloride solution is dropped into the mixed dispersion (mixing step), and the mixture is allowed to stand after stirring for a predetermined time. For example, a lithium chloride aqueous solution is dropped into the mixed dispersion (may be mixed with lithium chloride), and the mixture is allowed to stand after stirring for 3 to 10 minutes (preferably 5 minutes). The lithium chloride aqueous solution is dropped to improve the adhesion between titanium dioxide and carbon particles. The aqueous lithium chloride solution corresponds to the “aqueous solution containing chlorine ions”, and the lithium chloride corresponds to the “chloride compound”.

  In the above process, the surface of the carbon particles is coated with titanium dioxide, but in actuality, it is not necessarily in a completely coated state, and the lithium particles are not coated with titanium dioxide. It adheres not only to the surface of carbon but also to the surface of carbon particles. As described above, since the recesses are formed by ultrasonic waves on the surface of the carbon particles, at least some of the lithium particles are fitted into the recesses.

  Then, 50 g of titanium dioxide-coated particles could be obtained by draining the mixed water of the mixed dispersion and drying the mixture in the mixed dispersion, that is, the precipitate with a dryer. In this case, the drying temperature is 70 to 90 ° C. (preferably 80 ° C.), and the drying time is 6 to 10 hours (preferably 8 hours). In addition, titanium hydroxide becomes titanium dioxide even when the mixed dispersion is heated, but the titanium hydroxide is sufficiently changed to titanium dioxide by heating in this drying. In this way, the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are obtained by coating the surface of carbon particles with titanium dioxide, and more strictly, lithium particles are attached to the surface of carbon particles or the surface of titanium dioxide particles.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere (firing step), whereby the titanium dioxide becomes titanium suboxide and 50 g of the photocatalyst-coated particles can be obtained. Since the photocatalyst-coated particles are basically in a state in which titanium suboxide is coated around the black carbon particles, a black pigment can be obtained. The produced pigment can also be referred to as a photocatalyst-coated pigment. In this case, for example, nitrogen gas or argon gas is used as the inert gas. The firing temperature is 350 ° C. to 950 ° C., and the firing time is 20 to 110 minutes (preferably 90 minutes). As described above, the action of changing titanium dioxide to titanium suboxide is that titanium dioxide is changed to titanium suboxide by firing in an inert gas atmosphere, Titanium dioxide is changed to titanium suboxide by partial vaporization of carbon. In other words, in the above example, firing is performed in an inert gas, but titanium dioxide is sub-oxidized due to partial vaporization of carbon in the carbon particles even when firing in a vacuum rather than in an inert gas. Change to titanium. At that position, the firing temperature may be any temperature at which carbon vaporizes.

  The X-ray analysis of the photocatalyst-coated particles produced above confirmed that the substance covering the carbon particles was titanium suboxide, and the electron microscope showed that the titanium suboxide coated the carbon particle surfaces. It was confirmed that The produced photocatalyst-coated particles have an average particle size of 20 μm.

  In the above description, the mixed dispersion is heated with a heater in a vacuum state and then heated with a heater. However, the mixed dispersion may be heated while being irradiated with an ultrasonic wave in a vacuum state.

  The method of using the coating material of this embodiment will be described. In the coating material of this embodiment, a coating film is formed by coating on the application surface. In the coating material of this example, since the photocatalyst-coated particles are contained, an extremely excellent photocatalytic function can be achieved. In particular, since the photocatalyst-coated particles are coated with titanium suboxide around the black carbon particles, the photocatalyst function by the titanium suboxide can be fully exhibited because it easily absorbs light. Since the particles contain titanium suboxide, the photocatalytic function can be sufficiently exerted even by visible light.

  In addition, according to the coating material of this example, since the photocatalyst-coated particles are attached to the surface of the silicic acid irregularly shaped colloid, the photocatalyst-coated particles can be efficiently irradiated with light, and have a stable photocatalytic function. Therefore, the photocatalytic function can be sufficiently exerted even on a thin coating film.

  Further, in the coating material of this example, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are included, so that the adhesive strength with the photocatalyst-coated particles is increased, and the coating surface and the coating material on which the coating material is applied The adhesion strength of the film can be increased to form a thin film.

  Moreover, according to the photocatalyst-coated particles of this example, it can be used as a pigment in addition to the case of using as a raw material for a paint as described above, and even in that case, an extremely excellent photocatalytic function can be achieved.

  In addition, since the photocatalyst-coated particles and the photocatalyst-coated particles in the paint of this example contain lithium particles, the effects of the presence of the lithium particles, for example, the electrical characteristics (for example, the electronic properties of the lithium particles) Movement promotion function). That is, for example, when this pigment is used as an electrode coating material for a solar battery, a power storage function can be obtained from the lithium particles.

  In the above description, carbon is used in the production of the photocatalyst-coated particles, and the surface of the carbon particles is coated with titanium suboxide. However, carbon or activated carbon may be used instead of carbon. When carbon is used, the surface of the carbon particles is coated with titanium suboxide, and when activated carbon is used, the surface of the activated carbon particles is coated with titanium suboxide.

  Next, Example 2 will be described. The paint of Example 2 is the same as the paint of Example 1 above, but the manufacturing method is different.

  That is, the coating material of Example 2 is mainly composed of photocatalyst-coated particles (which may be photocatalyst-coated pigment particles) in which the surfaces of carbon particles are coated with titanium suboxide particles. That is, the surface of black particles is coated with a photocatalytic substance. Further, in the photocatalyst-coated particles, lithium particles are attached to the surfaces of the carbon particles and the titanium suboxide particles. As will be described later, in the production process of the photocatalyst-coated particles, since heating is performed after irradiating ultrasonic waves, a plurality of (specifically, a large number of) recesses are formed on the surface of the carbon particles, and the titanium suboxide particles Some lithium and lithium particles are fitted in the recesses.

  In the coating material of this example, the photocatalyst-coated particles are dispersed in a mixed solution of a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid aqueous solution (colloidal solution). . Thereby, since the silicic acid irregular-shaped body colloid is exhibiting the shape where the colloidal particle | grains were connected to the net shape, the photocatalyst covering particle | grains and the lithium silicate particle are in the state which adhered to this silicic acid irregular-shaped body colloid.

  Further, the photocatalyst-coated particles are obtained by coating the surfaces of carbon particles (pigment particles, carbon material particles) with titanium suboxide particles (photocatalyst particles). Lithium particles adhere to the surface of the titanium suboxide particles. That is, titanium suboxide particles with lithium particles adhering to the surface or lithium particles adhering to the surface of the carbon particles, which cover the carbon particles. Note that the degree of adhesion of lithium particles to titanium suboxide particles is not necessarily the same for each titanium suboxide, and in fact, lithium particles cover the entire surface of titanium suboxide particles. It may be coated or partially attached to the surface of titanium suboxide, and the degree of adhesion of lithium particles to the titanium suboxide particles varies depending on the individual titanium suboxide. Yes.

The titanium suboxide in the photocatalyst-coated particles includes, for example, titanium suboxide having a composition of Ti ₂ O _3. The composition of titanium suboxide includes not only Ti ₂ O ₃ but also Ti _X O _Y. Is mentioned. This is the same in the following description of this embodiment.

  The average particle diameter of the photocatalyst-coated particles is, for example, about 20 μm, and the average particle diameter of carbon particles in the photocatalyst-coated particles is, for example, about 20 μm. The particle size is, for example, 5 to 10 nm.

  A method for producing the paint having the above-described configuration will be described. First, an aqueous titanium hydroxide solution and an aqueous solution in which surface-treated carbon and titanium metal are dispersed are mixed and dispersed to produce a mixed dispersion, and the aqueous lithium chloride solution is dropped into the mixed dispersion and stirred for a predetermined time. Leave it later. That is, an aqueous solution containing titanium hydroxide, carbon as pigment particles, titanium metal, and lithium chloride is produced. Thereafter, the mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. In heating, the mixed dispersion is heated while stirring. Thereafter, an aqueous lithium chloride solution is dropped into the mixed dispersion and left to stand after stirring for a predetermined time. Thereafter, the mixed dispersion is dehydrated by drying the mixture in the mixed dispersion by drying the mixture water. Titanium-coated particles are obtained.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere, whereby the titanium dioxide becomes titanium suboxide and the photocatalyst-coated particles are obtained.

  Then, the produced photocatalyst-coated particles are dispersed in water to produce a dispersion, and the dispersion is mixed with a mixed liquid obtained by mixing a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid. By doing so, a paint was obtained.

  The above manufacturing method will be described more specifically as follows. First, 1000 g of aqueous titanium hydroxide (for example, 2% solid content), 5 g of titanium metal (average particle size: 40 μm), and carbon subjected to surface treatment with alcohol or nitric acid (for example, average particle size of 20 μm, specific gravity of 0.3) A mixed dispersion is prepared by mixing and dispersing 1030 g of an aqueous solution in which 25 g is dispersed. That is, in the case of Example 1, an aqueous solution in which carbon is dispersed is used in the production of the mixed dispersion, whereas in this embodiment, an aqueous solution in which metallic titanium and carbon are dispersed is used. The titanium hydroxide aqueous solution can be obtained, for example, by allowing ammonia to act on titanium tetrachloride, and by adding hydrogen peroxide to the titanium hydroxide gel, an amorphous titanium hydroxide sol can be obtained. However, an aqueous solution of this titanium hydroxide sol is used.

  Then, an aqueous lithium chloride solution is dropped into the mixed dispersion and left to stand after stirring for a predetermined time. For example, a lithium chloride aqueous solution is dropped into the mixed dispersion (may be mixed with lithium chloride), and the mixture is allowed to stand after stirring for 3 to 10 minutes (preferably 5 minutes). The lithium chloride aqueous solution is dropped to improve the adhesion between titanium hydroxide and carbon particles. The mixed dispersion in which the lithium chloride aqueous solution is dropped corresponds to the “target aqueous solution”. That is, this mixed dispersion is obtained by mixing “an aqueous solution that is an aqueous solution containing titanium hydroxide, pigment particles and a chloride compound” or “an aqueous solution containing titanium hydroxide and pigment particles and an aqueous solution containing chloride ions. The target aqueous solution which is an aqueous solution. The aqueous lithium chloride solution corresponds to the “aqueous solution containing chlorine ions”, and the lithium chloride corresponds to the “chloride compound”.

  The mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. That is, with the mixed dispersion in the sealed container, the sealed container is evacuated, and the mixed dispersion is heated after irradiating ultrasonic waves from the outside of the sealed container.

  Specifically, using the ultrasonic heating device P as shown in FIG. 1, the mixed dispersion is put into the container 12 and the temperature adjusting agent 30 is put between the sealed container 10 and the container 12. Then, the inside of the sealed container 10 is evacuated, and then ultrasonic waves are irradiated by the ultrasonic vibrator 7 (ultrasonic irradiation process). Then, a plurality (specifically, a large number) of recesses are formed on the surface of the carbon particles by ultrasonic waves.

Then, the mixed dispersion is heated by the heater 14 (heating step). In addition, the heating is performed while stirring the mixed dispersion with the stirrer 16. Then, titanium hydroxide becomes titanium dioxide (strictly, anatase type titanium dioxide) by this heating. In this case, the heating temperature is 70 ° C. to 90 ° C. (preferably 80 ° C.), and the heating time is 15 minutes to 25 minutes (preferably 20 minutes). The degree of vacuum is about 10 ⁻⁴ to 10 ⁻¹⁰ Torr. In addition, at least a part of the titanium dioxide particles are fitted into the recesses formed on the surface of the carbon particles. Moreover, since it heats in the pressure_reduction | reduced_pressure state called a vacuum state, a titanium dioxide particle is easy to be fitted in this recessed part. In the production of the photocatalyst-coated particles, the mixed dispersion is heated in a vacuum state, that is, in an oxygen deficient state, so that the carbon particles are prevented from burning.

  In the above process, the surface of the carbon particles is coated with titanium dioxide, but in actuality, it is not necessarily in a completely coated state. It adheres not only to the surface of carbon particles. In addition, since the recessed part was formed in the surface of the carbon particle by the ultrasonic wave as mentioned above, the lithium particle fits in this recessed part.

  Then, 50 g of titanium dioxide-coated particles could be obtained by draining the mixed water of the mixed dispersion and drying the mixture in the mixed dispersion, that is, the precipitate with a dryer. In this case, the drying temperature is 70 to 90 ° C. (preferably 80 ° C.), and the drying time is 6 to 10 hours (preferably 8 hours). It should be noted that titanium hydroxide is also converted into titanium dioxide even when the mixed dispersion is heated, but it is sufficiently changed to titanium dioxide by heating during the drying. In this way, the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are in a state where the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are obtained by coating the surface of carbon particles with titanium dioxide, and more strictly, lithium particles are attached to the surface of carbon particles or the surface of titanium dioxide particles.

  In this example, since titanium metal is included, the surface of the titanium metal particles is also covered with titanium dioxide. Strictly speaking, lithium particles adhere to the surfaces of the titanium metal particles and the titanium dioxide particles.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere (firing step), whereby the titanium dioxide becomes titanium suboxide and 50 g of the pigment particles can be obtained. The pigment particles are composed of carbon particles coated with titanium suboxide and titanium suboxide particles (that is, titanium dioxide and metal titanium are converted to titanium suboxide by firing the titanium dioxide coated titanium dioxide). Are made up of). Since the pigment particles are basically in a state where the black carbon particles are coated with titanium suboxide, a black pigment can be obtained. The produced pigment can also be referred to as a photocatalyst-coated pigment. In this case, the inert gas is, for example, nitrogen gas or argon gas. The firing temperature is 350 ° C. to 950 ° C., and the firing time is 20 to 110 minutes (preferably 90 minutes). In addition, titanium dioxide changes into titanium suboxide by firing titanium dioxide in an inert gas atmosphere to change titanium dioxide into titanium suboxide, and some of the carbon in the carbon particles is vaporized. By doing so, titanium dioxide changes to titanium suboxide. In other words, in the above example, firing is performed in an inert gas, but titanium dioxide is sub-oxidized due to partial vaporization of carbon in the carbon particles even when firing in a vacuum rather than in an inert gas. Change to titanium. At that position, the firing temperature may be any temperature at which carbon vaporizes. A pigment is produced according to the above-described pigment production process.

  The X-ray analysis of the photocatalyst-coated particles produced above confirmed that the substance covering the carbon particles was titanium suboxide, and the electron microscope showed that the titanium suboxide coated the carbon particle surfaces. It was confirmed that The produced photocatalyst-coated particles have an average particle size of 20 μm.

  In the above description, the mixed dispersion is heated with a heater in a vacuum state and then heated with a heater. However, the mixed dispersion may be heated while being irradiated with an ultrasonic wave in a vacuum state.

  In the above, the mixed dispersion liquid in which the titanium hydroxide aqueous solution and the carbon-dispersed aqueous solution are mixed and dispersed is heated after being irradiated with ultrasonic waves in vacuum. The lithium chloride aqueous solution may be dropped into the mixed dispersion and the subsequent steps may be performed. Alternatively, metallic titanium may be mixed just before firing, and the metallic titanium may be fired to change to titanium suboxide.

  Next, 50 g of the produced pigment particles are dispersed in 100 g of water to produce a dispersion. The dispersion is made up of 30 g of a lithium silicate aqueous solution (solid content 40%) and a titanium hydroxide aqueous solution (solid content 20%) 60 g. And 60 g of silicic acid irregularly shaped body colloid (solid content 20%) were mixed (dispersion manufacturing step) to obtain 300 g of a coating material. This paint is a black paint because the photocatalyst-coated particles as the main component are black pigments. In addition, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are mixed as a binder, so that these binders increase the adhesive strength with the photocatalyst-coated particles, and the coating surface and coating material on which the coating material is applied. It is possible to form a thin film by increasing the adhesive strength.

  In addition, with respect to said manufacturing method, you may manufacture photocatalyst covering particle | grains with the following manufacturing methods. That is, first, a mixed dispersion is prepared by mixing and dispersing a titanium hydroxide aqueous solution and an aqueous solution in which surface-treated carbon and titanium metal are dispersed. Thereafter, the mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. In heating, the mixed dispersion is heated while stirring. Thereafter, an aqueous lithium chloride solution is dropped into the mixed dispersion and left to stand after stirring for a predetermined time. Thereafter, the mixed dispersion is dehydrated by drying the mixture in the mixed dispersion by drying the mixture water. Titanium-coated particles are obtained.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere, whereby the titanium dioxide becomes titanium suboxide and the photocatalyst-coated particles are obtained.

  Then, the produced photocatalyst-coated particles are dispersed in water to produce a dispersion, and the dispersion is mixed with a mixed liquid obtained by mixing a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid. By doing so, a paint was obtained.

  The above manufacturing method will be described more specifically as follows. First, 1000 g of aqueous titanium hydroxide (for example, 2% solid content), 5 g of titanium metal (average particle size: 40 μm), and carbon subjected to surface treatment with alcohol or nitric acid (for example, average particle size of 20 μm, specific gravity of 0.3) A mixed dispersion is prepared by mixing and dispersing 1030 g of an aqueous solution in which 25 g is dispersed. That is, in the case of Example 1, an aqueous solution in which carbon is dispersed is used in the production of the mixed dispersion, whereas in this embodiment, an aqueous solution in which metallic titanium and carbon are dispersed is used. This mixed dispersion corresponds to the target aqueous solution. The titanium hydroxide aqueous solution can be obtained, for example, by allowing ammonia to act on titanium tetrachloride, and further adding hydrogen peroxide to the titanium hydroxide gel to obtain an amorphous titanium hydroxide sol. However, an aqueous solution of this titanium hydroxide sol is used.

  The mixed dispersion is heated after being irradiated with ultrasonic waves in a vacuum state. That is, with the mixed dispersion in the sealed container, the sealed container is evacuated, and the mixed dispersion is heated after irradiating ultrasonic waves from the outside of the sealed container.

  Specifically, an ultrasonic heating device P as shown in FIG. 1 is used. That is, while the mixed dispersion liquid is put into the container 12 and the temperature adjusting agent 30 is put between the sealed container 10 and the container 12, the inside of the sealed container 10 is evacuated. Irradiate ultrasonic waves (ultrasonic irradiation process). Then, a plurality (specifically, a large number) of recesses are formed on the surface of the carbon particles by ultrasonic waves.

Then, the mixed dispersion is heated by the heater 14 (heating step). In addition, the heating is performed while stirring the mixed dispersion with the stirrer 16. Then, titanium hydroxide becomes titanium dioxide (strictly, anatase type titanium dioxide) by this heating. In this case, the heating temperature is 70 ° C. to 90 ° C. (preferably 80 ° C.), and the heating time is 15 minutes to 25 minutes (preferably 20 minutes). The degree of vacuum is about 10 ⁻⁴ to 10 ⁻¹⁰ Torr. In addition, at least a part of the titanium dioxide particles are fitted into the recesses formed on the surface of the carbon particles. Moreover, since it heats in the pressure_reduction | reduced_pressure state called a vacuum state, a titanium dioxide particle is easy to be fitted in this recessed part. In the production of the photocatalyst-coated particles, the mixed dispersion is heated in a vacuum state, that is, in an oxygen deficient state, so that the carbon particles are prevented from burning.

  Thereafter, an aqueous lithium chloride solution is dropped into the mixed dispersion (mixing step), and the mixture is allowed to stand after stirring for a predetermined time. For example, a lithium chloride aqueous solution is dropped into the mixed dispersion (may be mixed with lithium chloride), and the mixture is allowed to stand after stirring for 3 to 10 minutes (preferably 5 minutes). The lithium chloride aqueous solution is dropped to improve the adhesion between titanium dioxide and carbon particles. The lithium chloride aqueous solution corresponds to the “aqueous solution containing a base”, and the lithium chloride corresponds to the chloride compound.

  In the above process, the surface of the carbon particles is coated with titanium dioxide, but in actuality, it is not necessarily in a completely coated state, and the lithium particles are not coated with titanium dioxide. It adheres not only to the surface of carbon but also to the surface of carbon particles. As described above, since the recesses are formed by ultrasonic waves on the surface of the carbon particles, at least some of the lithium particles are fitted into the recesses.

  Then, 50 g of titanium dioxide-coated particles could be obtained by draining the mixed water of the mixed dispersion and drying the mixture in the mixed dispersion, that is, the precipitate with a dryer. In this case, the drying temperature is 70 to 90 ° C. (preferably 80 ° C.), and the drying time is 6 to 10 hours (preferably 8 hours). It should be noted that titanium hydroxide is also converted into titanium dioxide even when the mixed dispersion is heated, but it is sufficiently changed to titanium dioxide by heating during the drying. In this way, the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are in a state where the surface of the carbon particles is coated with titanium dioxide. The titanium dioxide-coated particles are obtained by coating the surface of carbon particles with titanium dioxide, and more strictly, lithium particles are attached to the surface of carbon particles or the surface of titanium dioxide particles.

  In this example, since titanium metal is included, the surface of the titanium metal particles is also covered with titanium dioxide. Strictly speaking, lithium particles adhere to the surfaces of the titanium metal particles and the titanium dioxide particles.

  Thereafter, the titanium dioxide-coated particles are fired in an inert gas atmosphere (firing step), whereby the titanium dioxide becomes titanium suboxide and 50 g of the pigment particles can be obtained. The pigment particles are composed of carbon particles coated with titanium suboxide and titanium suboxide particles (that is, titanium dioxide and metal titanium are converted to titanium suboxide by firing the titanium dioxide coated titanium dioxide). Is made up of). Since the pigment particles are basically in a state where the black carbon particles are coated with titanium suboxide, a black pigment can be obtained. The produced pigment can also be referred to as a photocatalyst-coated pigment. In this case, for example, nitrogen gas or argon gas is used as the inert gas. The firing temperature is 350 ° C. to 950 ° C. (preferably 900 ° C.), and the firing time is 20 to 110 minutes (preferably 90 minutes). As described above, the action of changing titanium dioxide to titanium suboxide is that titanium dioxide is changed to titanium suboxide by firing in an inert gas atmosphere, Titanium dioxide is changed to titanium suboxide by partial vaporization of carbon. In other words, in the above example, firing is performed in an inert gas, but titanium dioxide is sub-oxidized due to partial vaporization of carbon in the carbon particles even when firing in a vacuum rather than in an inert gas. Change to titanium. At that position, the firing temperature may be any temperature at which carbon vaporizes.

  The X-ray analysis of the photocatalyst-coated particles produced above confirmed that the substance covering the carbon particles was titanium suboxide, and the electron microscope showed that the titanium suboxide coated the carbon particle surfaces. It was confirmed that The produced photocatalyst-coated particles have an average particle size of 20 μm.

  In the above description, the mixed dispersion is heated with a heater in a vacuum state and then heated with a heater. However, the mixed dispersion may be heated while being irradiated with an ultrasonic wave in a vacuum state.

  The method of using the coating material of this embodiment will be described. In the coating material of this embodiment, a coating film is formed by coating on the application surface. In the coating material of this example, since the photocatalyst-coated particles are contained, an extremely excellent photocatalytic function can be achieved. In particular, since the photocatalyst-coated particles are coated with titanium suboxide around the black carbon particles, the photocatalyst function by the titanium suboxide can be fully exhibited because it easily absorbs light. Since the particles contain titanium suboxide, the photocatalytic function can be sufficiently exerted even by visible light.

  In addition, according to the coating material of this example, since the photocatalyst-coated particles are attached to the surface of the silicic acid irregularly shaped colloid, the photocatalyst-coated particles can be efficiently irradiated with light, and have a stable photocatalytic function. Therefore, the photocatalytic function can be sufficiently exerted even on a thin coating film.

  Further, in the coating material of this example, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are included, so that the adhesive strength with the photocatalyst-coated particles is increased, and the coating surface and the coating material on which the coating material is applied The adhesion strength of the film can be increased to form a thin film.

  Moreover, according to the photocatalyst-coated particles of this example, it can be used as a pigment in addition to the case of using as a raw material for a paint as described above, and even in that case, an extremely excellent photocatalytic function can be achieved.

  In addition, since the photocatalyst-coated particles and the photocatalyst-coated particles in the paint of this example contain lithium particles, the effects of the presence of the lithium particles, for example, the electrical characteristics (for example, the electronic properties of the lithium particles) Movement promotion function). That is, for example, when this pigment is used as an electrode paint of a solar battery, an electron movement promoting function and a power storage function can be obtained by the lithium particles.

  In this example, titanium titanium is added in the production of the photocatalyst-coated particles, so that not only titanium suboxide-coated carbon particles but also titanium suboxide particles can be mixed in the pigment. The photocatalytic function can be further enhanced.

  In the above description, carbon is used in the production of the photocatalyst-coated particles, and the surface of the carbon particles is coated with titanium suboxide. However, carbon or activated carbon may be used instead of carbon. When carbon is used, the surface of the carbon particles is coated with titanium suboxide, and when activated carbon is used, the surface of the activated carbon particles is coated with titanium suboxide.

  In addition, in the said Example 1 and Example 2, although demonstrated as performing ultrasonic irradiation and a heating in a vacuum state, it is good also as performing ultrasonic irradiation and a heating in the pressure reduction state below atmospheric pressure.

  Further, in Example 1 and Example 2, an aqueous lithium chloride solution is dropped, but an aqueous solution containing a base may be used as another aqueous solution, and another chloride compound may be used instead of lithium chloride. Also good. That is, if it is the aqueous solution and chloride compound containing a base, titanium hydroxide (or titanium dioxide) and a pigment particle can be drawn near, and these adhesiveness can be improved.

  Moreover, in the said Example 1 and Example 2, although the lithium chloride aqueous solution is dripped, you may abbreviate | omit this.

  Next, Example 3 will be described. The paint of Example 3 is a black paint similar to Example 1 or Example 2 above, in which the surface of black particles is coated with a photocatalytic substance, but the surface of activated carbon particles is rutile titanium dioxide. The main difference is that it is coated.

  That is, the coating material of Example 3 is mainly composed of photocatalyst-coated particles in which the surface of activated carbon particles is coated with rutile titanium dioxide particles. In addition, as will be described later, in the manufacturing process of the photocatalyst-coated particles, heating is performed after irradiating ultrasonic waves, so that a plurality of (specifically, many) recesses are formed on the surface of the carbon particles, and the rutile titanium dioxide Some particles are fitted into the recess.

  In the coating material of this example, the photocatalyst-coated particles are dispersed in a mixed solution of a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid aqueous solution (colloidal solution). . Thereby, since the silicic acid irregular-shaped body colloid is exhibiting the shape where the colloidal particle | grains were connected to the net shape, the photocatalyst covering particle | grains and the lithium silicate particle are in the state which adhered to this silicic acid irregular-shaped body colloid.

  The photocatalyst-coated particles are obtained by coating the surfaces of activated carbon particles (pigment particles, carbon material particles) with rutile titanium dioxide particles. As will be described later, this rutile-type titanium dioxide is produced by adding an alkaline aqueous solution to titanium hydroxide gel and heating it at a low pressure, and exhibits a photocatalytic function sufficiently even with visible light.

The titanium suboxide in the photocatalyst-coated particles includes, for example, titanium suboxide having a composition of Ti ₂ O _3. The composition of titanium suboxide includes not only Ti ₂ O ₃ but also Ti _X O _Y. Is mentioned. This is the same in the following description of this embodiment.

  The average particle diameter of the photocatalyst-coated particles is, for example, about 20 μm, and the average particle diameter of activated carbon particles in the photocatalyst-coated particles is, for example, about 20 μm. The average particle diameter is, for example, 5 to 10 nm.

  A method for producing the paint having the above-described configuration will be described. First, activated carbon particles are dispersed in a titanium tetrachloride aqueous solution, and then ammonia water is dropped to form and precipitate a titanium hydroxide gel. Then, after removing the upper water and adding ammonia water to the titanium hydroxide gel, heating is performed after irradiation with ultrasonic waves in a vacuum state. In heating, the mixed dispersion is heated while stirring. As a result, photocatalyst-coated particles in which the activated carbon surface is coated with rutile-type titanium dioxide are obtained.

  Then, the produced photocatalyst-coated particles are dispersed in water to produce a dispersion, and the dispersion is mixed with a mixed liquid obtained by mixing a lithium silicate aqueous solution, a titanium hydroxide aqueous solution, and a silicic acid irregularly shaped colloid. By doing so, a paint was obtained.

  The above manufacturing method will be described more specifically as follows. First, ammonia hydroxide is dropped into a dispersion in which activated carbon particles (for example, average particle size 20 μm) are dispersed in an aqueous titanium tetrachloride solution (for example, 45% solid content) to form and precipitate titanium hydroxide gel (titanium hydroxide gel generation step). ). Then, when the dispersion water is drained and ammonia water (alkaline aqueous solution) is added to the precipitated titanium hydroxide gel and activated carbon particles, the titanium hydroxide gel becomes a titanium hydroxide sol. Then, a solution obtained by diluting the titanium hydroxide sol and the activated carbon particles is heated after being irradiated with ultrasonic waves in a vacuum state. That is, in a state where the solution is placed in a sealed container, the inside of the sealed container is evacuated, and the solution is heated after being irradiated with ultrasonic waves from the outside of the sealed container.

  Specifically, using the ultrasonic heating device P as shown in FIG. 1, the container 12 contains the above solution (that is, a solution obtained by diluting titanium hydroxide sol and activated carbon particles) and is sealed. The inside of the sealed container 10 is evacuated with the temperature adjusting agent 30 between the container 10 and the container 12, and then ultrasonic waves are irradiated by the ultrasonic vibrator 7 (ultrasonic irradiation process). Then, a plurality (specifically, a large number) of concave portions are formed on the surface of the activated carbon particles by ultrasonic waves.

Then, the solution is heated by the heater 14 (heating step). In addition, the heating is performed while stirring the solution with the stirrer 16. In this case, the heating temperature is 90 ° C. to 110 ° C. (preferably 100 ° C.), and the heating time is 20 minutes to 40 minutes (preferably 30 minutes). The degree of vacuum is about 10 ⁻⁴ to 10 ⁻¹⁰ Torr. As a result, the titanium hydroxide sol becomes rutile titanium dioxide, and 50 g of photocatalyst-coated particles in a state where the surface of the activated carbon particles is coated with rutile titanium dioxide is obtained. Since the photocatalyst-coated particles are in a state where the surface of the activated carbon particles is coated with rutile-type titanium dioxide, a black pigment can be obtained. That is, a pigment is manufactured according to the above pigment manufacturing process.

  As described above, since the titanium hydroxide sol obtained by adding ammonia water to the titanium hydroxide gel is heated at a low pressure (that is, in a vacuum state), not anatase titanium dioxide but rutile titanium dioxide is generated. That is, when the titanium hydroxide gel is heated as it is, it becomes anatase type titanium dioxide, but in this example, the titanium hydroxide gel is heated at a low pressure on the alkali side by adding an alkaline aqueous solution, so the titanium hydroxide gel is a rutile type. Titanium dioxide. Thus, the activated carbon particles are coated with rutile titanium dioxide that exhibits a sufficient photocatalytic function even with visible light. In addition, at least a part of the rutile titanium dioxide particles will be fitted into the recesses formed on the surface of the carbon particles. Moreover, since it heats in the pressure_reduction | reduced_pressure state called a vacuum state, a titanium dioxide particle is easy to be fitted in this recessed part. In the production of the photocatalyst-coated particles, the solution is heated in a vacuum state, that is, in an oxygen deficient state, in order to prevent the activated carbon particles from burning.

  In addition, when the substance coat | covered on the surface of activated carbon particle was X-ray-analyzed, it became clear that the titanium oxide adhering to the surface of activated carbon particle was a rutile type titanium dioxide. Further, when the produced photocatalyst-coated particles are observed with an electron microscope, rutile-type titanium dioxide (average particle size of 5 to 10 nm) adheres to the surfaces of the activated carbon particles, and particularly the rutile is formed in the recesses formed on the surfaces of the activated carbon particles. It was confirmed that the particles of type titanium dioxide were fitted.

  Next, 50 g of the produced photocatalyst-coated particles are dispersed in 100 g of water to produce a dispersion, and the dispersion is made up of 30 g of a lithium silicate aqueous solution (solid content 40%) and a titanium hydroxide aqueous solution (solid content 20%). 60 g and 60 g of silicic acid irregular-shaped body colloid (solid content 20%) were mixed (mixed liquid production process) to obtain 250 g of paint. This paint is a black paint because the photocatalyst-coated particles as the main component are black pigments. In addition, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are mixed as a binder, so that these binders increase the adhesive strength with the photocatalyst-coated particles, and the coating surface and coating material on which the coating material is applied. It is possible to form a thin film by increasing the adhesive strength.

  The method of using the coating material of this embodiment will be described. In the coating material of this embodiment, a coating film is formed by coating on the application surface. In the coating material of this example, since the photocatalyst-coated particles are contained, an extremely excellent photocatalytic function can be achieved. In particular, since the photocatalyst-coated particles are in a state where the rutile titanium dioxide is coated around the black activated carbon particles, the photocatalytic function of the rutile titanium dioxide can be sufficiently exerted easily by absorbing light. Since the photocatalyst-coated particles contain rutile titanium dioxide, the photocatalytic function can be sufficiently exerted even by visible light.

  In addition, according to the coating material of this example, since the photocatalyst-coated particles are attached to the surface of the silicic acid irregularly shaped colloid, the photocatalyst-coated particles can be efficiently irradiated with light, and have a stable photocatalytic function. Therefore, the photocatalytic function can be sufficiently exerted even on a thin coating film.

  Further, in the coating material of this example, lithium silicate, titanium hydroxide, and silicic acid irregularly shaped colloid are included, so that the adhesive strength with the photocatalyst-coated particles is increased, and the coating surface and the coating material on which the coating material is applied The adhesion strength of the film can be increased to form a thin film.

  Moreover, according to the photocatalyst-coated particles of this example, it can be used as a pigment in addition to the case of using as a raw material for a paint as described above, and even in that case, an extremely excellent photocatalytic function can be achieved.

  In the above description, activated carbon is used in the production of the photocatalyst-coated particles, and the surface of the activated carbon particles is coated with rutile titanium dioxide. However, carbon or carbon may be used instead of activated carbon. When carbon is used, the surface of the carbon particles is coated with rutile titanium dioxide, and when carbon is used, the surface of the carbon particles is coated with rutile titanium dioxide.

  In Example 3, ultrasonic wave irradiation and heating may be performed in a vacuum state after a lithium chloride aqueous solution is dropped into a solution obtained by adding ammonia water to titanium hydroxide gel. By doing in this way, it becomes possible to improve a photocatalytic function because lithium particles adhere to the surface of activated carbon particles or the surface of rutile titanium dioxide.

  In each of the above embodiments, carbon material particles such as carbon particles, carbon particles, and activated carbon particles have been described as examples of pigment particles. However, the present invention is not limited to carbon material particles, and may be other pigment particles.

It is explanatory drawing which shows the structure of the ultrasonic heating apparatus used for the manufacturing method of the pigment of this invention.

Explanation of symbols

P Ultrasonic heating device 7 Ultrasonic vibrator 10 Sealed container 14 Heater

Claims (30)

A pigment,
With photocatalyst-coated particles,
Pigment particles, the surface of which is provided with concave portions by ultrasonic irradiation; and pigment particles;
A photocatalyst-coated particle having a photocatalyst particle coated on the surface of the pigment particle. The pigment according to claim 1, wherein the pigment further has lithium attached to the pigment particles and / or the photocatalyst particles. The pigment according to claim 1 or 2, wherein the pigment particles are carbon material particles that are particles composed of a carbon material. A pigment,
With photocatalyst-coated particles,
Carbon material particles that are particles composed of carbon material;
Photocatalyst particles coated on the surface of the carbon material particles;
A pigment characterized by comprising photocatalyst-coated particles having carbon material particles and / or lithium attached to the photocatalyst particles. The pigment according to claim 4, wherein a concave portion is formed on the surface of the carbon material particles by ultrasonic irradiation. The pigment is heated to an aqueous solution having titanium hydroxide, a carbon material, and lithium chloride at a pressure of subatmospheric pressure, followed by heating, and then drying the precipitate, The pigment according to claim 4 or 5, wherein the pigment is produced by firing in an inert gas atmosphere or in a vacuum state. The pigment according to claim 3, 4, 5, or 6, wherein the carbon material particles are at least one of carbon particles, carbon particles, and activated carbon particles. The pigment according to claim 1, 2, 3, 4, 5, 6, or 7, wherein the photocatalyst particles are titanium suboxide. The said pigment further has a titanium suboxide particle | grain formed by baking a metal titanium particle in inert gas atmosphere, The 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 characterized by the above-mentioned. Pigments. The photocatalyst particles are rutile titanium dioxide produced by heating a solution obtained by mixing titanium hydroxide and an alkaline aqueous solution in a pressure state equal to or lower than atmospheric pressure. Or 5 or 6 or 7 or 8 or 9. Paint,
A pigment according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10;
A colloidal solution;
A paint characterized by comprising: 12. The coating material according to claim 11, wherein the colloidal solution is a solution having a silicic acid irregular shape colloid. The paint according to claim 11 or 12, wherein the paint further comprises at least one of lithium silicate and titanium hydroxide. A method for producing a pigment, comprising:
For a target aqueous solution that is an aqueous solution containing titanium hydroxide, pigment particles, and a chloride compound, or a target aqueous solution that is an aqueous solution obtained by mixing an aqueous solution containing titanium hydroxide and pigment particles and an aqueous solution containing chlorine ions , An ultrasonic irradiation step of irradiating ultrasonic waves in a pressure state below atmospheric pressure;
A heating step of changing at least a part of titanium hydroxide into titanium dioxide by heating the target aqueous solution irradiated with ultrasonic waves in the ultrasonic irradiation step;
A baking step of changing the titanium dioxide into titanium suboxide by baking the precipitate generated in the heating step in an inert gas atmosphere;
A method for producing a pigment, comprising: A method for producing a pigment, comprising:
An ultrasonic irradiation step of irradiating the target aqueous solution, which is an aqueous solution having titanium hydroxide and pigment particles, with ultrasonic waves in a pressure state of atmospheric pressure or lower;
A heating step of changing at least a part of titanium hydroxide into titanium dioxide by heating the target aqueous solution irradiated with ultrasonic waves in the ultrasonic irradiation step;
A mixing step of mixing the aqueous solution heated in the heating step with an aqueous solution or chloride compound containing chlorine ions;
A baking step of changing titanium dioxide into titanium suboxide by baking the precipitate in the aqueous solution produced in the mixing step in an inert gas atmosphere;
A method for producing a pigment, comprising: The method for producing a pigment according to claim 14 or 15, wherein the chloride compound is lithium chloride, and the aqueous solution containing chlorine ions is an aqueous lithium chloride solution. A method for producing a pigment, comprising:
An ultrasonic irradiation step of irradiating the target aqueous solution, which is an aqueous solution having titanium hydroxide and pigment particles, with ultrasonic waves in a pressure state of atmospheric pressure or lower;
A heating step of changing at least a part of titanium hydroxide into titanium dioxide by heating the target aqueous solution irradiated with ultrasonic waves in the ultrasonic irradiation step;
A baking step of changing titanium dioxide into titanium suboxide by baking the precipitate in the aqueous solution produced in the heating step in an inert gas atmosphere;
A method for producing a pigment, comprising: The method for producing a pigment according to claim 14, 15, 16, or 17, wherein the target aqueous solution further contains titanium metal. The method for producing a pigment according to claim 14, 15, 16, 17, or 18, wherein metallic titanium is added before the firing step. A drying step for drying the precipitate to be fired is provided immediately before the firing step, and in the firing step, the precipitate dried in the drying step is fired in an inert gas atmosphere. Item 14. The method for producing a pigment according to Item 14 or 15 or 16 or 17 or 18 or 19. A method for producing a pigment, comprising:
A method for producing a pigment, comprising a heating step of changing a titanium hydroxide to rutile type titanium dioxide by heating a mixed solution of pigment particles, titanium hydroxide and an alkaline aqueous solution. A method for producing a pigment, comprising:
A titanium hydroxide gel production step of producing a titanium hydroxide gel by mixing titanium tetrachloride aqueous solution, pigment particles and ammonia, and reacting titanium tetrachloride with ammonia;
An ultrasonic irradiation step of irradiating the target solution, which is a solution obtained by adding an aqueous alkali solution to the generated titanium hydroxide gel and pigment particles, under a pressure state of atmospheric pressure or lower,
Heating the target solution to produce photocatalyst-coated particles in which the surface of the pigment particles is coated with rutile-type titanium dioxide; and
A method for producing a pigment, comprising: The method for producing a pigment according to claim 21 or 22, wherein the alkaline aqueous solution is ammonia water. The method for producing a pigment according to claim 14, 15 or 16, or 17 or 18 or 19 or 20, wherein the pigment particles are carbon material particles which are particles composed of a carbon material. 24. The method for producing a pigment according to claim 21, 22 or 23, wherein the pigment particles are carbon material particles which are particles composed of a carbon material. The method for producing a pigment according to claim 24 or 25, wherein the carbon material particles are at least one of carbon particles, carbon particles, and activated carbon particles. The method for producing a pigment according to claim 24, wherein, in the baking step, baking is performed in a vacuum state instead of an inert gas. A method of manufacturing a paint,
A pigment production process for producing a pigment by the method for producing a pigment according to claim 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27;
A dispersion production process for producing a solution in which a colloidal solution and the pigment produced by the pigment production process are dispersed in water;
The manufacturing method of the coating material characterized by having. The method for producing a coating material according to claim 28, wherein the colloidal solution is a solution having a silicic acid irregularly shaped body colloid. 30. The method for producing a paint according to claim 28 or 29, wherein in the dispersion producing step, at least one of lithium silicate and titanium hydroxide is mixed.

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