JP2001200627A - Tile having photocatalyst function and manufacturing method for the tile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tile excellent in a deodorizing function, an antibacterial (germicidal) function, and an antifouling function. SOLUTION: A binder layer 2 made of material having a softening temperature lower than the softening temperature of a base material is formed on the base material 1, and subsequently, a photocatalyst layer 3 made by photocatalyst particles is formed on the binder layer 2. The layers are heat in atmospheric temperature higher that the softening temperature of the binder layer within the range from 30C deg.C to 300 deg.C and also lower than the softening temperature of the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing function,
The present invention relates to a tile exhibiting functions such as a fungus function and an antifouling function, and a method for producing the tile.

[0002]

By irradiating the Related Art UV, to cause adsorption or desorption of oxygen molecules with respect to organic compounds such as malodorous components, as a substance that serves the function of promoting the decomposition (oxidation), TiO _2, V ₂ O ₅ , ZnO, WO _{3 and the} like are known,
In particular, TiO ₂ particles having an anatase crystal form have a high effect as a photocatalyst. Therefore, it has been proposed to form a photocatalyst layer on the surface of a wall material, a tile, a glass (mirror), a circulating filtration device, a sanitary ware, or the like. I have.

As a method for forming the photocatalyst layer, the following method has been conventionally used. On the surface of base material such as plastic, ceramic, resin, etc.
A method in which a photocatalytic layer composed of TiO ₂ particles or the like is directly formed by a VD method, a sputtering method, an electron beam evaporation method, or the like. Photocatalyst particles are kneaded with a binder and applied to the substrate surface by spray coating, etc.
A method of performing heat treatment after dip coating by a coating method (JP-A-5-201747).

[0004]

When the CVD method, the sputtering method, the electron beam evaporation method, or the like is used, the equipment becomes large-scale and the yield is poor, so that the manufacturing cost increases.

On the other hand, in order for the photocatalyst particles such as TiO ₂ particles to exhibit the effect as a photocatalyst, it is necessary to irradiate the photocatalyst particles with ultraviolet rays and to contact the photocatalyst particles with a substance to be decomposed such as an odorous gas. Japanese Patent Application Laid-Open No. 5-2017
If the photocatalyst particles were kneaded with a binder and applied to a substrate as in JP-B-47, many photocatalyst particles would be buried in the binder layer, and would not reach ultraviolet rays or come in contact with odorous gas. , Cannot exhibit a sufficient catalytic function.

[0006]

Means for Solving the Problems In order to solve the above problems, the present invention has the following means.

In a tile having a photocatalytic function in which a photocatalyst layer is held on a base material surface via a binder layer, an upper layer of the photocatalyst layer is exposed from the binder layer so as to be in contact with the outside air, and a lower layer of the photocatalyst layer. Was buried partially in the binder layer. With this configuration, the upper layer of the photocatalyst layer is exposed, so that the catalytic function can be sufficiently exhibited. The lower layer of the photocatalyst layer is partially embedded in the binder layer, so that the photocatalyst layer is partially buried in the binder layer. Particles are less likely to peel from the substrate.

Here, a tile is used as the base material.

The photocatalyst particles include TiO ₂ , Zn
O, SrTiO ₃ , Fe ₂ O ₃ , CdS, CdSe, WO ₃ , Fe
TiO ₃ , GaP, GaAs, RuO ₂ , MoS ₃ , LaRhO ₃ ,
CdFeO ₃ , Bi ₂ O ₃ , MoS ₂ , In ₂ O ₃ , CdO, SnO ₂
And any of these may be used.
Incidentally, TiO ₂ , SrTiO ₃ , Fe ₂ O ₃ , CdS, WO ₃ , Mo
For S ₃ , Bi ₂ O ₃ , MoS ₂ , In ₂ O ₃ , CdO, etc., since the absolute value of the redox potential in the equivalent electronic band is larger than the absolute value of the redox potential in the conduction band, the oxidizing power is more than the reducing power. It is also excellent in deodorant action, antifouling action and antibacterial action due to decomposition of organic compounds. TiO ₂ , Fe ₂ O ₃ and ZnO are advantageous in terms of raw material cost.

Further, the binder layer may be made of, for example, a glaze,
It is made of a thermoplastic material such as inorganic glass, thermoplastic resin, and solder. By configuring the binder layer with a thermoplastic material in this manner, a photocatalyst can be applied on the binder layer at a normal temperature by a simple and inexpensive method such as a spray coating method. And the photocatalyst can be firmly bonded, which is advantageous in the production cost.

The tile having a photocatalytic function according to the present invention is constituted by laminating a photocatalyst layer composed of photocatalyst particles on a sheet-like binder layer composed of a thermoplastic material or embedding a part thereof. By heating such a sheet-shaped multifunctional material after attaching it on an existing tile, it is possible to add functions such as deodorant, antifouling, antibacterial and antifungal properties to the existing tile later. Can be.

The average particle size of the photocatalyst particles constituting the photocatalyst layer is preferably less than 0.3 μm in order to increase the specific surface area and enhance the photocatalytic activity.

Further, in order to enhance the abrasion resistance of the photocatalyst layer,
It is preferable that the photocatalyst particles constituting a portion of the photocatalyst layer exposed from the binder layer are bonded to each other.

The photocatalyst layer has a thickness of 0.1 μm to 0.9 μm.
μm is preferred. If the thickness is less than 0.1 μm, the photocatalyst particles are locally embedded in the binder layer, and a portion where the catalytic activity cannot be exerted on the surface of the multifunctional material occurs. I do. On the other hand, when the thickness exceeds 0.9 μm, the thickness varies greatly, and it becomes difficult to remove stains when stains adhere to the sample. Here, the thickness of the photocatalyst layer is a thickness including the portion from the outermost surface to the portion embedded in the lower layer of the binder layer, and the thickness of each unevenness.

Here, a design effect can be obtained by changing the thickness of the photocatalyst layer. That is, when the thickness is set to 0.2 μm or more and less than 0.4 μm, an iris pattern can be formed by the interference of light with respect to the photocatalyst layer film thickness portion. Alternatively, if only the combination thereof is desired, the portion that causes the light interference action is excluded from 0.1 μm or more and less than 0.2 μm or 0.4 μm.
The thickness of the photocatalyst layer should be less than 1 μm. Such an approach is applicable to tiles.

As a method of bonding the photocatalyst particles constituting the portion of the photocatalyst layer exposed from the binder layer, for example, the gap between the photocatalyst particles is filled with particles having a smaller particle size than the gap. In the case where the photocatalyst particles are bonded to each other only by the photocatalyst particles, there is no alternative but to adsorption or sintering of the photocatalyst particles. However, when utilizing the sintering action between photocatalyst particles, sintering must be carried out at a considerably high temperature. On the other hand, in the case of adsorption, if the specific surface area of the photocatalyst particles is made very large and the packing property is not improved, the binding property will be high. In order to produce a multifunctional material having sufficient catalytic activity and abrasion resistance, for example, the method consumes only the active site adsorption amount of the photocatalyst particles. Further, if particles larger than the gap between the photocatalyst particles are used to strengthen the bond between the photocatalyst particles, not only a sufficient bonding force cannot be obtained, but also the photocatalyst particles exposed on the surface of the multifunctional material are partially covered. As a result, there is a portion on the surface of the multifunctional material where no catalytic activity can be exerted, and bacteria remain in that portion, so that the antibacterial property is significantly deteriorated. Here, the gap between the photocatalyst particles means the photocatalyst particles 3b and 3b as shown in FIG.
3b and both pores between the photocatalyst particles 3b, 3b as shown in FIG. 3 (b). Therefore, the particles 3c having a particle size smaller than the gap between the photocatalyst particles referred to here are particles smaller than any gap between the neck portion between the photocatalyst particles and the pores between the photocatalyst particles.

The material of the small particles to be filled in the gaps between the photocatalyst particles is not basically limited, but those having excellent adsorption power are preferable. An extremely weak material cannot achieve the purpose of binding the photocatalyst particles to each other, and a material having an extremely strong adsorption capability covers the active points on the surface of the photocatalyst particle rather than being inserted into a gap. This is because the probability increases. From this viewpoint, the preferable material of the particles filled in the gap between the photocatalyst particles is Sn, Ti, Ag, Cu, Zn, Fe, Pt, Ct.
Metals or oxides such as o, Pd, Ni, etc., and zeolite, activated carbon, clay and the like conventionally used as an adsorption carrier are not preferred. Of the above metals or oxides, tin oxide is preferable in that it has an appropriate adsorption capacity,
In addition, metals or oxides such as Ag and Cu have unique antibacterial properties and deodorant properties in addition to binding the photocatalyst particles to each other. Therefore, the action of the photocatalyst especially in the absence of light irradiation in applications utilizing this function. It is preferable in that it also has a function of assisting.

It is preferable that the average particle size of the particles filled in the gaps between the photocatalyst particles is 4/5 or less of the average particle size of the photocatalyst particles. Particles filling the gaps between the photocatalyst particles adhere to not only the gaps between the photocatalyst particles but also onto the photocatalyst particles to some extent in the current manufacturing method. The particle size of the particles filling the gap is 4 / the average particle size of the photocatalyst particles.
If it exceeds 5, the probability of adhering to the surface of the photocatalyst particles is higher than the gap between the photocatalyst particles, and the bonding strength between the photocatalyst particles decreases. Also, if the particles filling the gap are larger than the photocatalyst particles, they will partially cover the photocatalyst particles, and there will be a part on the surface of the multifunctional material that cannot exhibit catalytic activity, so that bacteria can stay in that part. Therefore, the antibacterial property may be significantly deteriorated.

The average particle diameter of the particles filled in the gaps between the photocatalyst particles is less than 0.008 μm.
It is preferable because the specific surface area is increased and an appropriate adsorption force can be obtained.

The amount of the particles filled in the gaps between the photocatalyst particles with respect to the photocatalyst particles is 10% or more and 6% or more in terms of molar ratio.
It is preferably 0% or less. When fixing the photocatalyst layer via a binder to the base material by heat treatment in a temperature range where sintering of the photocatalyst particles does not occur, if the amount of particles filling the gap is too small, the photocatalyst particles do not strongly bind to each other, On the other hand, if the amount of particles that fill the gap is too large, the amount of particles covering the photocatalyst particles will increase, and a portion that cannot exhibit catalytic activity on the surface of the multifunctional material will occur, and bacteria will be able to stay in that portion, Particularly, the above range is preferable because the antibacterial property is significantly deteriorated.

Further, as the substance constituting the particles to be filled in the gaps between the photocatalyst particles, a substance having a vapor pressure higher than the vapor pressure of the substance constituting the photocatalyst particles is selected and filled in the gap between the photocatalyst particles. Preferably, the particles are aggregated at the neck between the photocatalyst particles. This is because, in order to obtain a stronger bond between the photocatalyst particles and increase the peel strength of the photocatalyst layer, it is better not only to fill but also to sinter. Further, if such a substance having a high vapor pressure is selected as the particles for filling the gap, it functions as a sintering aid and can lower the sintering temperature. Examples of such a substance having a high vapor pressure include tin oxide, bismuth oxide, and zinc oxide, and tin oxide is preferable in terms of safety.

The thickness of the layer containing the particles filled in the gaps between the photocatalyst particles is preferably 0.1 μm or more. If the thickness of this layer is less than 0.1 μm, photocatalyst particles (and particles that fill gaps depending on the manufacturing method) are locally embedded in the binder layer, resulting in a portion where the catalytic activity cannot be exhibited on the surface of the multifunctional material. Since bacteria can be retained in the portion, the antibacterial property is particularly remarkably deteriorated.
Here, the thickness of the layer containing the particles to be filled in the gaps between the photocatalyst particles includes the portion from the outermost surface to the portion embedded in the lower layer of the binder, and is a uniform thickness of each of the irregularities.

Here, a design effect can be obtained by changing the thickness of the photocatalyst layer. That is, when the thickness is set to 0.2 μm or more and less than 0.4 μm, an iris pattern can be provided by the interference effect of light on the photocatalytic layer film thickness portion. Also, if there is no coloring by the particles that fill the gaps, if the appearance only needs to be the ground color of the base material, the pattern, or the combination thereof, the portion that causes the above-described light interference is excluded.
The thickness of the photocatalyst layer may be formed to be not less than m and less than 0.2 μm or not less than 0.4 μm and less than 1 μm. Such an approach is
Applicable to tiles.

The depth of burying the photocatalyst particles constituting the lowermost layer of the photocatalyst layer in the binder layer is １ ／ of the particle size.
As described above, it is preferable that the photocatalyst particles are embedded in the binder layer by a thickness less than the thickness of the layer including the particles that fill the gap. By embedding the photocatalyst particles in the binder layer in a size of at least 1/2 of the particle size, the lowermost layer of the photocatalyst particle layer and the binder layer are firmly bonded to each other, and the thickness of the layer containing the particles that fills the gap with the photocatalyst particles is larger than the thickness of the layer. If buried, the photocatalyst particles will not be exposed on the outermost surface, which will not be able to exhibit catalytic activity on the surface of the multifunctional material. Becomes significantly worse.

Further, the base material can be used for a tile used as an artificial waterfall or a fountain stone in a water circulation system in a park or a department store. By using a tile having a photocatalytic function for such an application, it is possible to decompose organic waste deposited in water using light including artificial lighting and natural light ultraviolet rays with circulation. In addition, it is possible to prevent breeding of bacteria, molds and the like, generation of algae, and accompanying water odor, thereby creating a cleaner environment.

The tile having a photocatalytic function according to the present invention is used as a device for preventing bacterial infection in hospitals, but can be used as an antifungal and antiviral device because other organic substances can be decomposed.

Further, according to the method for producing a tile having a photocatalytic function according to the present invention, a binder layer made of a thermoplastic material is formed on a substrate made of ceramic, resin, metal, or the like.
Next, a photocatalyst layer made of photocatalyst particles is formed on the binder layer. Thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then solidified. Here, if the viscosity of the binder layer is too high, the binder layer and the photocatalyst particles do not bond sufficiently. Conversely, if the viscosity is too low, the photocatalyst particles are buried in the binder layer. The degree of softening of the binder layer is determined in consideration of these factors, since the antibacterial properties are significantly deteriorated due to the stagnation.

Another method for manufacturing a tile having a photocatalytic function according to the present invention is to form a photocatalyst layer made of photocatalyst particles on a sheet-shaped binder layer made of a thermoplastic material, and to form the sheet-shaped binder layer on a ceramic. After that, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then solidified. According to this method, existing tiles, sanitary ware, building materials, etc. are later deodorized,
Functions such as antifouling property, antibacterial property and antifungal property can be added.

Further, another method of manufacturing a tile having a photocatalytic function according to the present invention provides a photocatalytic function in which the gap between the photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A method for producing a tile having a binder layer made of a thermoplastic material on a substrate made of ceramic, resin, metal, or the like, and then forming photocatalyst particles and the particles on the binder layer. A photocatalyst layer is formed by applying a mixture of small particles in a sol or precursor state to form a photocatalyst layer.After that, the binder layer is softened and a part of the lower layer of the photocatalyst layer is embedded in the binder layer. Solidify. According to this method,
It is simple, and the mixture of the particles that fill the gap and the photocatalyst particles in a sol or precursor state is applied to form a photocatalyst layer, so that the mixing ratio of the photocatalyst particles and the particles that fill the gap can be controlled. It is convenient.

In another method for producing a tile having a photocatalytic function according to the present invention, the gap between the photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. It is a method of producing a tile having, this method, on a sheet-like binder layer made of a thermoplastic material, apply a mixture of photocatalyst particles and the small particles of the particle size mixed in a sol or precursor state. To form a photocatalyst layer, a sheet-like binder layer on which the photocatalyst layer is formed is placed or adhered on a substrate made of ceramic, resin, metal, or the like, and thereafter, the binder layer is softened to form a photocatalyst layer. Part of the lower layer is embedded in the binder layer and then solidified.

Further, another method of manufacturing a tile having a photocatalytic function according to the present invention provides a photocatalytic function in which a gap between photocatalyst particles is filled with particles having a smaller particle size than the gap and the photocatalyst particles are bonded to each other. A method for producing a tile having a binder, comprising: forming a binder layer made of a thermoplastic material on a substrate made of ceramic, resin, metal, or the like; and then forming a photocatalyst comprising photocatalyst particles on the binder layer. A layer is formed, and thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified. The particles having the small particle diameter are fixed to the photocatalyst particles by coating and heat treatment. This method can be carried out relatively easily when the particles filling the gaps are oxides, and can make a large amount of particles filling the gaps when a relatively porous photocatalytic layer is formed. .

Further, another method for producing a tile having a photocatalytic function according to the present invention provides a photocatalytic function in which the gap between the photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. It is a method of manufacturing a tile having, the method comprises forming a photocatalyst layer made of photocatalyst particles on a sheet-shaped binder layer made of a thermoplastic material, and then forming the sheet-shaped binder layer formed with the photocatalyst layer on a ceramic, It is placed or adhered on a resin or metal substrate, and then the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified. A solution containing the small particles is applied to the layer, and the solution is heat-treated to fix the small particles to the photocatalyst particles.

Further, another method for manufacturing a tile having a photocatalytic function according to the present invention is directed to a photocatalytic function in which metal particles having a smaller particle size than the gap are filled in the gaps between the photocatalyst particles and the photocatalyst particles are bonded to each other. This method comprises forming a binder layer made of a thermoplastic material on a substrate made of ceramic, resin, metal, or the like, and then forming photocatalyst particles on the binder layer. After forming a photocatalyst layer, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified. A tile having a photocatalytic function, wherein a tile containing a photocatalyst is applied by applying a solution containing, followed by irradiation with light containing ultraviolet rays to reduce metal ions and immobilize the metal ions on the photocatalyst particles. Manufacturing method. This method can be carried out relatively easily when the particles filling the gap are metal, and can fix the metal in a very short time (several minutes). Further, a lamp used for ultraviolet irradiation may be any of an ultraviolet lamp, a BLB lamp, a xenon mercury lamp, and a fluorescent lamp.

Another method for producing a tile having a photocatalytic function according to the present invention is a photocatalytic function in which metal particles having a smaller particle size than the gap are filled in the gaps between the photocatalyst particles and the photocatalyst particles are bonded to each other. This is a method for producing a tile having a photocatalyst layer formed of photocatalyst particles on a sheet-shaped binder layer made of a thermoplastic material, and then the sheet-shaped binder layer formed with the photocatalyst layer is formed of ceramic. Placed or adhered on a substrate such as resin or metal, after this, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified. A solution containing the ions of the metal particles having the small particle diameter is applied to the photocatalyst layer, and then irradiated with light including ultraviolet rays to reduce the metal ions and immobilize the metal ions on the photocatalyst particles. .

Another method for producing a tile having a photocatalytic function according to the present invention is a photocatalytic function in which metal particles having a smaller diameter than the gap are filled in the gaps between the photocatalyst particles and the photocatalyst particles are bonded to each other. This method comprises forming a binder layer made of a thermoplastic material on a substrate made of ceramic, resin, metal, or the like, and then forming photocatalyst particles on the binder layer. A photocatalyst layer is formed, a solution containing ions of the metal particles having the small particle size is applied to the photocatalyst layer, and thereafter, the metal ions are reduced by irradiating light containing ultraviolet rays to fix the metal ions to the photocatalyst particles. The binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified. According to this method, the heat treatment step can be performed only once, so that the productivity is improved.

Further, another method of manufacturing a tile having a photocatalytic function according to the present invention is directed to a photocatalytic function in which metal particles having a smaller diameter than the gap are filled in the gaps between the photocatalyst particles and the photocatalyst particles are bonded to each other. This method comprises the steps of: forming a photocatalyst layer made of photocatalyst particles on a sheet-like binder layer made of a thermoplastic material; and forming an ion of the metal particles having the small particle size on the photocatalyst layer. Is applied, followed by irradiation with light including ultraviolet rays to reduce metal ions and immobilize them on the photocatalyst particles. Further, the sheet-like binder layer on which the photocatalyst layer is formed is made of a ceramic, resin or metal base material. Place or stick on top,
Thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the binder layer is solidified.

The photocatalyst particles can be ZnO, and the metal particles filling the gaps between the photocatalyst particles can be Ag or Ag ₂ O. Here, Ag or Ag ₂ O particles not only strengthen the bond between the ZnO particles that are photocatalysts, but also enhance the photocatalytic effect of ZnO,
It also has a deodorizing effect. In addition, by selecting ZnO as a photocatalyst, coloring due to Ag ions can be eliminated, and the color of the background of the substrate, the pattern, or the design effect due to the combination thereof can be improved.

Further, a solution containing a salt which forms a colorless or white salt which is insoluble with a metal ion filled in the gap between the photocatalyst particles is brought into contact with the photocatalyst layer, and thereafter, a light containing ultraviolet light is irradiated. May be irradiated. By doing so, the coloring due to the particles filling the gap can be eliminated without depending on the combination of ZnO and Ag or Ag ₂ O, and the background color of the base material can be eliminated. The design effect due to the patterns or their combination can be improved.

The photocatalyst particles may be made of TiO _2, and the heat treatment temperature for softening the binder layer may be 800 ° C. or more and 1000 ° C. or less. Ti above 800 ° C
Since a neck portion is formed between the O ₂ particles by the initial sintering, the bonding strength between the TiO ₂ particles is improved.
If the temperature exceeds 0 ° C., the process shifts to the middle-stage sintering process, and the volume of the photocatalytic layer shrinks significantly due to the solid phase sintering of TiO ₂ , so that cracks are easily generated.

The photocatalyst particles are made of TiO ₂ , the metal particles filled in the gaps between the photocatalyst particles are made of Ag, and a solution containing salts which form insoluble and colorless or white salts with ions of the metal. May be used as an aqueous solution of a halide such as KI, KCl, and FeCl ₃ . Since Ag forms an insoluble and colorless or white salt such as AgI and AgCl with an alkali halide, it is possible to improve the design of the base material by improving the background color, pattern, or combination thereof.

Further, the binder layer is selected to have a softening temperature lower than the softening temperature of the base material. The softening temperature of the binder layer is more than 20 ° C. and less than 320 ° C., preferably 40 ° C. or more and 300 ° C. or less. The heat treatment is performed at an ambient temperature in the range of not more than ℃ and lower than the softening temperature of the substrate. If the heat treatment temperature is lower than the temperature 20 ° C. higher than the softening temperature of the binder layer, the viscosity of the binder layer is too high, so that the binder layer and the photocatalyst particles are not sufficiently bonded, and conversely, the temperature is 320 ° C. lower than the softening temperature of the binder layer. If the heat treatment temperature is higher than ℃ higher temperature, the viscosity of the binder layer is too low and the photocatalyst particles will be buried in the binder layer, and if it occurs locally, bacteria will stay there, resulting in a decrease in antibacterial properties It depends.

When a dispersing step is provided as a step prior to the step of applying the photocatalyst particles on the binder layer, a dispersant for dispersing the sol or precursor to be the photocatalyst particles in the dispersion step in the solution. It is preferable to use only components that vaporize at a temperature lower than the heat treatment temperature for softening the binder layer. In the prior art,
Had no deodorant below 320 ° C., the dispersion step the dispersion agent is sufficiently vaporized attached to TiO ₂ particle surface in, for remaining in the not evaporate sufficiently TiO ₂ particle surface to the substrate top surface Because the photocatalytic function became insufficient. As the dispersant that evaporates at a low temperature, an organic dispersant having a molecular weight of 10,000 or less and a phosphoric acid-based dispersant are preferable.

When the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer is δb, 0 ≦ δt−δb ≦ 3.
It is preferably 0. If the specific gravity difference is too small, the photocatalyst particles are not sufficiently embedded in the binder layer, and the binder layer and the photocatalyst particles are not sufficiently bonded.If the specific gravity difference is too large, the photocatalyst particles are buried in the binder layer. If it occurs locally, bacteria stay on the bottom and the antibacterial property is reduced. As an application method of this method, δt
Even when −δb> 3.0 is required, a second binder layer satisfying 0 ≦ δt−δb ≦ 3.0 may be interposed between the binder layer and the photocatalyst particles. Also δt
When −δb <0, pressurizing during the heat treatment has the same effect as increasing the specific gravity difference Δt−δb. Therefore, H
By IP processing and hot press processing, 0 ≦ δt−δb ≦
The same effect as in the case of 3.0 can be obtained.

[0044]

The photocatalyst particles constituting the lower layer on the binder layer side of the photocatalyst particles constituting the photocatalyst layer are partially retained in the binder layer, and the photocatalyst constituting the surface layer of the photocatalyst layer which is in contact with the outside air. Since the particles are bonded to each other with the surface substantially exposed to the outside, the photocatalytic effect is sufficiently exhibited.

[0045]

Embodiments of the present invention will be described below with reference to the accompanying drawings. Here, FIG. 1 is a view for explaining a method for manufacturing a tile having a photocatalytic function according to the present invention, and FIG. 2 is a view showing FIG.
2 is an enlarged view of a main part of FIG.
As shown in (1), a substrate 1 is prepared.

Then, a binder layer 2 is formed on the surface of the substrate 1 as shown in FIG. The binder layer 2 is selected from a material whose softening temperature is lower than the softening temperature of the substrate 1. For example, when the substrate 1 is a tile, an enamel or a ceramic, the glaze layer or the printed layer can be used as the binder layer 2 as it is.

Next, a photocatalyst layer 3 made of photocatalyst particles such as TiO ₂ particles is formed on the binder layer 2 as shown in FIG. At this time, the photocatalyst layer 3 only needs to be mounted on the binder layer 2 with such a bonding force that the photocatalyst layer 3 does not fall off the binder layer 2 in the subsequent baking.

Alternatively, a binder layer 2
Before forming a photocatalyst layer, a photocatalyst layer 3 is formed on the binder layer 2 as shown in FIG.
May be placed on the substrate 1.

Thereafter, heat treatment is performed at an ambient temperature higher than the softening temperature of the binder layer 2 and higher than 20 ° C. and lower than 320 ° C. and lower than the softening temperature of the base material 1 to obtain the heat treatment shown in FIG. As shown in FIG. 2, a part of the photocatalyst particles 3 a constituting the lower layer of the photocatalyst layer 3 on the binder layer side is settled in the molten binder layer and the binder layer is solidified, so that the part is in the binder layer. Buried in and firmly held. Further, as shown in FIG. 3A, a part of the photocatalyst particles 3b constituting the surface layer of the photocatalyst layer 3 which is in contact with the outside air is bonded to each other by intermolecular force and sintering by sintering. Are separated from each other as shown in FIG. That is, the surface of the photocatalyst particles 3b is exposed to the outside substantially in the surface layer.

Here, the reason why the heat treatment temperature is set higher than the softening temperature of the binder layer 2 in the range of more than 20 ° C. and less than 320 ° C. is that if the temperature is lower than 20 ° C., it takes time for the softening of the binder layer and the photocatalyst becomes harder. On the other hand, when the temperature exceeds 320 ° C., the photocatalyst particles are buried in the binder layer due to the rapid melting of the binder layer, and irregularities are generated. Desirably, the temperature is 40 ° C. or more and 300 ° C. or less.

When the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer 2 is δb, 0 ≦ δt−δb ≦ 3.0.
Preferably, the relationship of 0.5 ≦ δt−δb ≦ 2.0 is satisfied. This is because, when the difference in specific gravity between the photocatalyst particles and the binder layer is too small, when the binder layer is melted, the vertical movement speed of the photocatalyst particles in the binder layer becomes slow, and the photocatalyst particles are easily separated after firing, If the difference in specific gravity between the photocatalyst particles and the binder layer is too large, the moving speed of the photocatalyst particles in the vertical direction increases, and most of the photocatalyst particles may be buried in the binder layer. The gap between the photocatalyst particles constituting the portion exposed from the binder layer 2, specifically, the photocatalyst particles 3 shown in FIG.
b, or the photocatalyst particles 3b shown in FIG.
Between the particles 3c (Sn,
Metals or oxides such as Ti, Ag, Cu, Zn, Fe, Pt, Co, Pd, and Ni) may be filled to bond the photocatalyst particles 3b to each other.

Specific examples will be described below. (Example 1) On the surface of a ceramic tile substrate of 150 squares, S
iO_Two-Al_TwoO_Three-Na / K _TwoBinder made of O frit
Layer was formed by spray coating and dried
Later, 15% TiO_TwoSpray coating with sol solution
0.8 μm thick TiO_TwoForm a layer
Then, the binder layer and TiO_TwoSubstrate with laminated layers
The ambient temperature with a roller hearth kiln
After heating and firing, cool and solidify to obtain a multifunctional material
Was. Here TiO_TwoThe sol aqueous solution is, for example, TiCl
Under hydrothermal conditions in the range of 100 to 200 ° C in a
The crystallite diameter obtained by hydrolyzing is about 0.007 to 0.2 μm
Degree anatase type TiO_TwoThe sol in the form of nitric acid, hydrochloric acid, etc.
Several percent in basic aqueous solution or basic aqueous solution such as ammonia
~ Several tens% dispersed to improve dispersibility
Triethanolamine and trimethylo as surface treatment agents
Organic amines of pentaamine, pentaerythritol, trimethyi
Rolled propane, etc. added within 0.5%
It is. In addition, TiO_TwoImage processing of sol particle size by SEM observation
The crystallite diameter is calculated from the integral width of powder X-ray diffraction
did. The application method is spray coating.
However, dip coating method, spin coating
It is expected that similar results will be obtained with the aging method. Obtained
Of anti-bacterial and abrasion resistance of multifunctional materials
Was done. For antibacterial properties, Escherichia coli
 W3110 strain). 70% in advance
Bacterial solution 0.15 on top of multifunctional material sterilized with ethanol
ml (1-5.times.10@4 CFU), and the glass plate (1
0 × 10cm) and adhere to the outermost surface of the substrate to obtain a sample.
Was. Irradiated with white light (3500 lux) for 30 minutes
The bacterial solution of the irradiated sample and the sample maintained
Wipe off with sterile gauze and collect in 10 ml of physiological saline.
The survival rate was determined and used as an index for evaluation. About wear resistance
Performs sliding wear using a plastic eraser,
The changes were compared and evaluated. The following (Table 1)
Porcelain tile, SiO for binder_Two-Al_TwoO_Three-Na / K_Two
Antibacterial property with the change of firing temperature when using O frit,
Shows the change in wear resistance.

[0053]

[Table 1]

Here, the SiO _2- used as a binder was used.
The specific gravity of the Al ₂ O ₃ —Na / K ₂ O frit was 2.4, the film thickness when applied was 200 μm, and the softening temperature was 680 ° C. The TiO ₂ obtained in (Table 1) was No. 1 to No. 3.
Is anatase type, specific gravity is 3.9, No.
About 4 and 5, it was a rutile type and specific gravity was 4.2.

In Table 1, No. 1 shows that the sintering temperature was only 20 ° C. higher than the softening temperature of the binder, and the viscosity of the binder did not become sufficiently low. TiO ₂ particles are not sufficiently embedded in a binder layer, therefore contains the scratches sliding 5-10 times in the abrasion resistance test, it had peeled off. Regarding antibacterial properties, it is an anatase type having excellent photocatalytic activity, and at 300 ° C. or higher, organic components are almost decomposed and vaporized by TG-DTA observation of TiO ₂ sol.
It is understood that the dispersant such as a surface treatment agent attached to the O ₂ surface is naturalized, but the firing temperature is 700 ° C., which is a much higher processing temperature, so that the excellent value of ++ was obtained. .

Nos. 3 to 5 have sintering temperatures of 800 ° C. or higher and 10
In each case, the durability was extremely excellent without any change even in a sliding test of 40 times or more. This may be due to the formation of a neck due to the initial firing of the TiO ₂ particles on the surface. In the case of treatment at 1100 ° C., cracks occurred in the TiO ₂ layer on the surface of the multifunctional material taken out from the roller hearth kiln after cooling and solidification. Judging from the TMA measurement of the TiO ₂ test piece, this is considered to be due to the medium-term sintering accompanied by significant volume shrinkage of the TiO ₂ particles.

In Nos. 4 and 5, the antibacterial properties were all negative. There are two possible causes for this. One is Ti
Another is that the O ₂ particles are in a rutile phase transition, and the other is that the firing temperature is 300 ° C. higher than the softening temperature of the binder.
It is conceivable that the TiO ₂ particles constituting the photocatalyst layer were buried in the binder layer because the viscosity was too high and the viscosity of the binder was too low. Here, it cannot be considered that the only cause is that the TiO ₂ particles undergo a rutile type phase transition. This is because rutile-type TiO ₂ is slightly inferior to anatase-type TiO _2, but has some photocatalytic activity. For example, the antibacterial property of the material obtained by spray-coating a TiO ₂ sol directly on a porous alumina substrate, firing at 950 ° C., and solidifying by cooling was +. Therefore, the firing temperature is higher than the softening temperature of the binder by more than 300 ° C., and the viscosity of the binder is too low, so that the TiO ₂ particles constituting the photocatalyst layer are buried in the binder layer. It is understood that.

The elemental analysis of Ti and Si (the main component of the binder) by EPMA or the like in the cross-sectional direction of the sample shows that a layer in which Ti and Si are mixed is observed, and that TiO _{2 as} photocatalyst particles is embedded. Was confirmed.

Example 1 above, that is, at least the photocatalyst was TiO ₂ and the binder layer was SiO ₂ —Al ₂ O ₃ —Na / K ₂
At the time of O frit, the following was confirmed. When the multifunctional material is manufactured under the condition that the sintering temperature is higher than the softening temperature of the binder by more than 20 ° C. and not higher than 300 ° C., the multifunctional material having good antibacterial property and abrasion resistance can be manufactured. The cause is considered to be that the viscosity of the binder is adjusted to a value at which the TiO ₂ can be appropriately embedded in the binder layer in the above temperature range. In the multifunctional material prepared in the above, embedding of TiO ₂ particles in the binder layer was confirmed. When the firing temperature is 800 ° C or higher and 1000 ° C or lower,
In each case, the abrasion resistance was extremely excellent without any change even in a sliding test of 40 times or more. This is thought to be due to the strong bond between the TiO ₂ particles and the formation of the neck.

(Example 2) SiO ₂ -Al ₂ was coated on the surface of a 100 × 100 × 5 alumina base material (alumina purity: 96%).
Spray the binder layer composed of O ₃ -PbO frit
After forming by coating method and drying, 15% Ti
An O ₂ sol aqueous solution (same as in Example 1) is applied by a spray coating method to form a TiO ₂ layer having a thickness of 0.8 μm, and then a base material on which a binder layer and a TiO ₂ layer are laminated is rolled. After heating and firing in a hearth kiln at different ambient temperatures for each example, the solidified material was cooled and solidified to obtain a multifunctional material.

The following Table 2 shows the change in antibacterial and abrasion resistance with the change in firing temperature when alumina is used as the base material and SiO ₂ -Al ₂ O ₃ -PbO frit is used as the binder.

[0062]

[Table 2]

Here, the SiO ₂ − used as a binder was used.
The softening temperature of the Al ₂ O ₃ —PbO frit was 540 ° C., the specific gravity was 3.8, and the film thickness when applied was 150 μm. The crystal forms of the obtained TiO ₂ were all anatase.

In the wear resistance test of (Table 2), No. 6
Was scratched and stripped by sliding less than 10 times,
Nos. 7 and 8 were not damaged even after 10 or more slides.
In o.9 and 10, good results were obtained in which no damage was caused even after sliding more than 40 times.

[0065] The wounds in 40 times or more sliding No.9,10 were not pulled, since the firing temperature of 800 ° C. or higher, the neck is produced between the TiO ₂ particles, TiO ₂ strongly between the particles Probably because of the combination. No. 6 caused scratching and peeling by sliding less than 10 times, because the firing temperature was only 20 ° C. higher than the softening temperature of the binder, and the viscosity of the binder did not become sufficiently low. This is probably because the anatase-type TiO ₂ particles constituting the lowermost layer of the photocatalyst layer were not sufficiently embedded in the binder layer. On the other hand, in No. 7 and 8, no damage was found even after sliding 10 times or more because the difference between the sintering temperature and the softening temperature of the binder did not reach the temperature at which the neck portion was formed. It is considered that the viscosity was adjusted to a value at which TiO ₂ could be appropriately embedded in the binder layer. On the other hand, in the antibacterial test of (Table 2), Nos. 6 to 9 obtained good results of +++ or ++, but No. 10 became +. This is considered to be because the firing temperature was higher than the softening temperature of the binder by 320 ° C., and the viscosity of the binder was too low, so that the TiO ₂ particles constituting the photocatalyst layer were embedded in the binder layer.

Example 3 An SiO ₂ —Al ₂ O ₃ —BaO frit was melted in a mold, cooled and solidified, and then processed to 100%.
× 100 × 1 glass sheet is prepared and 15%
TiO ₂ sol solution (same as Example 1) was applied by spray coating method, the film thickness is 0.8 [mu] m TiO ₂
A layer was formed. Thereafter, the glass sheet was placed on an alumina base material (100 × 100 × 5), heated and fired in a siliconit furnace at different atmospheric temperatures for each example, and then cooled and solidified to obtain a multifunctional material.

The following Table 3 shows changes in antibacterial properties and abrasion resistance of the above-mentioned multifunctional materials according to the firing temperature.

[0068]

[Table 3]

Here, the SiO ₂ − used as a binder was used.
The softening temperature of the Al ₂ O ₃ —BaO frit is 620 ° C., the specific gravity is 2.8, and the crystal form of TiO ₂ on the multifunctional material is No. 11 to 13.
No. 14 was an anatase type, and No. 14 was a rutile type.

In the wear resistance test of (Table 3), No. 1
No. 1 was scratched and peeled by sliding less than 10 times, but No. 12 was not damaged even by sliding more than 10 times, and No. 13 and 14 was more than 40 times sliding. However, good results were obtained in which no scratches occurred.

[0071] The wounds in 40 times or more sliding No.13,14 were not pulled, since the firing temperature of 800 ° C. or higher, the neck is produced between the TiO ₂ particles, TiO ₂ strongly between the particles Probably because of the combination. In No. 11, scratches were caused by sliding less than 10 times and peeled off because the firing temperature was only 20 ° C. higher than the softening temperature of the binder, and the viscosity of the binder did not become sufficiently low. This is probably because the anatase-type TiO ₂ particles constituting the lowermost layer of the photocatalyst layer were not sufficiently embedded in the binder layer.
On the other hand, in No. 12, no scratch was found even after 10 times of sliding, but the difference between the sintering temperature and the softening temperature of the binder did not reach the temperature at which the neck was formed, but the viscosity of the binder was reduced. It considered from being adjusted to a value TiO ₂ can be appropriately embedded in the binder layer. On the other hand, in the antibacterial test of (Table 3), No. 11 to 13 obtained good results as +++ or ++, but No. 14 became-. This is because the TiO ₂ is of rutile type, the sintering temperature is 320 ° C. higher than the softening temperature of the binder, and the viscosity of the binder becomes too low, so that the TiO ₂ constituting the photocatalyst layer is formed.
It is considered that the particles were buried in the binder layer for two reasons.

From the above, TiO ₂ was previously added to the binder.
In the method of obtaining the multifunctional material by applying the particles and then sticking and firing on the substrate, the same effect as the method of applying the binder to the surface of the substrate and then applying the TiO ₂ particles to obtain the multifunctional material is obtained. Was obtained.

Example 4 An acrylic resin binder was applied to the surface of a 100 × 100 × 5 polyimide resin base material, and then a 15% TiO ₂ sol aqueous solution was applied by a spray coating method. 0.8 μm TiO ₂
After forming the layer, the substrate on which the binder layer and the TiO ₂ layer were laminated was fired at 150 ° C. in a nichrome furnace to obtain a multifunctional material.

The following Table 4 shows changes in the antibacterial and abrasion resistances of the above-mentioned multifunctional materials according to the firing temperature.

[0075]

[Table 4]

In Table 4, the method of preparing the 15% TiO ₂ sol aqueous solution was changed as follows. No. 15: The 15% TiO ₂ sol aqueous solution used in Example 1 was used as it was. No. 16: TiCl aqueous solution was placed in an autoclave at 110-1.
After hydrolysis at 50 ° C., the product was adjusted to pH 0.8 with nitric acid, dispersed without using a surface modifier, and then used after removing aggregates. In this case, spray coating was performed immediately after removing the aggregates.

Here, the specific gravity of TiO ₂ is 3.9, the crystal type is anatase, the specific gravity of the acrylic resin is 0.9, and the temperature at which the viscosity corresponding to the glass softening point is 70 ° C.

Regarding the abrasion resistance, no scratch was found in any of Nos. This is presumably because the range of the difference between the sintering temperature and the softening temperature of the binder was such that the viscosity of the binder could be adjusted to a value at which TiO ₂ could be properly embedded in the binder layer.

On the other hand, regarding the antibacterial test, NO.
However, it was found that multifunctional materials having antibacterial properties can be produced even at a temperature lower than 30 ° C. by obtaining favorable results of ++ for .16. This difference is DTA-T
In G, 200 to 350 in the TiO ₂ sol of No. 15
Although some components decompose and evaporate at ° C, they are not recognized in NO.16, and it is considered that this is caused by the presence or absence of organic components covering TiO ₂ . Here, the specific gravity difference between the anatase and the acrylic resin was 3, but it was confirmed that with such a difference, the TiO ₂ particles constituting the photocatalytic layer had good antibacterial properties without being embedded in the binder layer. .

Example 5 A binder layer made of frit or the like having a different specific gravity was formed by spray coating on the surface of a 100 × 100 × 5 alumina substrate, and dried to form a 15% TiO ₂ sol. The aqueous solution is spray-coated to form a 0.8 μm-thick TiO ₂ layer, and then the substrate on which the binder layer and the TiO ₂ are laminated is heated and fired at 750 ° C. with a roller hearth kiln and then cooled and solidified. Multifunctional material was obtained.

The following Table 5 shows changes in antibacterial properties and abrasion resistance of the above multifunctional materials with changes in firing temperature.

[0082]

[Table 5]

Regarding the antibacterial test, all of the samples Nos. 17 to 20 were as good as +++. In any case, the sintering temperature is 30 ° C. or more and 300 ° C. or higher than the softening temperature of the binder.
It is considered that the range of the difference between the sintering temperature and the softening temperature of the binder was a value in which the viscosity of the binder was adjusted to a value at which TiO ₂ could be appropriately embedded in the binder layer.

Regarding the abrasion resistance, No. 17 was scratched and peeled off by sliding 5 times or less,
In No. 20, no scratch was found even after sliding 10 times or more. As the cause, unlike other in NO.17, since towards the specific gravity of the binder is greater than the specific gravity of TiO _2, anatase TiO ₂ particles constituting the outermost layer of the photocatalyst layer is Na' is sufficiently embedded in the binder layer It is thought that it is because. Therefore, it has been found that the abrasion resistance of the multifunctional material is also affected by the specific gravity of TiO ₂ and the binder, and the specific gravity of the binder is deteriorated when the specific gravity of the binder is larger than that of TiO ₂ .

Example 6 An SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature of 6) was applied to the surface of a 150 square porcelain tile base material.
20 ° C.), and a Ti layer is formed thereon.
An aqueous solution obtained by mixing and stirring an O ₂ sol and a SnO ₂ sol was applied by a spray coating method, and then baked at 750 ° C. and cooled and solidified to obtain a multifunctional material. The TiO ₂ sol concentration is 4 ~
In 6 wt% adjusted to PH11 with NH3 aqueous solution, TiO ₂
The crystallite diameter of the particles is 0.01 μm, and the crystallite diameter of the SnO ₂ particles is 0.0035 μm.

The results of the antibacterial test and the abrasion resistance test for the tiles thus produced when the amount of SnO _{2 to} TiO ₂ (molar ratio) was variously changed are shown in Table 6 below.

[0087]

[Table 6]

The abrasion resistance test improved with an increase in the amount of SnO _2. With addition of 10% or more, no damage was caused and no change occurred even after 40 times of the sliding test. Regarding the antibacterial test, if the range was up to 20% or more, it was +++ as in the case of no addition, and it stopped at ++ up to 60%. If more is added, the T
The probability of covering the SiO ₂ particles increases, and the antibacterial property deteriorates.
At 0%, it became-. Therefore, the amount of SnO ₂ added should be 10% or more and 60% or less, preferably 10% or less, of the amount of TiO ₂ in molar ratio.
% To 20% or less, a tile excellent in both antibacterial properties and abrasion resistance can be provided.

Here, the abrasion resistance is improved with an increase in the amount of SnO ₂ by the following mechanism. That is, SnO ₂ is T
Since the vapor pressure is higher at a temperature higher than 600 ° C. than that of iO ₂ ,
Before sintering, the interval between the TiO ₂ particles 3b is L _O as shown in FIG. 4 (a), but the vapor pressure is high on the surface of the TiO ₂ particles 3 having a positive curvature, and the negative curvature is reduced. The surface of the neck, that is, the surface of the neck where the two TiO ₂ particles 3b come into contact, has a low vapor pressure. As a result, SnO ₂ having a higher vapor pressure than TiO ₂ enters the neck portion as shown in FIG.
As shown in FIG. 4 (c), it is condensed and sintered by a vaporization-condensation mechanism. When sintering is performed by the vaporization-condensation mechanism, cracks and the like do not occur because the interval L ₂ between the TiO ₂ particles after sintering is substantially equal to the interval L _O before sintering. As described above, the TiO ₂ is provided on the surface of the base material via the binder.
In the composite member holding the particle layer, if the SnO ₂ particles are filled in the gaps between the TiO ₂ particles exposed at the outermost surface and fired at 600 ° C. or more, the cracks are not generated and the neck portion between the TiO ₂ particles does not occur. Can be combined, so that the wear resistance is improved.

Comparative Example 7 A binder layer made of SiO ₂ -Al ₂ O ₃ -BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150 square porcelain tile base material in the same manner as in Example 6. An aqueous solution obtained by mixing and stirring a TiO ₂ sol and a SiO ₂ sol thereon is applied by a spray coating method, and then 750
It was baked at ℃ and solidified by cooling to obtain a multifunctional material. Note that TiO ₂
The sol concentration is adjusted to PH11 with an aqueous NH3 solution at 4 to 6 wt%, and the crystallite size of the particles is 0.01 μm as in Example 6.
However, the crystallite diameter of the SnO ₂ particles was as large as 0.008 μm.

The antibacterial test and the abrasion resistance test were performed on the tile thus manufactured, and the results of comparison with Example 6 are shown in Table 7 below.

[0092]

[Table 7]

[0093] As a result, the effect of improving wear resistance of the SnO ₂ particles 0.008μm is weaker than with SnO ₂ particles 0.0035Myuemu, the molar ratio TiO ₂ particles finally 40 more than 60% No damage was found in the sliding test, and no change occurred. In the antibacterial test, as in the case of using SnO ₂ particles of 0.0035 μm, if the range was up to 20% or more, it was +++ as in the case of no addition, and if it was 60% or less, it stopped at ++.
When added more, the probability of covering the TiO ₂ particles on the surface of the substrate increased, and the antibacterial property deteriorated.
Therefore, when 0.01 μm TiO ₂ particles are used, it is difficult to add 0.008 μm SnO ₂ particles to provide a tile excellent in antibacterial properties and abrasion resistance. This is due to the fact that the vapor pressure of the SnO ₂ particles decreases as the particle size increases, and that the SnO ₂ particles remaining without vaporization are reduced to 0.1%.
In the case of 0035 μm, it was present in the gap between the TiO ₂ particles and the bonding strength could be improved.
This is probably because the SnO ₂ particles are larger than the gaps between the O ₂ particles, so that the SnO ₂ particles do not enter the gaps, but rather have a higher probability of coming on the TiO ₂ particles. The size of the SnO ₂ particles should fill the gap of the TiO ₂ particles from the above, compared TiO ₂ particle size is preferably less than 4/5.

Example 8 A binder layer made of SnO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150 square porcelain tile base material.
After applying the aqueous solution of the TiO ₂ sol by the spray coating method, the composite member baked at 750 ° C. and cooled and solidified is subjected to Sn coating.
An O ₂ sol aqueous solution was applied by a spray coating method and then heat-treated at 110 ° C. to obtain a multifunctional material. At this time Ti
The use of the same as in Example 6 to O ₂ sol solution, SnO ₂
The sol used was 0.0035 μm.

The results of the antibacterial test and the abrasion resistance test performed on the tile thus manufactured are shown in Table 8 below.

[0096]

[Table 8]

The abrasion resistance test improved as the amount of SnO ₂ increased.
No damage was found in the rotational sliding test, and no change occurred. For the antibacterial test, if it is in the range up to 20% or more, it is +++ as in the case of no addition, and 60%
Until then, I stopped at ++. If more is added, the probability of covering the TiO ₂ particles on the substrate surface increases, and the antibacterial property deteriorates,
At 100%, it became-. In this test, SnO ₂ sol was 11
Since the heat treatment is performed at a low temperature of 0 ° C., the sintering by the vaporization-condensation mechanism shown in Example 6 does not occur. Nevertheless, the abrasion resistance was improved, but this was due to the smaller particle size than the TiO ₂ particles, that is, S having a large specific surface area and excellent adsorption power.
Since the nO ₂ particles filled the gaps between the TiO ₂ particles, Ti
It is considered that the bonding between the O ₂ particles was strengthened.

Example 9 A binder layer made of SiO ₂ -Al ₂ O ₃ -BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150 square porcelain tile base material.
An aqueous solution of copper acetate is applied to the composite member that has been baked at 750 ° C. and cooled and solidified after applying an aqueous solution of the TiO ₂ sol by a spray coating method, and then dried. While fixing to the photocatalyst layer, a multifunctional material was obtained. Here, a mercury lamp was used as the irradiation lamp. Here, the average size of the Cu particles fixed to the photocatalyst layer was about 0.004 μm.

The results of the antibacterial test and the abrasion resistance test performed on the tiles thus produced are shown in Table 9 below.

[0100]

[Table 9]

The wear resistance test improved with an increase in the amount of Cu, and the addition of a molar ratio of 20% or more did not cause any damage or change even in the 40 times of the sliding test. Regarding the antibacterial test, if the range was up to 20% or more, it was +++ as in the case of no addition. Since Cu itself has an antibacterial activity, deterioration of the antibacterial activity by adding a large amount was not observed. However, when the amount of Cu added is small, the photocatalytic action of the TiO ₂ particle layer is predominant, and when the amount of Cu added is large, C
It can be considered that the action by u is dominant. Cu
When only the action is expected, Cu is gradually eluted when used in a liquid, and therefore, it is considered that the life is shorter as compared with the case without a photocatalyst. Also, when the amount of Cu added becomes large, the cost increases accordingly. Therefore, it seems that it is meaningless to set the Cu amount too large. According to this example, it was confirmed that not only an oxide such as SnO ₂ but also a metal such as Cu could be a particle that fills the gap of the TiO ₂ particle layer.

Example 10 A binder layer made of SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150-square ceramic tile substrate, and a TiO ₂ sol was formed thereon. An aqueous solution is applied by a spray coating method, and then applied to a composite member which is baked at 950 ° C. and cooled and solidified, and then applied to a photocatalytic layer while irradiating light including ultraviolet rays to reduce copper ions. And multifunctional material was obtained.
At this time, irradiation was performed for several minutes using a BLB lamp as an irradiation lamp. TiO ₂ undergoes a phase transition from anatase to rutile during the heat treatment process. The thickness of TiO ₂ was adjusted to 0.4 μm during spray coating.

The tile thus produced was subjected to an antibacterial test and an abrasion resistance test. Regarding the abrasion resistance test, good results are shown in this temperature range even without addition. Cu
As in the case of no addition, no damage was found in the 40 times of the sliding test, and no change occurred. The antibacterial test is shown in FIG. TiO ₂ when not added
Is bad because of rutile. The antibacterial property of adding Cu increased. And not only when irradiating the BLB lamp,
When the amount of supported Cu is 0.7 μg / cm ² or more even when irradiation is not performed, the antibacterial activity becomes ++ and the amount of supported Cu is 1.2%.
If it is more than μg / cm ² , the antibacterial activity becomes +++. More to provide a multifunctional material having excellent wear resistance antimicrobial from it, Cu supported amount is 0.7 [mu] g / cm ² or better, more preferably 1.2 ug / cm ² or more is good .

Incidentally, the amount of supported Cu is dramatically improved when a drying step is performed before the irradiation with the BLB lamp after the application of the aqueous copper acetate solution. FIG. 6 shows the relationship. This is presumably because the concentration of metal ions when photoreduced is higher when dried.

The amount of Cu carried was optimized for the amount of Cu applied.
(Figures 7 and 7 show copper acetate with a Cu concentration of 1 wt%
In the case of FIG. 7, the application amount is 0.7 μg / cm.^Two
0.2mg / cm^Two2.7 mg / c or more
m^TwoBelow, 1.2 μg / cm ^Two0.3m to get over
g / cm^Two2.4 mg / cm or more^TwoWhat should be done below.

Example 11 A binder layer made of SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 680 ° C.) was formed on the surface of a 150-square ceramic tile base material, and a TiO ₂ sol was formed thereon. An aqueous solution is applied by a spray coating method, and then applied at a temperature of 950 ° C. to a cooled and solidified composite member, an aqueous solution of silver nitrate is applied, dried, and then irradiated with light including ultraviolet rays to reduce silver ions and form a photocatalytic layer. It was fixed to obtain a multifunctional material. At this time, irradiation was performed for several minutes using a BLB lamp as an irradiation lamp. In addition, TiO ₂ undergoes a phase transition from anatase to rutile during the heat treatment process. The thickness of TiO ₂ was adjusted to 0.4 μm during spray coating.

The tiles thus produced were subjected to an antibacterial test and an abrasion resistance test. Regarding the abrasion resistance test, good results are shown in this temperature range even without addition. Ag
As in the case of no addition, no scratch was found in the sliding test for 40 times, and no change occurred.

FIG. 5 shows the antibacterial test. When it was not added, TiO ₂ was rutile, and was poor as +. The addition of Ag increased the antibacterial properties. In addition, the Ag carrying amount is 0.0
When the concentration is 5 μg / cm ² or more, the antibacterial activity becomes ++ and A
When the amount of supported g becomes 0.1 μg / cm ² or more, the antibacterial activity becomes +++. Therefore, in order to provide a multifunctional material excellent in both antibacterial properties and abrasion resistance, the amount of supported Ag is 0.05 μg.
/ Cm ² or more, more preferably 0.1 μg / cm ²
The above is good. However, when the amount of Ag carried is large, the color is changed from brown to black, and the appearance is poor. However, the Ag loading amount is 1
If it is less than μg / cm ^2, there is no coloring. From the above, Ag
The loading amount is preferably 0.05 μg / cm ² or more and 1 μg / cm ² or less, more preferably 0.1 μg / cm ² or more and 1 μg / cm ^2.
cm ² or less is good.

(Example 12) A binder layer made of SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 680 ° C.) was formed on the surface of a 150 square ceramic tile base material, and a TiO ₂ sol was formed thereon. An aqueous solution is applied by a spray coating method, and then applied at a temperature of 950 ° C. to a cooled and solidified composite member, an aqueous solution of silver nitrate is applied, dried, and then irradiated with light including ultraviolet rays to reduce silver ions and form a photocatalytic layer. It was fixed to obtain a multifunctional material. At this time, irradiation was performed for several minutes using a BLB lamp as an irradiation lamp. In addition, TiO ₂ undergoes a phase transition from anatase to rutile during the heat treatment process.

[0110] The tile thus manufactured was made of TiO ₂
Abrasion resistance test, antibacterial test and stain resistance test were carried out while changing the film thickness of the film to various values. Regarding the abrasion resistance test, good results were obtained in the range of 2 μm or less tested this time, and no damage was caused and no change occurred in the 40 times of the sliding test. In the antibacterial test, the film thickness becomes ++ when the film thickness is 0.1 μm or more and ++ when the film thickness is 0.2 μm or more. Therefore, the thickness of TiO ₂ is preferably 0.1 μm or more.
Preferably, it is 0.2 μm or more.

Example 13 A binder layer made of SiO ₂ —Al ₂ O 3 —BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150-square ceramic tile base material, and a zinc chloride aqueous solution or Spray TiO ₂ sol solution
After coating and drying by a coating method, an aqueous solution of silver nitrate was applied, and then fixed to the photocatalytic layer while irradiating with light including ultraviolet rays to reduce silver ions. After that, 900 ° C or more and 1000
It was baked at below ℃ and solidified by cooling to obtain a multifunctional material. At this time, irradiation was performed for several minutes using a BLB lamp as an irradiation lamp.
In addition, TiO ₂ undergoes a phase transition from anatase to rutile during the heat treatment process. In addition, Ag whose surface is fixed is
Since the color changed from brown to white, it is considered that the color changed to silver oxide during firing. However, the adhesion of Ag was fixed discretely, and the observation showed that the growth of Ag particles before and after calcination was hardly observed.

The thus prepared tiles were subjected to an antibacterial test and a wear resistance test. Regarding the abrasion resistance test, good results are shown in this temperature range even without addition. Ag
In the same manner as in the case where no was added, even in the case of no addition, no damage was caused in 40 sliding tests, and no change occurred.
The antibacterial test is shown in FIG. Ti without additive
O ₂ is bad because it is rutile. The addition of Ag increased the antibacterial properties.

Example 14 A binder layer made of SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150 square ceramic tile base material, and a TiO ₂ sol was formed thereon. An aqueous solution is applied by a spray coating method, and then an aqueous solution of silver nitrate is applied to a composite member that has been baked at 900 ° C. or more and 1000 ° C. or less and cooled and solidified, and then irradiated with light including ultraviolet rays to reduce silver ions and photocatalyst. It was fixed to a layer, and a 0.1 mol / l KI aqueous solution was further applied thereon at a rate of 0.1 cc / cm ² and further irradiated with ultraviolet rays for about 5 seconds to obtain a multifunctional material. At this time, the supported amount of Ag was 2μ.
g / cm ² . By applying a 0.1 mol / l KI aqueous solution at a rate of 0.1 cc / cm ² and further irradiating with ultraviolet rays for about 5 seconds, the brown-black multifunctional material is decolorized to white, and its appearance is improved. Improved.

(Example 15) A binder layer made of SiO ₂ —Al ₂ O ₃ —BaO frit (softening temperature: 620 ° C.) was formed on the surface of a 150-square ceramic tile base material, and a TiO ₂ sol was formed thereon. After applying the aqueous solution by the spray coating method, the multifunctional material obtained by baking at 820 ° C. and cooling and solidifying is placed at an angle, and the multifunctional material is irradiated with light including ultraviolet rays onto the multifunctional material. The bath water collected in a public bath was circulated over the tub, and continuously dropped to observe the change in the bath water. For comparison, a similar device was dropped on a substrate having no photocatalyst layer. In the observation after 14 days, the bath water dropped on the multifunctional material showed a unique difference in the degree of turbidity as compared with the bath water dropped on the substrate not provided with the photocatalytic layer. Although it was not possible, there was a difference in the water odor. That is, in the bath water that was dropped on the substrate without the photocatalyst layer, a rather strong drenched water odor was observed, and slime-like slime and organic precipitates were observed on the substrate, whereas None of the bath water was dropped on the multifunctional material. According to the above simulation experiment, it is considered that this tile can be used as a paving stone for artificial waterfalls and fountains of the water circulation system in parks, department stores, and the like.

[0115]

As is apparent from the above description, according to the present invention, the photocatalyst particles are fixed via the binder layer made of a material lower than the softening temperature of the base material. Since the photocatalyst particles constituting the photocatalyst particles are not buried in the binder layer, the surface of the photocatalyst particles is substantially exposed to the outside, and the photocatalytic effect can be sufficiently exhibited. Further, among the photocatalyst particles, some of the particles constituting the lower layer of the photocatalyst layer are buried in the binder layer, so that the holding power of the photocatalyst layer is greatly improved, and peeling or the like hardly occurs.

[Brief description of the drawings]

FIG. 1 is a diagram illustrating a method for manufacturing a tile having a photocatalytic function according to the present invention.

FIG. 2 is an enlarged view of a main part of FIG. 1 (d).

FIG. 3 is an enlarged view between TiO ₂ particles.

4 (a) to 4 (c) are views for explaining the mechanism of sintering of TiO ₂ particles.

FIG. 5 is a graph showing test results of an antibacterial test.

FIG. 6 is a graph showing test results on the amount of supported Cu when a drying step is performed before irradiation with a BLB lamp.

FIG. 7 is a graph showing the relationship between the amount of Cu carried and the amount of Cu applied;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Binder layer, 3 ... Photocatalyst layer, 3a ... Photocatalyst particle which comprises the lower layer of the binder layer side of the photocatalyst layer, 3b ... Photocatalyst particle which comprises the surface layer in contact with outside air among the photocatalyst layers, 3c ... Particles filled to combine photocatalytic particles.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C04B 41/86 C04B 41/86 A // A61L 9/00 A61L 9/00 C C04B 41/85 C04B 41 / 85 Z (72) Inventor Keiichiro Norimoto 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture Inside Totoki Equipment Co., Ltd. (72) Eiichi Kojima 2-1-1, Nakajima, Kokurakita-ku, Kitakyushu City, Fukuoka Prefecture No. Totoki Equipment Co., Ltd. (72) Mitsuyoshi Machida, Inventor 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Totoki Equipment Co., Ltd. (72) Yoshimitsu Saeki 2, Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Tatsuhiko Kuga 2-1-1, Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture 1-1-2 Toto Kiki Co., Ltd. (72) Inventor Yasushi Nakajima 2-1, 1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka

Claims (19)

[Claims] 1. A photocatalytic function in which a photocatalyst layer is held on a base material surface via a binder layer, wherein an upper layer of the photocatalyst layer is exposed from the binder layer so as to be in contact with the outside air, and a lower layer of the photocatalyst layer. The part is a tile having a photocatalytic function part of which is embedded in the binder layer, and the average particle diameter of the photocatalyst particles constituting the photocatalyst layer is 0.3 μm.
m, wherein the tile has a photocatalytic function. 2. The tile having a photocatalytic function according to claim 1, wherein the binder layer is made of a thermoplastic material such as glaze, inorganic glass, thermoplastic resin, and solder. 3. A tile having a photocatalytic function, wherein a photocatalyst layer made of photocatalyst particles is laminated on a sheet-like binder layer made of a thermoplastic material or a part of the photocatalyst layer is buried in the tile. A tile having a photocatalytic function, wherein an average particle diameter of constituent photocatalytic particles is less than 0.3 μm. 4. A binder layer made of a thermoplastic material is formed on a substrate made of ceramic, resin or metal, and then a photocatalyst layer made of photocatalyst particles is formed on the binder layer. In a method for manufacturing a tile having a photocatalytic function of softening the binder layer and embedding a part of the lower layer of the photocatalyst layer in the binder layer, and then solidifying,
When the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer is δb, 0 ≦ δt−δb ≦ 3.0, wherein the tile has a photocatalytic function. 5. A photocatalyst layer made of photocatalyst particles is formed on a sheet-shaped binder layer made of a thermoplastic material, and this sheet-shaped binder layer is placed or adhered on a substrate made of ceramic, resin, metal or the like. Thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is buried in the binder layer, and then the method for producing a tile having a photocatalytic function of solidifying is performed. Where δb is the specific gravity of 0 ≦ δt−δb ≦
A method for producing a tile having a photocatalytic function, wherein the tile is 3.0. 6. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A binder layer made of a thermoplastic material is formed on a base material such as a resin or a metal, and then a mixture obtained by mixing photocatalyst particles and the small particles having the above-mentioned particle diameter in a sol or precursor state on the binder layer is formed. Forming a photocatalyst layer by coating, and thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the method for producing a tile having a photocatalyst function of solidifying is performed. When the specific gravity is δt and the specific gravity of the binder layer is δb, 0 ≦ δt−δb ≦
A method for producing a tile having a photocatalytic function, wherein the tile is 3.0. 7. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A photocatalyst layer is formed by coating a mixture of photocatalyst particles and particles having the above-mentioned small particle size in the form of a sol or a precursor on a sheet-like binder layer made of a material, thereby forming a photocatalyst layer. The layer is placed or adhered on a substrate made of ceramic, resin, metal, or the like, and thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is embedded in the binder layer, and then the photocatalytic function is solidified. Wherein the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer is δb, wherein 0 ≦ δt−δb ≦ 3.0. A method for producing a tile having: 8. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A binder layer made of a thermoplastic material is formed on a base material such as a resin or a metal, and then a photocatalyst layer made of photocatalyst particles is formed on the binder layer, and then the binder layer is softened to form a photocatalyst. Part of the lower layer of the layer is embedded in the binder layer, then the binder layer is solidified, a solution containing the particles having the small particle diameter is applied to the photocatalyst layer, and heat treatment is performed to reduce the particles having the small particle diameter to the photocatalyst particles. In the method for producing a tile having a photocatalytic function to be immobilized to, when the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer is δb,
A method for producing a tile having a photocatalytic function, wherein 0 ≦ δt−δb ≦ 3.0. 9. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A photocatalyst layer made of photocatalyst particles is formed on a sheet-shaped binder layer made of a material, and then the sheet-shaped binder layer formed with the photocatalyst layer is placed or adhered on a base material such as ceramic, resin or metal. Thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is buried in the binder layer, the binder layer is solidified, and a solution containing the particles having the small particle diameter is further applied to the photocatalyst layer. In the method for producing a tile having a photocatalytic function of immobilizing the small-sized particles to the photocatalytic particles, the specific gravity of the photocatalytic particles is δ
t, when the specific gravity of the binder layer is δb, 0 ≦ δt
A method for producing a tile having a photocatalytic function, wherein -δb ≦ 3.0. 10. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with metal particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A binder layer made of a thermoplastic material is formed on a base material such as a resin or a metal, and then a photocatalyst layer made of photocatalyst particles is formed on the binder layer, and thereafter, the binder layer is softened. Part of the lower layer of the photocatalyst layer is embedded in the binder layer,
Next, the binder layer is solidified, and a solution containing the ions of the metal particles having the small particle diameter is applied to the photocatalyst layer. Thereafter, light containing ultraviolet rays is irradiated to reduce the metal ions and fix the photocatalyst particles to the photocatalyst. In the method for producing a tile having a function, when the specific gravity of the photocatalyst particles is δt and the specific gravity of the binder layer is δb, 0 ≦ δt−δb ≦ 3.
0. A method for producing a tile having a photocatalytic function, which is 0. 11. A method of manufacturing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with metal particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A photocatalyst layer made of photocatalyst particles is formed on a sheet-shaped binder layer made of a plastic material, and then the sheet-shaped binder layer formed with the photocatalyst layer is placed or adhered on a substrate made of ceramic, resin or metal. Thereafter, the binder layer is softened, a part of the lower layer of the photocatalyst layer is buried in the binder layer, and then the binder layer is solidified. Coating, followed by irradiating light containing ultraviolet light to reduce metal ions and immobilize the photocatalyst particles on the tile, the method comprising the steps of: When the specific gravity of the binder is δt and the specific gravity of the binder layer is δb, 0 ≦ δt−δb ≦ 3.0, wherein the tile has a photocatalytic function. 12. A method for manufacturing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with metal particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A binder layer made of a thermoplastic material is formed on a base material such as a resin or metal, and then a photocatalyst layer made of photocatalyst particles is formed on the binder layer. A solution containing ions of particles is applied, and thereafter, a metal ion is reduced by irradiating light containing ultraviolet rays to fix the metal ions to the photocatalyst particles. In the method for manufacturing a tile having a photocatalytic function of solidifying the binder layer, the specific gravity of the photocatalyst particles is δt, and the specific gravity of the binder layer is δb. In the case, 0 ≦ δt−δb ≦ 3.0, a method for producing a tile having a photocatalytic function. 13. A method for producing a tile having a photocatalytic function in which a gap between photocatalyst particles is filled with metal particles having a smaller particle size than the gap, and the photocatalyst particles are bonded to each other. A photocatalyst layer made of photocatalyst particles is formed on a sheet-like binder layer made of a plastic material, and a solution containing ions of the metal particles having the small particle diameter is applied to the photocatalyst layer, and then irradiated with light containing ultraviolet rays. The metal ions are reduced and fixed to the photocatalyst particles, and the sheet-like binder layer on which the photocatalyst layer is formed is placed or adhered on a base material made of ceramic, resin, metal, or the like. A method for producing a tile having a photocatalytic function of softening and embedding a part of a lower layer of a photocatalyst layer in a binder layer, and then solidifying the binder layer, comprising: The method for producing a tile having a photocatalytic function, wherein 0 ≦ δt−δb ≦ 3.0, where δt is the weight and δb is the specific gravity of the binder layer. 14. The method for producing a tile having a photocatalytic function according to claim 12 or 13, wherein the photocatalyst particles are ZnO, and the metal particles filled in the gaps between the photocatalyst particles are Ag or Ag ₂ O. A method for producing a tile having a photocatalytic function, characterized in that: 15. The method for producing a tile having a photocatalytic function according to claim 6, wherein an insoluble colorless or white salt is formed between the photocatalytic particles and metal ions filling the gaps between the photocatalytic particles. A method for producing a tile having a photocatalytic function, comprising bringing a solution containing salts into contact with a photocatalyst layer, and thereafter irradiating light containing ultraviolet rays. 16. The method for manufacturing a tile having a photocatalytic function according to claim 4, wherein the photocatalyst particles are TiO ₂ , and a heat treatment temperature for softening the binder layer is 800 ° C. or more and 1000 ° C. or less. A method for producing a tile having a photocatalytic function, characterized in that: 17. The method for producing a tile having a photocatalytic function according to claim 15, wherein the photocatalytic particles are made of TiO _2.
The metal particles filled in the gaps of the photocatalyst particles are Ag, and the solution containing salts which form insoluble and colorless or white salts with ions of the metal is KI, KC
l, a manufacturing method of a tile having a photocatalyst function, which is a halide solution, such as FeCl _3. 18. The method for producing a tile having a photocatalytic function according to claim 4, wherein the binder layer is selected from those having a softening temperature lower than the softening temperature of the substrate. 20 ° C below softening temperature
A method for producing a tile having a photocatalytic function, wherein the heat treatment is performed at an ambient temperature in the range of more than 320 ° C. and lower than the softening temperature of the substrate. 19. The method of manufacturing a tile having a photocatalytic function according to claim 4, wherein the manufacturing method includes a dispersing step as a step before the step of applying the photocatalyst particles on the binder layer. A photocatalytic function characterized by using only a component that evaporates at a temperature lower than a heat treatment temperature for softening a binder layer, as a dispersant for dispersing a sol or a precursor to be a photocatalyst particle in a process in a solution. A method for producing a tile having: