Multi-functional material with photocatalytic functions and method of manufacturing same

The first multifunctional material with photocatalytic function and its manufacturing method This application is that the application date is December 9, 1994, the application number is 02122422. 6, the title of the invention is "multifunctional material with photocatalytic function and its manufacturing method" Divisional application of the application.

TECHNICAL FIELD The present invention relates to a multifunctional material exhibiting de-agricultural function, antibacterial function, sterilization function, antifouling function, and the like, and a method for producing scorpion.

2. Description of the Related Art So far, TiOz, ν are known as substances that cause the adsorption or desorption of oxygen molecules by organic compounds such as malodorous components and promote their decomposition (oxidation) by irradiating ultraviolet rays.₂ 0,> ZnO> V0₃Etc., especially the crystalline anatase type ΤίΟζ particles have high effect as a photocatalyst, so it has been suggested to form a photocatalyst layer on the surface of wall materials, tiles, glass (mirror), circulating filter devices or sanitary ceramics, etc. .

The method of forming the above-mentioned photocatalyst layer is known to use CVD method (chemical phase deposition method), machine injection method, electron beam evaporation method, etc. on the surface of substrates such as plastics, porcelain, and tree food. Method of photocatalyst layer composed of TiOz particles and the like.

However, when the CVD method, the right beam method, the electron beam vapor deposition method, etc. are used, the equipment scale is large and the yield is low, so the manufacturing cost is high.

Other methods of forming the photocatalyst layer are known as the method of smelting the photocatalyst particles into the binder and coating them on the surface of the substrate by spraying methods, or applying heat treatment after dip coating by dip coating. Method (Special Publication No. 5 -201747).

However, in order for the photocatalyst particles such as TiOz particles to exert the photocatalyst effect, it is necessary to irradiate the photocatalyst particles with ultraviolet rays and expose the photocatalyst particles to decomposing substances such as malodorous gases. However, if the photocatalyst is used as in JP 5-201747 If the particles are kneaded into the binder and then applied to the substrate, the Kudo photocatalyst glumes will be buried in the binder layer, which cannot be reached by ultraviolet rays, and cannot be exposed to malodorous gases, so that the catalytic function cannot be fully exerted. .

200610101461.3 Another known method for forming the catalyst layer is the alkane gas based compound method disclosed in Shikai Hei 5-7394. In this method, titanium alkoxide is coated on a glass substrate, coal is dried and then calcined at several hundred degrees (Celsius) to form a photocatalyst layer, and the photocatalyst layer is irradiated with ultraviolet rays to decompose organic matter in the water.

The above-mentioned alkoxy compound method can form a thin film at a lower temperature. This is an advantage. As a substrate, it is possible to effectively use substrates that are difficult to soften up to 50 °C, such as visual glass and quartz glass, as raw materials. However, for example, in the case of using a material with a low melting point such as soda lime glass as the substrate, the substrate is already softened at the temperature at which the film is formed, and the formed photocatalyst film is embedded in the substrate, so the light cannot reach the distance. The photocatalyst layer causes the so-called failure of the photocatalytic function.

In addition, in JP 1-288321, the TiOw sol is sprayed on the cake-based material ceramic paper, heat-treated at 400-700Ό, then Sn()2 sol is sprayed, and heat-treated at 400700'C to form a Photocatalyst coating that improves the oxidation and decomposition of aldehydes.

In the method disclosed in JP Hei I-288321, the entire surface of the coating film is covered with SnOz, which is less active than TiO=. Moreover, when the film strength is increased, cracks are likely to occur. That is, as shown in FIG. 1(a), a sol containing TiOz particles 101 is applied to the surface of the tile 100, and if it is heat-treated (sintered), cracks 102 are generated as shown in FIG. 1(b). The reason for this is not only the volume shrinkage (increase in density) caused by the transformation to the rutile phase, but also because the interval between the TiOz particles 101 before sintering is Lo as shown in Figure 2(a), but the rutile type is shown in Figure 2 after sintering. As shown in (b), due to the diffusion to the volume of the other party, the interval between the particles is shortened to L] (Ll<L.). Therefore, it can be considered that the pattern is produced as a result.

On the other hand, Japanese Patent Application Publication No. 4-46609 discloses a method for cleaning and deodorizing the interior of the vehicle. This is a method of decomposing or modifying the odorous substances contained in the odor of the air in the vehicle cabin to purify the interior of the vehicle. The odor method is characterized by irradiating a semi-specified body with a semiconductor solid photocatalyst formed by supporting a metal or a metal oxide while contacting the air in the cabin to be purified with the photocatalyst, thereby decomposing by photochemical reaction Or modify the malodorous substances contained in the underworld in the empty scroll.

However, when a substrate coated with a photocatalyst on its surface is used in environments such as sewage and outer walls, the atmosphere or water contains macromolecules, dirt, fungi, etc., and it is easy to adhere to pollutants, because it adheres to different types of pollutants. Pollutants, there are cases where the function of the photocatalyst is reduced.

200610101461.3 The first strategy to deal with the degradation of photocatalyst function caused by the adhesion of pollutants can be found in Special Publication No. 6-7905. In Special Publication No. 6-7905, a deodorization device using a photocatalyst is disclosed. It consists of a semiconductor photocatalyst layer, and The oppositely arranged ultraviolet lamp, heating element and hair dryer are formed to move the photoabrasive agent layer or heating element, or the photocatalytic penalty layer and heating element to sequentially heat the entire photocatalyst, and remove high molecules and dust by heating to around 40LC Contamination caused by the like causes the regeneration of the photocatalyst layer.

However, with this method of photocatalyst regeneration, it is difficult to actually implement the parts used in the equipment installed indoors. Therefore, it is desirable that the contamination is not removed after the photocatalyst layer has adhered to it. Of course, the contamination is not easy to adhere. Or to solve the problem fundamentally, so that the adhesion of pollution will not reduce the photocatalyst function.

In addition, in Tehei 6-7906, it is revealed that the strong light of ultraviolet intensity is used to irradiate the photochemical agent to remove the malodor in the home and office. However, when the strong light of ultraviolet intensity is irradiated, the structure of the photocatalyst is different. The decomposition rate of malodor is different. In addition. In the above example, the substrate is porous, and sufficient mechanical strength is obtained by impregnation, etc. However, when the substrate is non-porous materials such as glazed tiles and denser and fine ceramics, sufficient mechanical strength cannot be obtained. Mechanical strength.

In addition, in TiOz, there are different crystal forms such as anatase, brookite, and rutile. In terms of photoactivity, the anatase type is superior, and the photoactivity of other crystal types is not so good. However, even rutile-type Ti (b, supporting metals such as P t and Ag can also improve photoactivity (Reported in "Surface" magazine 1987, Vo] 25), but it has excellent odor removal rate, compactness and Adhesiveness is not sufficient. Especially when metals Ag and AgO are added, they are not suitable for ceramics and building materials because they are black.

In addition, because the titanium sol prepared by hydrothermal method or sulfuric acid method is composed of ultrafine particles, it is easy to agglomerate. If the polymer is coated on the surface of the substrate, it will become the cause of light spots and cracks. Therefore, in order to prevent agglomeration, a method of attaching an organic dispersant such as triethanolamine to the surface of the titanium oxide sol has been adopted.

However, when an organic dispersant such as triethanolin is used to adhere to the surface of the titanium oxide sol, a monodispersed oxidized soft sol is coated on a substrate with low heat resistance, such as a resin substrate, if it is less than 30 ( TC is used for calcining the stomach, because the active point organic dispersant of the titanium oxide sol is firmly fixed, and it is not fully evaporated and decomposed even during the calcining process, so it is obtained in this way.

200610101461.3 The first member does not have sufficient photocatalysis, and the deodorization and antibacterial properties are not sufficient.

In addition, Japanese Patent Laid-Open No. 5-253544 discloses a method of mixing sharp-drinking ore-type titanium oxide into a binder, coating it on the surface of the substrate, and then performing a heat treatment. The method is to form an adhesive layer on the surface of a plate-shaped member constituting the wall, floor or ceiling surface of the living space, and spray the photocatalyst mainly composed of anatase titanium oxide on the surface of the adhesive layer Fine powder, with a part of it exposed from the adhesive layer, so that it adheres to the surface of the adhesive layer, and then heated in the range of 30°C or more and 9°C or less to melt the adhesive layer, and then cool , In order to cure the adhesive.

In this method, if the heat treatment is performed at a temperature above 30°C and below 900*C., the deodorization performance is good, but good deodorization performance cannot be obtained at a low temperature below 30°C. Therefore, it is difficult to obtain good deodorization performance in heat-labile plastics. A photocatalyst with excellent release properties is added to the material. The reason can be considered to be that in order to uniformly coat the photocatalyst particles on the substrate, it is necessary to monodisperse the photocatalyst fine particles in a suspension. The organic dispersant is not fully decomposed, vaporized, and left to cover the active sites on the photocatalyst particles below 302C.

Therefore, the object of the present invention is to provide a multifunctional material capable of fully exerting the photocatalytic effect in such a way that the photostiffening agent layer is exposed from the base material, and using the base material to protect the specific photocatalyst layer particularly well.

In addition, the object of the present invention is to form a photocatalyst layer that is not easy to peel off on relatively dense substrates such as glass, ceramic tiles, metals, and plastics.

In addition, the object of the present invention is to form a photocatalyst layer on a low-melting-point substrate, such as a soda lime glass that is relatively inexpensive and easy to process.

In addition, the object of the present invention is to provide such a multifunctional material that is not easy to adhere to contaminants, can prevent functional degradation caused by contaminants, has antibacterial or deodorant properties, and has excellent mechanical strength.

In addition, the object of the present invention is to provide a multifunctional material with excellent peeling strength even with a photocatalyst layer mainly composed of titanium ore type ΤΙΟζ.

In addition, the object of the present invention is to improve the photocatalytic activity of a photocatalyst layer mainly composed of rutile type T10ζ.

Furthermore, the purpose of the present invention is to use rutile TiOz as the main photocatalyst

200610101461.3 Ag is supported on the first layer to improve the photocatalytic activity and at the same time decolor the photocatalyst layer to make the appearance better. In addition, the object of the present invention is to provide a multifunctional material having a good photocatalytic function even if it is subjected to low-temperature heat treatment below 3DITC.

Disclosure of the Invention The present invention provides a multifunctional material with photocatalytic function, comprising a substrate; having a photocatalytic function and a photocatalyst layer provided on the surface of the substrate, the photocatalyst layer containing exposed to the outside At least one surface layer of the surface layer, the surface layer is composed of fine photocatalyst particles, the photocatalyst particles are combined to form a gap with a predetermined porosity; particles smaller than the gap are filled in the gap; The particles filled in the gaps formed between the photocatalyst particles have photocatalytic activity.

The present invention also provides a method for preparing a multifunctional material with photocatalytic function. The material has photocatalyst particles that form gaps between the photocatalyst particles and is filled with particles having a particle diameter smaller than these gaps. The method includes the following steps : Forming a photocatalytic layer on the surface of the substrate, then coating a metal alkoxide or organic metal salt on the surface of the photocatalytic layer, and then drying and heating the coated metal alkoxide or The organic metal salt fills the gap formed between the photocatalyst particles with particles smaller than the gap.

In one embodiment, the method further includes the following steps: coating the dried material with an aqueous solution of at least one metal ion among Cu, Ag, Zn, Fe, Co, Ni, Pd and Pt, and photoreduced The solution is applied to precipitate and fix metal particles.

In one embodiment, wherein the photocatalyst particles are bonded together.

The present invention also provides a method for preparing a multifunctional material with photocatalytic function, which has photocatalyst particles that form gaps between photocatalyst particles and is filled with particles having a particle diameter smaller than these gaps, and the photocatalyst particles are Together, the method includes the following steps: Coating a mixture of photocatalyst particles and the smaller particles on a thermoplastic substrate in the form of a sol, precursor or suspension, thereby forming a photocatalyst layer, and thereafter The thermoplastic substrate is softened to embed the lower part of the photocatalyst layer in the thermoplastic substrate, and then the thermoplastic substrate is cured.

In one embodiment, the method further comprises the following steps: before coating the photocatalyst particles on the thermoplastic substrate, dispersing the photocatalyst and the sol, precursor or suspension of smaller particles with a dispersant into the solution In this, the dispersant consists of only one component, which vaporizes at a temperature lower than the heat treatment temperature to soften the thermoplastic substrate.

In one embodiment, the method further includes the following steps: prepare the titanium dioxide sol according to the hydrothermal method or the sulfuric acid method, form photocatalyst particles, fix the fine metal particles on the surface of the titanium dioxide sol particles, and then apply the dispersant or the surface A treatment agent such as a surfactant is added to the titanium dioxide sol.

In one embodiment, the method further includes the following steps:

200610101461.3 First, the photocatalyst layer is contacted with the salt-containing solution to form an insoluble, colorless or white salt with the metal ions of the particles filled in the gaps between the photocatalyst particles, and then the solution is irradiated with light containing ultraviolet rays. Preferably, wherein the photocatalyst particles are made of Ti. ? Made, the metal particles filled in the gaps between the photocatalyst particles are made of Ag, and the solution contains a salt to be compatible with halides such as KI, KCL·FeCl₃The metal ions of other aqueous solutions form insoluble, colorless or white salts.

In one embodiment, the method further includes the following steps: coating an aqueous solution of at least one metal ion among Ni, Pd, and Pt on the buried photocatalyst layer, and photoreducing the coated solution to Precipitate and fix metal particles.

The multifunctional material of the present invention is a material obtained by forming a photocatalytic agent layer directly or through a binder layer on the surface of ceramics, sanitary ceramics, glass and other ceramics, resins, metals, woods, etc. The type and size of the photocatalyst particles of the photocatalyst layer, the gaps formed between the photocatalyst particles, the porosity, the relationship between the binder layer and the photocatalyst layer, the floating particles that fill the gaps between the photocatalyst particles, especially those fixed in the light There are no special requirements for the metal particles on the surface of the catalyst particles. With these, a multifunctional material with excellent photocatalytic effect as a photocatalyst layer for deodorization, etc., and excellent antibacterial and abrasion resistance can be obtained.

Brief description of the drawings

1(a) is a circle showing the state of the conventional TiOw sol before sintering, and (b) is a diagram showing the state of the rutile type after sintering.

Fig. 2 (a) is a diagram showing the state of a conventional TiOw grain before sintering, and (b) is a diagram showing the state after sintering.

3 is a diagram showing a state in which the photocatalyst particles constituting the photocatalyst layer are combined with each other by potential energy in the multifunctional material with photocatalytic function of the present invention.

Fig. 4 is a diagram schematically showing a state in which the photocatalyst particles constituting the photocatalyst I layer are solid-phase sintered and bonded in the same multifunctional material.

Fig. 5 is a diagram schematically showing a state in which small particles are filled in the thinning formed between the photocatalyst particles constituting the photocatalyst layer in the same multifunctional material.

Fig. 6 schematically shows a state in which metal particles are immobilized on the surface of the photocatalyst particles of the multifunctional material shown in Fig. 3.

FIG. 7 is a diagram schematically showing a state where metal particles on the surface of the photocatalyst particles of the multifunctional material shown in FIG. 4 are nationalized.

Fig. 8 is a schematic diagram showing the surface of the photocatalyst particles of the multifunctional material shown in Fig. 5

200610101461.3 The state diagram of the upper metal particles being immobilized.

FIG. 9 is a diagram schematically showing a state in which the photocatalyst layer is combined with the substrate through the binder layer in the same multifunctional material, and the photocatalyst particles constituting the photocatalyst layer are combined with each other by potential energy.

prison10 is a diagram schematically showing that in the same multifunctional material, the photocatalyst layer is joined to the substrate through the adhesive layer, and the photocatalyst particles constituting the photocatalyst layer are combined with each other by solid-phase sintering. .

Fig. 11 is a diagram schematically showing the state in which the photocatalyst layers are joined by the adhesive layer in the same multifunctional material, and the gaps formed between the photocatalyst particles are filled with small particles.

Fig. 12 is a diagram schematically showing a state in which metal particles are immobilized on the surface of the photocatalyst particles of the multifunctional material shown in Fig. 9.

FIG. 13 is a diagram schematically showing a state in which the metal linked particles are identified on the surface of the photocatalyst particles of the multifunctional material shown in FIG. 1D.

Fig. 14 is a diagram schematically showing a state in which metal particles are immobilized on the surface of the photocatalyst particles of the multifunctional material shown in Fig. 11.

Figure 15 is a diagram illustrating the manufacturing method of the multifunctional material with photocatalytic function of the present invention. Figure 16 (a) and (b) are enlarged views of Ti-particles.

Figure 1 7 (a)-(c) is to explain T)0₂Diagram of the sintering mechanism of the particles.

Fig. 18 shows the curve of the fruit of the antibacterial test.

Figure 19 shows when entering the drying process and not entering the drying process before the BLB lamp is irradiated.

The test results and results of C u Carried Tong are compared to Quqian.

Ring 20 represents the relationship curve between the Cu support amount and the Cu coating amount.

Fig. 21 is a manufacturing process diagram showing another embodiment.

Figure 22 shows the test result curve of the antibacterial test.

Close 2 3 means when entering the dry image process and not entering the dry process before the BLB lamp is irradiated,

Comparison curve of test results of Cu loading capacity.

Figure 24 shows the relationship between the Cu loading and the Cu coating.

Figure 25 shows the relationship between Ag loading and bacterial survival rate.

200610101461.3 Fig. 26 A conceptual diagram of the basic distribution of multifunctional materials when observing the cross-sectional direction of the multifunctional material with EPMA (Electron Beam Microanalyzer).

Fig. 27 is a conceptual diagram of the basic distribution when observing the cross-sectional direction of the multifunctional material with EPMA (Electron Beam Microanalyzer). Fig. 28 shows the relationship curve between the combination of TiOz and SnOz and the film strength and smoothness.

Figure 29 shows the relationship between heat treatment temperature and finish.

Fig. 30 is a diagram illustrating the method of measuring the activity of the photocatalyst thin film.

Fig. 31 is a diagram illustrating a method for measuring the activity of a photocatalyst thin film.

Figure 32 is a diagram illustrating the method of measuring the activity of the photocatalyst thin film.

Figure 33 shows the relationship between the UV irradiation time and the change in pH.

Figure 34 shows Rs. The relationship curve with the amount of pH change.

Figure 35 shows the relationship between porosity and deodorization (Rs.) and abrasion resistance.

Figure 36 shows the relationship between the film thickness and the anti-Half property (R 3.).

Figure 4 Curve.

7 represents the relationship curve between film thickness and deodorization (R 3.) and peel resistance.

The relationship curve between the amount of addition and the deodorization (R") and abrasion resistance. The relationship curve between the amount of addition and the difficulty of pollution adhesion.

The relationship between the amount of addition and the open porosity on the surface of the TiO? layer.

The relationship between the addition amount and the width of the open pores on the surface of the Ti (h layer).

The relationship between the amount added and the deodorant R"(L) and peeling resistance

8 means SnOz

9 means SnOz

0 means SnOz

1 means SnOz

2 shows SnON. Figure 43 shows the relationship curve between the number of coatings and the difficulty of dirt adhesion.

Figure 44 shows the relationship between the number of coatings and abrasion resistance.

Figure 45 shows the relationship between the number of coatings and the open porosity of the Ti(h layer).

Figure 46 shows the irradiation of ultraviolet rays to give priority to the thermosetting resin on the photocatalyst particles

200610101461.3 The photocatalyst particles are exposed to the air through decomposition and vaporization.

Fig. 47 is the same diagram as Fig. 47 showing other embodiments.

Fig. 48 is the same diagram as Fig. 47 showing other embodiments.

Fig. 49 is a diagram showing a state in which small particles are filled in the gaps of the photocatalyst particles.

Fig. 50 is a block diagram showing the manufacturing process of a multifunctional material using rutile TiOw.

Figure 51 shows the relationship curve between the concentration of the G u solution and the photoactivity when the Cu solution is dried for photoreduction.

Figure 52 shows the relationship between the concentration of the Cu solution and the photoactivity when the Cu solution is not dried for photoreduction.

Figure 53 shows the Cu solution concentration and malodor removal rate R.3 when Cu is used as the supporting metal on the rutile TiOz film. (The reduction of metal ions is carried out after drying the metal salt aqueous solution).

Figure 54 shows the Cu solution concentration and the odor removal rate Rs when the wall tiles are used as the base and Cu is used as the supporting metal on the rutile Ti5 film. (The reduction of metal ions is carried out after the metal salt aqueous solution is dried).

Figure 55 shows the relationship curve between the burning temperature of the rutile-type Ti(h) film and the odor removal rate R3 after the immobilization of Cu.

Figure 56 shows the relationship curve between the solution concentration of A g and Cu and the color difference.

Figure 57 shows porosity and R3. And the relationship curve of wear resistance.

Fig. 5B shows the relationship curve between the amount of copper supported and the survival rate of the bacteria.

Figure 59. Shows the relationship between the amount of copper coating and the amount of copper supported.

Figure 60 shows the relationship between the amount of silver carried and the survival rate of bacteria.

Fig. 61 is a graph showing the relationship between the amount of silver supported and the chromatic aberration.

Figure 62 shows the effect curve of the decolorization treatment with the KI aqueous solution.

200610101461.3 Figure 63 shows the performance of the KI aqueous solution before and after the decolorization treatment with the KI aqueous solution.

PH change and malodor removal rate Rs. Change the relationship curve.

Figure 64 is a graph comparing antibacterial effects.

Fig. 65 shows a graph of the abrasion resistance relative to the weight ratio of tin oxide in the film.

Figure 66 shows a graph of the photoactivity relative to the weight ratio of tin oxide in the thin film.

Fig. 67 is a graph showing abrasion resistance with respect to the weight ratio of tin oxide in a thin film as a comparative example.

Fig. 68 shows a graph of the photoactivity relative to the weight ratio of tin oxide in the thin film as a comparative example.

Figure 69 shows the relationship between the amount of silver carried and the survival rate of bacteria.

Best Mode for Carrying Out the Invention In order to describe Kui's invention in more detail, the invention will be explained in accordance with the accompanying drawings.

Figures 3 to 14 divide the structure of the multifunctional material with photocatalytic function of the present invention into various types, and the multifunctional material with photocatalytic function of the present invention belongs to one of the structures.

In the multifunctional material shown in FIG. 3, a photocatalyst layer 2 with a photocatalytic function is directly provided on the surface of a substrate 1. The photocatalyst layer 2 is composed of fine photocatalyst particles 3 with surface energy and curved surface energy between each other. It is composed of a combination of potential energy.

In the multifunctional material shown in FIG. 4, a photocatalyst layer 2 having a photocatalytic function is directly arranged on the fur surface of the substrate 1, and the photocatalyst layer 2 is formed by the solid phase bonding of the photocatalyst particles 3.

In the multifunctional material shown in FIG. 5, a photocatalyst layer 2 having a photocatalytic function is directly provided on the surface of a substrate 1, and the gaps formed between the photocatalyst particles 3 constituting the photocatalyst layer 2 are filled more than this Particles 4 with smaller gaps are formed by combining photocatalyst particles 3 with each other through such small particles 4.

In addition, in this figure, it shows a structure in which particles 4 are filled into the internal gap.

200610101461.3 However, the particles 4 may be filled at least in the gaps of the surface layer photocatalyst particles 3. That is, in terms of the mechanical strength of the photocatalyst layer, in order to attenuate the transmission of external force internally, it can be considered that the surface bonding is required. Therefore, it is possible to fill fine particles only in the gaps of the photocatalyst particles on the surface layer. However, at this time, the internal photocatalyst particles are combined by potential energy. In order to obtain sufficient photocatalyst layer strength, the average particle size of the photocatalyst particles is preferably 0.04μπΐο. In the multifunctional material shown in FIG. The photocatalyst particles 3 directly forming the photocatalyst layer 2 on the surface of 1 are combined with each other with potential energy. On the surface of the photocatalyst particles 3, electron trap particles 5 such as Ag, Cu and Cun 0 are also fixed.

In the multifunctional material shown in FIG. 7, the photocatalyst particles 3 constituting the photocatalyst layer 2 directly formed on the surface of the substrate 1 are bonded to each other by a solid phase sintering phase, and A is also fixed on the surface of the photocatalyst particles 3 Metal particles 5 such as g and P t. In the multifunctional material shown in FIG. 8, a photocatalyst layer 2 having a photocatalytic function is directly provided on the surface of the substrate 1, and the photocatalyst particles constituting the photocatalyst layer 2 The gap formed between 3 is filled with particles 4 smaller than the gap. Through this small particle 4, the photocatalyst particles 3 are combined with each other, and Ag and P t are also fixed on the surface of the photocatalyst particle 3 ο In the multifunctional material shown in FIG. 9, a photocatalyst layer 2 with a photocatalytic function is provided on the surface of the substrate 1 through an adhesive layer 6. The photocatalyst layer 2 is exposed to the outside while the lower layer It is embedded in the adhesive layer 6, and the fine photocatalyst particles 3 on the surface layer are combined with each other by potential energy.

In the multifunctional material shown in FIG. 10, the photocatalyst layer 2 is also provided by the binder layer B. On the surface of the photocatalyst layer 2, the photocatalyst particles 3 are combined with each other by a solid phase sintering phase.

Figure 1! In the multifunctional material shown, the photocatalyst layer 2 is provided on the substrate i through the adhesive layer 6, and the photocatalyst layer 2 is formed between the photocatalyst particles 3 constituting the photocatalyst layer 2.

200610101461.3 The first gap is filled with particles 4 smaller than the gap, and the small particles 4 photocatalyst particles 3 are combined with each other.

In the multifunctional material shown in Fig. 12, a photocatalyst layer 2 is formed on the surface of a base material 1 through an adhesive layer 6, and the photocatalyst particles 3 constituting the photocatalyst layer 2 are bonded to each other with potential energy. Ag, Cu and Cu are also fixed on the surface of the photocatalyst particles 3₂ 0 Iso electron capture particles 5.

In the multifunctional material shown in FIG. 13, a photocatalyst layer 2 is formed on the surface of a substrate 1 through a binder layer 6, and the photocatalyst particles 3 constituting the photocatalyst layer 2 are bonded to each other by a solid phase sintering phase. , On the surface of the photocatalyst particles 3, electron trap particles 5 such as Ag, Cu, and Cuz 0 are also fixed.

In the multifunctional material shown in FIG. 14, the photocatalyst layer 2 is provided on the base material 1 through the adhesive layer 6, and the gap formed between the photocatalyst particles 3 constituting the photocatalyst layer 2 is filled more than the gap The small particles 4 are combined with each other through the photocatalyst particles 3, and metal particles 5 such as Ag and Pt are also fixed on the surface of the photocatalyst particles 3.

Among the above multifunctional materials, as the base material 1, ceramics such as ceramic tiles, sanitary ware, glass, resin, metal, wood, or composites thereof may be used.

In addition, the so-called photocatalyst particles 3 are semiconductor particles having a very large forbidden band width in order to perform photocatalytic functions such as antibacterial function and deodorizing function. As the reason why the photocatalyst particles have antibacterial properties, although there is a saying that they are electrocuted by applying a voltage higher than a predetermined value, it is generally considered that, like the deodorization function, it is the cause of the generation of active oxygen when light is irradiated. In order to generate active oxygen, one of the conduction bands of the semiconductor is required to be above the hydrogen generation potential when represented by the energy band model, and the upper end of the valence electron band must be below the oxygen generation potential. Among the semiconductors that meet this condition, there are Ti(h, SrTiih, ZnO> SiC, potassium phosphide, CdS. CdSes MoS₃Respect. In addition, if the particles are fine-grained, the position of the conduction band will move upward, so if fine particles of 1-10 run are formed, Sn(h, plus 3, FqCh,

200610101461.3 p.

B12 03 etc. are likely to produce active oxygen. Among them, anatase-type TiOz is particularly preferred because it is chemically stable and can obtain fine particles with high activity at a low cost.

In addition, the so-called electron trap particles refer to particles that trap electrons and prevent recombination of electrons and holes when light is irradiated on the photocatalyst to generate electrons and holes. Specific examples include Ag, Cu, Pt, and Pd. , Ni, Co, Fe, Cuz 0, etc.

In addition, the adhesive layer 6 is made of a thermoplastic material such as glaze, inorganic glass, thermoplastic resin, and solder. In this way, the adhesive layer is composed of a thermoplastic material, and the photocatalyst I can be coated on the adhesive layer at sound temperature by a simple and inexpensive method such as spraying method, and only heat treatment is required to make the substrate 1 and the adhesive layer adhere. The bonding agent layer 6 and the photocatalyst layer 2 are firmly bonded, which is advantageous in terms of manufacturing cost.

In addition, the multifunctional material with photocatalytic function of the present invention is formed by laminating a photocatalyst layer composed of photocatalyst grains on a sheet-shaped adhesive layer composed of a thermoplastic material or embedding a part of the photocatalyst layer in the adhesive layer. After attaching such a sheet-like multifunctional material to the original tiles, sanitary ceramics, building materials, etc., if heated, the original tiles and the like can be added with deodorant, antifouling, antibacterial, and anti-fogging functions.

Since the specific surface area is increased and the photocatalytic activity is improved, the average particle diameter of the photocatalyst particles 3 constituting the photocatalyst layer 2 is preferably 0.3 μm or less.

The thickness of the photocatalyst layer 2 is preferably 0.1 μm-0.9 μm or less, and the photocatalyst particles are partially embedded in the binder layer 6, and the surface of the multifunctional material cannot exhibit catalytic activity. Partially causes bacteria to accumulate in this part, so the antibacterial properties are particularly deteriorated. If it exceeds 0.9um, the deviation of the thickness will increase, and the contamination will not easily fall off when the contamination adheres to the sample. The thickness of the so-called photocatalytic punishment layer here includes from the outermost surface of the photocatalyst film to the part buried in the underglaze layer. Specifically, element analysis such as EPMA (electron beam microanalyzer) is performed to form the main part of the glaze layer. The value of the component element increases, and the distance from the uppermost part to the outermost surface of the part with a constant value is calculated and measured.

200610101461.3 In addition, the method of changing the thickness of the photocatalyst layer 2 can also obtain special effects. That is, if the thickness is 0.2 μm or more and 0.4 μm or less, the light interference effect in the thickness direction of the photocatalyst layer can be used to add an iridescent pattern. In addition, if you want to form only the base color of the substrate, the pattern or these in appearance In addition to the above-mentioned light interference effect, the photocatalyst layer film thickness may be 0.1um or more, 0.2 pm or less, or 0.4 μιη or more and 1 um or less. Such a method can be used in a wide range of tiles, sinks, bathtubs, toilets, sinks, kitchen tables, etc.

In the case where only the photoactive agent particles 3 are bonded to each other, only the potential energy (adsorption) or sintering between the photocatalyst particles is used. However, when using the mutual sintering effect of the photocatalyst particles, sintering must be carried out at a relatively high temperature. On the other hand, in the case of using adsorption, if the specific surface area of the photocatalyst particles is not made quite large, and if the filling performance is not made good , The bonding is not enough, only the active point adsorption part of the photocatalyst particles is consumed, and the production of multifunctional materials with sufficient catalytic activity and abrasion resistance is limited in terms of methods.

In addition, in order to strengthen the bonding of the photocatalyst particles 3, if particles larger than the gaps between the photocatalyst particles 3 are used, sufficient bonding force may not be obtained, and the photocatalyst particles exposed on the surface of the multifunctional material will be partially covered. Granules produce parts that cannot exhibit catalytic activity on the surface of the multifunctional material, and bacteria are retained on this part, so the antibacterial properties are significantly deteriorated.

In addition, the gap between the photocatalyst particles mentioned here refers to the necked part between the photocatalyst particles 3 and 3 as shown in FIG. 16(a), and as shown in FIG. 16(b), the photocatalyst particles 3 , 3 pores between. Therefore, the small particles 4 having a particle size smaller than the gap between the photocatalyst particles refer to particles having a smaller gap than either the necked portion between the photocatalyst particles and the pores between the photocatalyst particles. There is a particularly effective method for bonding the photocatalyst particles to each other as shown in Fig. 16(b).

The small particles 4 filled in the gaps of the photocatalyst particles 3 are basically not limited in material, but may be materials with good adsorption power. The material with extremely weak adsorption capacity cannot achieve the photocatalysis

200610101461.3 The purpose of combining the first chemical particles with each other. In addition, when a material with a strong adsorption capacity is used to cover the active points on the surface of the photocatalyst particle instead of being inserted into the gap, the probability increases. From this point of view, as the material of the particles filled in the gaps of the photocatalyst particles, metals or oxides such as Sn, Ti, Ag. Cu, Zn, Fe, Pt, Co, Pd, Ni, etc. are ideal. The zeolite, activated carbon, clay, etc. used in the body are not ideal. Among the above-mentioned metals or oxides, tin oxide is ideal in terms of having a moderate adsorption capacity. In addition to metals or oxides such as Ag and Cu, which combine the photocatalyst particles with each other, they also have antibacterial properties by themselves. , Odor resistance, so in the use of this function, especially when there is no light irradiation, the function of assisting the photocatalysis is ideal. That is, as the small particles 4 filled in the gaps of the photocatalyst particles 3, the above-mentioned metal particles 5 can be used.

Furthermore, the average particle diameter of the particles 4 filled in the gaps of the photocatalyst particles 3 is preferably 4/5 or less of the average particle diameter of the photocatalyst particles 3.

The particles 4 filling the gaps of the photocatalyst particles 3 are not only attached to the gaps between the photocatalyst particles but also on the photocatalyst particles by the current manufacturing method. Moreover, if the particle size filling the gap exceeds 4/5 of the average particle size of the photocatalyst particles, the probability of adhering to the surface of the photocatalyst particles is higher than the probability of filling the gaps of the photocatalyst particles. Therefore, the photocatalyst particles 3 are separated from each other. The bonding strength is reduced. If the particles filling the gaps are larger than the photocatalyst particles, it is equivalent to partially covering the photocatalyst particles. On the surface of the multifunctional material, there is a part that cannot exhibit catalytic activity. Since bacteria are retained on this part, there is particularly significant antibacterial activity. The possibility of deterioration.

In addition, the average particle diameter of the particles 4 filled in the gaps of the photocatalyst particles 3 is preferably 0.01 μni or less, so that the specific surface area is increased and a moderate adsorption force can be obtained.

Furthermore, the particles 4 filled in the gaps of the photocatalyst particles 3 are measured relative to the photocatalytic cut particles and the stones filled with the bumps 4, preferably in a molar ratio of 10 or more and 60 wax or less. Heat treatment in a temperature region where the photocatalyst particles are not sintered with each other, through

200610101461.3 When the photocatalyst layer is fixed on the substrate by the first adhesive layer, if the amount of particles filling the gap is too small, the photocatalyst particles cannot be firmly bonded to each other. On the other hand, if the particles filling the gap are not If the amount is too large, the amount of particles covering the photocatalyst particles will increase, and a part that cannot exhibit catalytic activity is formed on the surface of the multifunctional material. Since bacteria are retained on this part, the antibacterial property is particularly deteriorated. Therefore, the above range is ideal .

In addition, as the material constituting the particles 4 filled in the gaps of the photocatalyst particles 3, a material having a higher vapor pressure than the material constituting the photocatalyst particles is selected, and it is desirable to fill in the gaps of the photocatalyst particles. The particles agglomerate in the neck braid between the photocatalyst particles. In this way, a stronger bond between the photocatalyst particles can be achieved. In order to increase the peel strength of the photocatalyst layer, not only the filling method but also the sintering method can be used. In addition, if the particles 4 for filling the gap are selected from such a material with high vapor pressure, even if it is used as a sintering aid, the sintering temperature can be lowered.

Such substances with high vapor pressure include tin oxide, tin oxide, zinc oxide, etc., but tin oxide is best for safety reasons.

In addition, the thickness of the layer including the particles 4 filled in the gaps of the photocatalyst particles 3 is preferably 0.1 um or more. The thickness of this layer is less than 0.1 μm, and the photocatalyst particles (and the particles that fill the gap by the manufacturing method) are partially embedded in the adhesive layer 6, forming a part that cannot exhibit catalytic activity on the surface of the multifunctional material. It can retain bacteria on it, so the antibacterial property in particular deteriorates significantly. Here, the thickness of the layer including the particles 4 filled in the gaps of the photocatalyst particles includes the thickness from the outermost surface to the lower layer portion where the adhesive layer is embedded, and the average thickness of the respective convexities and concaves.

Figure 15 illustrates an example of the manufacturing method of the multifunctional material with photocatalytic function of the present invention. In the present invention. First, as shown in Figure 15(a), a substrate 1 is prepared, as shown in Figure (b), A salty adhesive layer 6 is formed on the fur surface of the base material 1. For the adhesive layer 6, a material having a softening temperature lower than that of the base material 1 is selected. As an example, the substrate 1 is

200610101461.3 In the case of ceramic tiles, hollow glass frit or ceramics, the glaze layer or printing layer can be used as the adhesive layer 6 as it is. Then, as shown in the figure (c), TiOz particles are formed on the adhesive layer 6 And other photocatalyst layer 2 composed of photocatalyst particles. At this time, the photocatalyst layer 2 is maintained with a bonding force that does not fall off from the adhesive layer 6 during subsequent firing, and may be supported on the adhesive layer 6.

Alternatively, before the adhesive layer 6 is formed on the surface of the substrate 1, as shown in the figure (b'), the photocatalyst layer 2 may be formed in advance on the adhesive layer 6, and the adhesive layer 6 Cut on the base material 1.

Thereafter, in the range of more than 2 (TC, 320 Ό or less, heat treatment is performed at an atmosphere temperature higher than the softening temperature of the adhesive layer 6 and lower than the softening temperature of the base material 1, as shown in Figure (d) or Figure 9 As shown in Figure 14, in the photocatalyst layer 2, a part of the lower layer on the adhesive layer side is deposited on the molten adhesive layer. Because the adhesive layer is solidified, this part is buried in the adhesive layer. In addition, in the photocatalyst layer 2, the photocatalyst particles 3 constituting the surface layer in contact with the external atmosphere utilize mutual potential energy, intermolecular force, and sintering caused by firing, as shown in Figure 16 ( As shown in a), one part is combined, and the other part is separated as shown in Fig. 16(b). That is, the surface of the photocatalyst particles in the surface layer is substantially exposed to the outside.

Here, the heat treatment temperature is increased to a range higher than the softening temperature of the adhesive layer 6 by more than 2 (TC, 32TC or less. If it is less than 20*C, the softening of the adhesive will take time, and it will not be sufficient. The retention of the photocatalyst particles 3a is completed. On the other hand, if it exceeds 32CTC, the photocatalyst particles will be embedded in the adhesive layer due to the rapid melting of the adhesive layer, resulting in uneven surfaces, and slamming and pores. So I hope 4 or above, 3oor below.

Furthermore, assuming that the specific gravity of the photocatalyst particles 3 is & t, the specific gravity of the adhesive layer H is ^δ b> is to form 0 <δ t-6b and 3.0, preferably 0.5< δ t- δ b<2.0

200610101461.3 The first series. If the specific gravity difference between the photocatalyst particles and the adhesive layer is too small, when the adhesive layer is melted, the moving speed of the photocatalyst particles in the vertical direction in the adhesive layer will slow down, and the photocatalyst particles will easily peel off after calcination. If the specific gravity difference between the photocatalyst particles and the binder layer is too large, the moving speed of the photocatalyst particles in the vertical direction will increase, and most of the photocatalyst particles will be buried in the binder layer. This phenomenon keeps bacteria on it and reduces the antibacterial properties.

Furthermore, as an application of this method, even when 6t-6b>3.0 is necessary, the second adhesive layer with 0 <δ t - can be interposed between the adhesive layer and the photocatalyst particles. .

In addition, in the case of -6bVD, if the pressure is applied during the heat treatment, there is the same effect as increasing the specific gravity-6b. Therefore, through HIP treatment, hot pressing treatment can obtain the same effect as when 0 <δ t-Sb<3.0.

In addition, the gaps between the photocatalyst particles constituting the exposed part of the adhesive layer 6 are specifically shown in FIG. 16(a), the necked part of the photocatalyst particles 3b, or the light as shown in FIG. 16(b). Between the catalyst particles 3, in order to combine the photocatalyst particles with each other, particles 4 (Sn, Ti, Ag, Cu, Zn, Fe, Pt, Co, P d, Ni and other metals) having a particle diameter smaller than the gap can be filled. Or oxide, etc.).

In addition, as another method of manufacturing the multifunctional material with photocatalytic function of the present invention, it is also possible to form an adhesive layer 6 composed of a thermoplastic material on a substrate 1 such as ceramics, resins, or metals, and then, on the adhesive The layer 6 is coated with a mixture of photocatalyst particles 3 and particles 4 with small particle diameters in a sol or precursor state to form the photocatalyst layer 2. After that, the adhesive layer 6 is softened to make the photocatalyst layer 2 A part of the lower layer is buried in the adhesive layer 6, and then cured.

According to this method, it is not only simple, but also because it is coated with a mixture of particles 4 and photocatalyst particles 3 pre-filled into the gap in a sol or precursor state to form a photocatalyst layer.

200610101461.3 Therefore, it is very convenient to control the mixing ratio of the photocatalyst particles 3 and the particles 4 buried in the gap.

In addition, as another manufacturing method of the multifunctional material with photocatalytic function of the present invention, the sheet-shaped adhesive layer 6 composed of a thermoplastic material may be coated with photocatalyst particles 3 and mixed in a sol or precursor state. A mixture of particles 4 with small particle diameters forms the photocatalyst layer 2. The flake-shaped adhesive layer 6 forming the photocatalyst layer 2 is planted or pasted on a substrate such as ceramic, resin, or metal, and then the above-mentioned bonding The agent layer is softened, and a part of the lower layer of the photocatalyst layer is embedded in the adhesive, and then cured.

Furthermore, as another method of manufacturing the multifunctional material with catalytic function of the present invention, it is also possible to form an adhesive layer 6 composed of a thermoplastic material on a substrate 1 such as ceramics, resins, or metals, and then, on the adhesive A photocatalyst layer 2 composed of photocatalyst particles 3 is formed on the layer 6. After that, the adhesive layer 6 is softened, a part of the lower layer of the photocatalyst layer 2 is buried in the adhesive layer, and then the adhesive layer is cured Then, the solution containing the small particle size particles is coated on the photocatalyst layer, and the small particle size particles 4 are fixed on the photocatalyst particles by heat treatment.

This method is easy to implement when the particles that fill the gaps are oxides, and when a porous photocatalyst layer is produced, a large number of particles that fill the gaps can be attached.

Also, as another method of manufacturing the multifunctional material with photocatalytic function of the present invention, it is also possible to form a photocatalyst layer 2 composed of photocatalyst particles 3 on a sheet-like adhesive layer 6 composed of a thermoplastic material, and then The sheet-like adhesive layer forming the photocatalyst layer is placed or pasted on a substrate 1 such as ceramic, resin, or metal. After that, the adhesive layer 6 is softened and a part of the lower layer of the photocatalyst layer 2 is buried in the adhesive. In the binder layer 6, the adhesive layer is then cured, and then a solution containing metal particles 4 is coated on the photocatalyst layer, and the above-mentioned small particle size particles are fixed on the photocatalyst particles 3 by heat treatment.

In addition, as other manufacturing methods of the multifunctional material with photocatalytic function of the present invention

200610101461.3 Method, it is also possible to form an adhesive layer 6 composed of a thermoplastic material on a substrate 1 such as ceramics, resins, or metals, and then form a photocatalyst layer 2 composed of photocatalyst particles 3 on the adhesive layer 6 After that, the above-mentioned adhesive layer is softened, a part of the lower layer of the photocatalyst is buried in the adhesive layer, and then the adhesive layer is cured, and then the photocatalyst layer is coated with ions containing small metal particles 4 The solution is then irradiated with ultraviolet light to reduce the metal ions and fix them on the photocatalyst particles.

This method is easy to implement when the particles in the filling gap are metal, and the metal can be fixed in a very short time (several minutes). In addition, the lamp used for ultraviolet irradiation may be any of an ultraviolet lamp, a BLB lamp, a gluten lamp, a mercury lamp, and a fluorescent lamp.

Furthermore, as another manufacturing method of the multifunctional material with photocatalytic function of the present invention, a photocatalyst layer composed of photocatalyst particles can also be formed on a sheet-shaped adhesive layer composed of a thermoplastic material, and then a photocatalyst layer is formed. The flaky adhesive layer 6 of the catalyst layer is placed or pasted on a substrate 1 such as ceramic, resin, or metal. After that, the adhesive layer 6 is softened, and a part of the lower layer of the photocatalyst layer is buried in the adhesive layer. In 6, the adhesive layer 6 is then cured, and then a solution containing the ions of the small particle size metal particles 4 is coated on the photocatalyst layer 2, and then light containing ultraviolet rays is irradiated to reduce the metal ions and fix them on the photocatalyst particles. on.

In addition, as another method of manufacturing the multifunctional material with photocatalytic function of the present invention, an adhesive layer 6 composed of a thermoplastic material may be formed on a substrate 1 such as ceramics, resins, or metals, and then bonded to A photocatalyst layer 2 composed of photocatalyst particles 3 is formed on the agent layer 6, and a solution containing the ions of the small particle size metal particles 4 is coated on the photocatalyst layer 2. In this case, light containing ultraviolet rays is irradiated to make the metal ions It is reduced and fixed to 3 ± of the amount of the photocatalyst, and then the adhesive layer 6 is softened, so that a part of the lower layer of the photocatalyst layer is buried in the adhesive layer. Then the adhesive layer is cured.

According to this method, because the heat treatment process can be completed at one time, the productivity can be improved.

200610101461.3 The first yield.

Furthermore, as another manufacturing method of the multifunctional material with photocatalytic function of the present invention, a photocatalyst layer 2 composed of photocatalyst particles 3 may also be formed on a sheet-like adhesive layer 6 composed of a thermoplastic material. The photocatalyst layer 2 is coated with a solution containing ions of metal particles 4 with small particle diameters, and then irradiated with light containing ultraviolet rays to reduce the metal ions to be fixed on the photocatalyst particles 3, and then the photocatalyst layer 2 is formed A sheet-like adhesive layer is placed or pasted on a substrate 1 such as ceramics, resins, or metals. After that, the adhesive layer 6 is softened, and a part of the lower layer of the photocatalyst layer 2 is embedded in the adhesive layer, and then Curing the adhesive layer.

Here, ZnO may be used as the photocatalyst particles, and Ag or Agw 0 may be used as the metal particles 4 filled in the gaps of the photocatalyst particles. Ag or Agz 0 particles not only strengthen the binding of the photocatalyst ZnO particles to each other, but also enhance the photocatalytic effect of ZnO, and they also have antibacterial and deodorant effects. In addition, because ZnO is selected as the photocatalyst, the coloring induced by Ag ions can be eliminated, and unexpected effects can be obtained by using the background color, pattern, or combination of the substrate.

In addition, between the metal ions filling the gaps of the photocatalyst particles, a solution containing a salt that forms an insoluble colorless or white salt may be brought into contact with the photocatalyst layer, and then light containing ultraviolet rays may be irradiated.

In this way, even if ZnO and Ag or Agz 0 are not combined, the coloring caused by the particles that fill the gap can be eliminated, and the base color, pattern, or their combination can be used to improve the effect of the outside.

In addition, TiOz is used as the photocatalyst particles, and the heat treatment temperature for softening the adhesive layer 6 can also be set at 80°C or higher and 1000°C. At 80°C or higher, the particles are generated due to the initial sintering between the particles. The tilting part, so although the bonding strength of TiOw particles to each other is improved, if it exceeds ioo(rc, it will move to the mid-term sintering process,

200610101461.3 The solid phase sintering of Ti(h) significantly consolidates the volume of the photocatalyst layer, which makes cracks prone to occur.

In addition, Ti(h· is used as the above-mentioned photocatalyst particles, and Ag is used as the particles 4 filled in the gaps of the photocatalyst particles, and aqueous solutions of halides such as KI, KC1, and FCls may also be used as the particles contained in the Ag ion. Insoluble colorless or white salt solutions are formed between A g and halogenated alkali. Insoluble colorless or white salts such as AgCl and AgCl are formed between Ag and alkali halide. Therefore, it is expected to improve the use of base color, pattern or their The combined effect.

In addition, when a dispersion process is provided as the previous process of the process of coating photocatalyst particles on the binder layer, it is used to disperse the sol or precursor that should become the photocatalyst particles in the dispersant of the dispersion process in the solution. It is preferable to use only a component that vaporizes at a temperature lower than the heat treatment temperature of the softening adhesive layer.

In the prior art, when the temperature is less than 32°C, there is no deodorization. This is because the dispersant attached to the surface of the TiOz particles during the dispersion process is not fully vaporized, evaporates and remains, so that the surface of the TiOz particles is not fully exposed. The outermost surface of the substrate cannot sufficiently achieve the photocatalytic function. Furthermore, as a dispersant that vaporizes at low temperatures, organic dispersants and phosphoric acid series dispersants with a molecular weight of 10,000 or less are preferred.

Specific examples are listed below.

Example 1 A binder layer composed of SiOz -Alz Os -Na/Kz 0 glass frit was formed by spraying on the surface of a 150 square ceramic tile substrate. After drying, 15% TiO was sprayed by spraying.₂The sol solution is used to form a Ti (h layer) with a thickness of 0.8μm. Then, the substrate on which the binder layer and the TiOz layer are laminated is heated and fired in a radial hearth furnace (atmosphere temperature varies with different examples), and then cooled and solidified , Get multifunctional materials.

In the waste, the so-called TiOw sol aqueous solution is, for example, TiCl is hydrolyzed in an autoclave under hydrothermal conditions in the range of 100200-C. to obtain a grain size of 0.007-0.2 μm.

200610101461.3 Ti(L·) of the anatase type, disperse this Ti(h in a sol state in an acidic aqueous solution such as nitric acid and hydrochloric acid or an alkaline aqueous solution such as ammonia to a few percent to a few percent+ to improve For dispersibility, it is possible to add organic surface treatment agents such as triethanolamine and trimethylamine, and surface treatment agents such as pentaerythritol and trimethylolpropane in the range of 0.5% or less. In addition, ΤίΟ₂The particle size of the sol is processed by image processing observed by SEM (Scanning Electron Microscope), and the crystal particle size is calculated from the integral width of powder X-ray diffraction.

In addition, although the coating method is performed by spray coating, it is expected that the dip coating method and the spin coating method will also obtain the same results.

The obtained multifunctional material was evaluated for antibacterial properties and abrasion resistance.

Regarding antibacterial properties, we tested the bactericidal effect against Escherichia coli V3110. Add 0.15ml (1-5 X 1 0) bacteria liquid on the surface of the multifunctional material pre-sterilized with 70% ethanol⁴ CFU), placed on a glass plate (10 10 c) and closely attached to the surface of the substrate as a sample. After irradiating with a white light (3500 lux) for 30 minutes, wipe the irradiated sample with sterile gauze and the bacterial solution of the sample kept under the light-shielding condition, and recover it in 10ml of physiological saline to determine the survival of the bacteria. Rate, as an evaluation indicator.

Regarding the abrasion resistance, the sliding abrasion using a plastic rubber was evaluated, and the change in appearance was compared.

Table 1 below shows that when the base material is a ceramic tile, the binder Si (k -Alz 03 -Na/K₂ 0 The change of the firing temperature of the glass frit, the change of the antibacterial and abrasion resistance.

(Table 1) Base material two ceramic tiles, binder two Si0₂ -AU 0₃ -Na/Kz 0 glass frit photocatalyst two Ti(b

200610101461.3 p.

<td>No.</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td>

<td>Roasting temperature (°C)</td><td>700</td><td>780</td><td>880</td><td>980</td><td>1000</td>

<td>And softening temperature (P)</td><td>20</td><td>100</td><td>200</td><td>300</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>—</td><td>—</td>

<td>Abrasion resistance</td><td>Δ</td><td>ο</td><td>◎</td><td>◎</td><td>◎</td>

⁺⁺+: The survival rate of Escherichia coli is 10% or less ++: The survival rate of Escherichia coli is 10% or more and 30% or less +: The survival rate of Escherichia coli is 30% or more and 70% or less

-: The survival rate of Escherichia coli is more than 70%

Ο: No change for 40 reciprocations

Ο: There are scratches in 10-40 sliding times, and the photocatalyst layer (TiOa film) is peeled off : There are scratches in 5-10 sliding times, and the photocatalyst layer (TiOz film) is peeled off X: In 5 times The following sliding has scratches, and the photocatalyst layer (TiOz film) is peeled. Here, SiOz-AU 0 is used as the adhesive layer.₃ -The specific gravity of the Na/Kz 0 glass frit is 2.4, the film thickness during coating is 200 μm, and the softening temperature is 68 (TC. In addition, in Table 1, in the obtained TiOz, No. 1-3 are anatase Type, specific gravity is 3.9, No. 4 and 5 are rutile type, specific gravity is 4.2.

In Table 1, the firing temperature of No. 1 is only 20 °C higher than the softening temperature of the adhesive layer. In order to not sufficiently reduce the viscosity of the adhesive layer, the anatase Ti (h The particles are not sufficiently buried in the binder, so in the abrasion resistance test, they are scratched and peeled after 5-10 times of sliding. This can be explained as the anatase type with excellent photocatalytic activity in terms of antibacterial properties. And above 3 (KTC, TG-DTA observation results of TiOz sol show that the organic components are generally decomposed, vaporized, and dispersants such as surface treatment agents attached to the surface of TiOz vaporized, but the calcination temperature is much higher than this temperature The processing temperature is 70 (TC

200610101461.3 No. ++ excellent value.

No.? -5 When the firing temperature of the tower is 80 °C or more and 1000 °C or less, the durability is very good, and there is no change even if the sliding test is more than 40 times. The reason can be considered to be the TiO that accompanies the surface_zBecause of the initial firing of the particles, the necked part is formed. In addition, during the 1100Ό treatment, cracks occurred on the TiO? layer on the surface of the multifunctional material taken out from the radial hearth furnace after cooling and solidification. Judging from the TMA measurement of the Ti(h sample, it can be considered that this is caused by the mid-stage sintering accompanied by the significant shrinkage of the volume of the Ti(h particles.

No. 4 and 5 have poor antibacterial properties, and both are one. It can be considered that there are two reasons. One is the phase transformation of TiOz particles into rutile type, and the other is that the firing temperature is higher than the softening temperature of the binder layer at 30°C or higher, and the viscosity of the binder layer becomes too low, which constitutes the Tio of the photocatalyst layer.₂The particles are buried in the binder layer. This cannot only be considered as the reason why the phase of Ti(h) particles transformed into rutile type. This is because although rutile type TWn is also inferior to anatase type TiOz, there is still a certain degree of photocatalysis activity. For example, in porous oxide clamp substrates The TiOz sol is sprayed directly on the surface. After calcination at 95 (rc), the antibacterial property of the material after cooling and solidification is +. Therefore, it can be explained that the calcination temperature is higher than the softening temperature of the adhesive layer by more than 300C, and the viscosity of the adhesive layer becomes If it is too low, the TiOz particles constituting the photocatalyst layer are buried in the binder layer, which is also one of the reasons.

In addition, using elemental analysis of τ i and Si (main component of the binder) in the cross-sectional direction of the sample, observation of the combined layer of Ti and si confirmed that the photocatalyst particles TiOz were buried.

The above example 1 confirmed the following facts when at least the photocatalyst was TiOz and the adhesive layer was Sia-Al2 0a-Na/Kz 0 glass frit.

(1) When the multifunctional material is manufactured under the condition that the firing temperature is higher than the softening temperature of the adhesive layer 2 (above TC, not exceeding SOO'C), it is possible to produce a multifunctional material with good antibacterial and anti-abrasive properties. Its The reason can be considered to be that the viscosity of the adhesive is adjusted in the above-mentioned temperature range.

200610101461.3 is adjusted to the value at which Ti(b can be appropriately buried in the adhesive layer.

(2) It has been confirmed that in the multifunctional materials made by (1), TiO_zThe particles are buried in the binder.

(3) When the firing temperature is above 80 (rc) and below 1000°C, the abrasion resistance is excellent, and the sliding test does not change even more than 40 times. It can be considered that the formation of the necked part between the TiOz particles produces a strong bond .

Example 2 On the surface of a 100X 100X 5 alumina substrate (alumina purity of 9 6%), SiOz -Alz was formed by spraying.₃ An adhesive layer composed of PbO glass frit, after drying, was sprayed with a 15% pore ()2 sol aqueous solution (same as in Example 1) to form a TiOz layer with a thickness of θ·8μm, and then The base material laminated with the adhesive layer and Ti(h layer) is heated and fired in the radial hearth furnace at different atmospheric temperatures depending on the example, and then cooled and solidified to obtain a multifunctional material.

In Table 2 below, when the substrate is alumina, the binder Si(h -Alz 0₃-PbO glass frit changes in firing temperature, changes in antibacterial and wear resistance.

(Table 2) Base material alumina plate (100X100X 5), binder two SiOw -Ah 0₃ -PbO glass frit photocatalyst two TiOz

<td>No.</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>Roasting temperature (°C)</td><td>560</td><td>580</td><td>740</td><td>840</td><td>860</td>

<td>Difference from softening temperature (9)</td><td>20</td><td>40</td><td>200</td><td>300</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>+</td>

<td>Abrasion resistance</td><td>Δ</td><td>1 °</td><td>ο</td><td>◎</td><td>◎</td>

200610101461.3 No. Here, the softening temperature of SiOz -Alz 03 -PbO glass used as a binder is 540°C, the specific gravity is 3.8, and the film thickness when coated is 150μιη_οIn addition, the crystal form of the obtained TiOz is already titanium ore type.

In the abrasion resistance test face in Table 2, No. 6 was scratched after 10 times of sliding and was peeled off, but No. 7 and 8 did not scratch even after sliding more than 10 times, and again, No. From 9# to the good result of no scratches even after sliding more than 40 times.

In No. 9, 10, there was no scratches even after 40 or more sliding times. This is considered to be because the firing temperature is 80°C or higher, and necking is formed between the TiOz particles, and the TiOz particles are firmly bonded to each other. .

In No. 6, there are scratches and peeling after sliding less than 10 times. This is considered to be because the calcination temperature is only higher than the softening temperature of the binder 2 (TC, the viscosity of the binder is not very low, constituting the photocatalyst The anatase type ΉΟν particles in the lowermost layer of the layer are not sufficiently buried in the binder layer.

On the contrary, in No. 7 and No. 8, there was no scratches even after 10 times of sliding. This is considered to be because the temperature of the necking formation temperature was not reached, and the difference between the firing temperature and the softening temperature of the binder was adjusted to The value that makes the viscosity of the adhesive TiOz buried in the adhesive layer moderately.

On the other hand, in the antibacterial property test of Table 2, No. 6-9 had good results of + + + or + +, but No. 10 was +. This is considered to be because the calcination temperature is 32°C higher than the softening temperature of the binder, and the viscosity of the binder is too low, and the TiOz particles constituting the photocatalyst layer are buried in the binder layer.

Example 3 SiOz -AU 0₃ -BaO glass frit is melted in the mold, and after cooling and solidification, it is processed into 100XW0X 1 glass flakes, and 15% ΤίΟ is coated on it by spraying._ζSol aqueous solution (same as in Example 1) to form a Ti(L·layer) with a thickness of 0.8 μm.

200610101461.3 Afterwards, put the glass sheet on the alumina substrate (100X100X 5 ), heat it in a silicon carbide rod furnace at a different atmosphere temperature depending on the example, and then cure it to obtain a multifunctional material .

Table 3 shows the changes in antibacterial properties and abrasion resistance as the firing temperature of the multifunctional material changes.

(Table 3) Base material alumina plate (100X100X 5), binder two SiS-AU Oa one BaO glass frit photocatalyst two TiOz

<td>No.</td><td>11</td><td>12</td><td>13</td><td>14</td>

<td>Roasting temperature (*C)</td><td>640</td><td>740</td><td>840</td><td>940</td>

<td>Difference from softening temperature (0</td><td>20</td><td>120</td><td>220</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>—</td>

<td>Abrasion resistance</td><td>X</td><td>Ο</td><td>◎</td><td>◎</td>

Here, Si(h -Alz 0₃ -BaO glass frit has a softening temperature of 62°C, a specific gravity of 2.8, the crystal form of Ti(h on the multifunctional material, No. 1 1 13 is an anatase type, and No. 1 4 is a rutile type.

In the abrasion resistance test of Table 3, No. 1 1 has scratches and peeled off after 10 times of sliding, but No. 12 has no scratches even after 10 times of sliding. . 1 3, 1 4 Get good results with no scratches even after sliding more than 40 times.

No. 1 3. 1 4 There is no scratches even after 40 or more sliding times. It is considered that because the firing temperature is 80°C or higher, necking is formed between the Ti(h particles, and the Ti(h particles are firmly connected to each other. Combination's sake.

200610101461.3 p.

No. 1 1 is scratched and peeled after sliding less than 10 times. It is considered that the burning temperature is only 2 O'C higher than the softening temperature of the adhesive, and the viscosity of the adhesive is not sufficiently low, which constitutes a photocatalyst. The anatase Ti(h) particles in the lowermost layer of the layer cannot be sufficiently buried in the binder layer.

In contrast, No. 12 has no scratches even after 10 times of sliding. It can be considered that although the firing temperature of the necking formation temperature is not reached, the difference between the firing temperature and the softening temperature of the binder is adjusted to make it sticky. The viscosity of the bonding agent is a value that appropriately embeds TiOz in the adhesive layer.

On the other hand, in the antibacterial property test of Table 3, No. 1 1-1 3 had good results of + + + or + +, but No. 14 was -. It can be considered that this is caused by two reasons: TiOz is rutile, and the firing temperature is 32°C higher than the softening temperature of the binder. The viscosity of the binder is too low, and the TiOz particles constituting the photocatalyst layer are buried in the binder.. The agent layer. The agent layer.

It can be confirmed from the above that the method of pre-coating Ti(h particles on the adhesive I, and then pasting it on the substrate for firing to obtain a multifunctional material is also compatible with coating the adhesive on the substrate and then coating it. Cloth Ti(h particles, get the same effect as the method of multifunctional materials.

Example 4 An acrylic resin binder was coated on the surface of a 100X 100X 5 substrate made of polyimide resin, and then 15% TiO was coated by spraying.₂The sol aqueous solution was used to form a TiOz layer with a thickness of 0.8 μm, and then a substrate on which the adhesive layer and the Ti(h layer) were laminated was fired in a nickel wire furnace at 150C.

Table 4 below shows the changes in antibacterial properties and abrasion resistance with changes in the firing temperature of the above-mentioned multifunctional materials.

200610101461.3 Section (Table 4) Substrate dimeric amide resin, binder diacrylic resin photocatalyst two TiOz, calcination temperature 15 (rc

<td>No.</td><td>15</td><td>16</td>

<td>Antibacterial</td><td>—</td><td>+ +</td>

<td>Abrasion resistance</td><td>ο</td><td>Ο</td>

In addition, in Table 4, the adjustment method of the 15% Ti(h) sol aqueous solution was changed as follows.

No. 15: The 15% TiOz sol aqueous solution used in Example 1 was used as it was.

No. 16: The TiCl aqueous solution is hydrolyzed in an autoclave at 110-150°C, and then the product is adjusted to pH 0.8 with nitric acid, and dispersed without using a surface modifier, and then a substance from which agglomerates are removed is used. Spraying is carried out immediately after removing the agglomerates.

Here, TiO₂The specific gravity of is 3·9, the crystal form is anatase, the specific gravity of acrylic resin is 0.9, and the temperature at which the viscosity corresponding to the softening point of glass is formed is 70 Όο Regarding wear resistance, in No. 1 5, 16 Under these conditions, no scratches will occur even if sliding more than 10 times. It is considered that this is because the difference range between the firing temperature and the softening temperature of the binder can adjust the viscosity of the binder to a value that allows TiOz to be appropriately buried in the binder layer.

On the other hand, regarding the antibacterial property test, it was found that No. 15 was but No. 16 had good results of + +, and even if it was below 3 O'C, it was possible to produce a multifunctional material with antibacterial properties. In DTA-TG, the TiOz sol of No. 15 has components that decompose and evaporate at 200-350°C, but it is not seen with No. 16, so there is no organic covering ΤίΟζ

200610101461.3 The first component is the reason for this difference.

In addition, the specific gravity difference between anatase-type TiOz and acrylic resin is 3, but it has been confirmed that under this degree of difference, the "o? particles constituting the photocatalyst layer are not buried in the binder layer, and have good properties. The antibacterial properties.

Example 5 On the surface of 100X100X 5 alumina substrate, a binder layer composed of glass frit with different specific gravity according to each example was formed by spraying method, and then dried, and then spraying method was used to coat 15% Ti0z sol aqueous solution , The formation of a TiOz layer with a thickness of 0.δμπι, then, in a radial hearth furnace at a temperature of 75 (rc), the base material laminated with the binder layer and the TiOz layer is heated and fired, and then cooled and solidified to obtain a multifunctional material .

Table 5 below shows the changes in antibacterial properties and abrasion resistance of the above-mentioned multifunctional materials with changes in firing temperature.

(Table 5) Base material alumina plate (100X100X 5), photocatalyst two TiOz

<td>No,</td><td>17</td><td>18</td><td>19</td><td>20</td>

<td>Types of binder</td><td colspan="2">SiOj-AkOj-PbO</td><td colspan="2">SiOj-AljOj-PbO</td>

<td>Proportion of Bond Penalty</td><td>5.3</td><td>3.8</td><td>2.8</td><td>24</td>

<td>TO proportion</td><td>3.9</td><td>3.9</td><td>3.9</td><td>3.9</td>

<td>Glass frit softening temperature</td><td>480</td><td>540</td><td>620</td><td>680</td>

<td>(Nei) Roasting temperature ('C)</td><td>750</td><td>750</td><td>750</td><td>750</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td>

<td>Abrasion resistance</td><td>X</td><td>ο</td><td>ο</td><td>ο</td>

Regarding the antibacterial test, Qu.1 to 20 have obtained positive results of + + abundance. In each sample, the firing temperature is higher than the softening temperature of the softener by more than 3 O*c, and it can be less than 300°C.

200610101461.3 It is believed that the range of the difference between the firing temperature and the softening temperature of the binder makes the viscosity of the binder adjusted to Tio₂A value that is moderately buried in the adhesive layer.

Regarding the abrasion resistance, No. 17 had scratches and peeled off after sliding less than 5 times, but No. 18-20 had no scratches even after sliding more than 10 times.

The reason is that No. 17 is different from others in that the specific gravity of the binder is larger than that of TiOz, and the anatase Ti (h particles) constituting the lower layer of the photocatalyst layer are not buried in the binder layer.

Therefore, TiO₂Both the specific gravity of the binder and the binder affect the wear resistance of the multifunctional material. If the specific gravity of the binder is greater than that of TiO?, the wear resistance will become worse.

Example 6 SiOz-AU 0 was formed on the surface of a 150 square ceramic tile substrate₃ -BaO glass frit (a binder layer composed of a softening temperature of 62 (TC), on which an aqueous solution of Ti (h sol and SnOz sol) is sprayed, mixed and stirred, and then fired at 75 (TC) and cooled Cured to obtain a multifunctional material.

In addition, the concentration of the TiOz sol is 4-6% (weight), and the -pH is adjusted to 1 1 with an aqueous NHs solution. The grain size of the TiOw particles is 0.01 μm, SnO₂The grain size of the particles is 0.0035 μm ο In the multifunctional material made in this way, the amount of SnO varies with respect to the total amount of TiOw and SnOz₂The amount (mol ratio) was tested for antibacterial properties and abrasion resistance, and the results are shown in Table 6 below Φ. ο

200610101461.3 Section (Table 6) Substrate two breast tiles, adhesive two SiOz -Alz Oa -BaO glass frit photocatalyst two TiOz, barrier particles two SnOz (0.0035μϊη)

<td>No.</td><td>21</td><td>22</td><td>23</td><td>24</td><td>25</td>

<td>SnO₂fi(mol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>One</td>

<td>Abrasion resistance</td><td>Ο</td><td>©</td><td>◎</td><td>◎</td><td>◎</td>

Regarding the abrasion resistance test face, it increased as the amount of Sn(h) increased. Due to the addition of 10% or more, there was no scratch and no change even in the 40 sliding tests.

Regarding the antibacterial face test, if it is in the range of 20% or more, it is the same as when it is not added. If it is 60%, it is limited to + +. If this value is increased further, the probability of covering the Ti(h) particles on the surface of the substrate becomes higher, and the antibacterial property deteriorates, and it becomes-at 100%.

Therefore, according to the mol ratio, if the addition amount of Sn(h is 10% or more and 60% or less of the total amount of TiOz and Sn(h, preferably 10% or more and 20% or less, it can provide antibacterial A multifunctional material with excellent durability and abrasion resistance.

Here, the increase in wear resistance as the amount of SnOz increases is due to the mechanism shown below: Because at a high temperature above 60°C, SnO₂The vapor pressure is higher than Ti(k, so before sintering, the spacing of TiOz particles 3 b is Lo as shown in Figure 17(a), but the vapor pressure becomes high on the surface of Ti(k particles 3 with positive curvature, with negative The surface of the curvature, that is, the surface of the constricted part where two TiOz particles 3 b meet, the steam pressure becomes lower. As shown in Fig. 17 (b), the Sn(k) whose steam pressure is higher than that of TiOw enters the constricted part. As shown in Figure 17(c), it is condensed and sintered according to the vaporization-condensation mechanism.

Moreover, if sintering is carried out according to the vaporization-condensation mechanism, the sintered TiOz particles

200610101461.3 The first interval L? is roughly equal to the interval Lo before sintering, so no cracks occur.

In the composite member in which the symptom layer is held on the surface of the base material by an adhesive, the gaps between the Ti(L·particles on the outermost surface) are filled with Sn(L·particles, if at 60(TC Without firing in the above, cracks will not occur, and the necked part between the TiOz particles can be combined, so the wear resistance is improved.

Comparative example 7 is the same as example 6, formed on the surface of 150 square ceramic tile base material made of SiD?AU 0₃ -BaO glass frit (a binder layer composed of a softening temperature of 62 (TC), on which an aqueous solution of mixed and stirred TiOz sol and SnOz sol is coated by spraying, and then fired at 75 (TC), cooled and solidified After obtaining multifunctional materials.

In addition, the TiOz sol concentration is 4 to 6% (weight), adjusted to pH1b with an aqueous solution of NH3. The grain size of the particles is 0.01 μm, the same as in Example 6, but the grain size of the SnOz particles is 0.008 μιη and slightly higher. Large particles.

The antibacterial resistance test and the abrasion resistance test were performed on the multifunctional material produced in this way, and the results of comparison with Example 6 are shown in Table 7 below.

(Table 7) Substrate two ceramic tiles, binder two Si (h -Alz 0a one BaO glass frit photocatalyst two Ti0_z,Interstitial particles two SnOz (0.0080μ in)&gt; heat treatment 75(TC

<td>No.</td><td>26</td><td>27</td><td>28</td><td>29</td><td>30</td>

<td>SnO: a (mol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>—</td>

<td>Abrasion resistance</td><td>ο</td><td>ο</td><td>ο</td><td>◎</td><td>◎</td>

Results The abrasion resistance of Sn particles of Ο.ΟΟδμηι is higher than that of 0.0035μm.

The SnOz particles of 200610101461.3 are weak, and the mol ratio to the total amount of TiOz and SnOz is about 60% or more, and there is no scratch or change even in the 4 Q sliding test.

Regarding the antibacterial face test, as in the case of using 0.0035 pm SnOz particles, if it becomes 20% or more, it is the same as when it is not added. If it becomes 60% or less, it is limited to + +. If this is further increased, the probability of covering Ti(b) particles on the surface of the base material becomes higher, and the antibacterial property deteriorates, which becomes-at 100%.

Therefore, when O.OiHmTiOz particles are used, it is difficult to obtain a multifunctional material with excellent antibacterial and abrasion resistance by adding 0.008pm SnOz particles. The reason can be considered to be that as the size of the SnOz particles increases, the pressure of the sludge becomes smaller. When the remaining SnOz particles are 0.008 μm without vaporization, the SnOz particles are larger than the gaps between the Ti(h particles). (h particles do not enter the gap, of course, the probability of reaching the TίΟζ particles becomes higher. This is the same as the non-vaporized remaining SnOz particles when the SnOz particles are 0.0035 μm. Sn(k exists in the gap between the TUL·particles, which can improve the bonding strength The situation is relatively.

From the above point of view, the size of the Sn(h particles in the interstices of Ti(L·particles) relative to the diameter of the TiOz particles should be filled, ideally 4/5 or less.

Example 8 Formation of Si0 on the surface of a 150 square ceramic tile substrate₂ -AU 0₃ -BaO glass frit (softening temperature 62 (TC) composition of the adhesive layer, after coating Ti(h sol water-soluble) on it by spraying method, fired at 750 °C, on the cooling solidified composite member, use After spraying the shunb sol aqueous solution, it is heat-treated at ii(rc) to obtain the multifunctional material. At this time, the same solution as in Example 6 is used in the Ti(h sol aqueous solution, and 0.0035um is used in the SnOz sol.

The antibacterial property test and the abrasion resistance test were performed on the multifunctional material thus produced, and the results are shown in Table 8 below.

200610101461.3 Section (Table 8) Substrate two ceramic tiles, binder two SiOz -Alz Οβ -BaO glass frit photocatalyst two TiOz, interstitial particles two Sn(b (0.0035 μ m). Heat treatment 750Ό/110Γ

<td>No.</td><td>31</td><td>32</td><td>33</td><td>34</td><td>35</td>

<td>SnOsSCmol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ten+</td><td>+ +</td><td>One</td>

<td>Abrasion resistance</td><td>ο</td><td>ο</td><td>◎</td><td>◎</td><td>◎</td>

Regarding the endurance test, it increases with the increase in the amount. Since the addition of 20% (mol ratio) or more, there is no scratch or change even in the 40 sliding test.

Regarding the antibacterial property test, if it is in the range of 20% or more, it is + + + as in the case of no addition, and if it is 60%, it is limited to + +. If this is further increased, the probability of covering the TiOw particles on the surface of the base material increases, and the antibacterial property deteriorates, which becomes-at 100%.

In this test, because the SnOz sol was heat-treated at a low temperature of 110t, sintering caused by the vaporization-condensation mechanism shown in Example 6 did not occur. Although the abrasion resistance is improved, this is considered to be because the particle size is smaller than the TiOw particles, that is, the SnOz particles have a larger specific surface area and good adsorption capacity to fill Ti0._zThe interstices of the particles strengthen the bonding between the Ti (h particles).

Example 9 On the surface of a 150 square ceramic tile base material, SiOz -AJ ₂ 0₃ -BaO glass frit (a binder layer composed of a softening temperature of 62 (TC), on which a TiOz sol aqueous solution is sprayed, fired at 75 (TC), and then coated on the composite member formed by cooling and solidification

200610101461.3 The first copper acetate aqueous solution is dried, and then irradiated with ultraviolet light to reduce copper ions, and at the same time, it is fixed on the photocatalyst layer to obtain a multifunctional material. Here, a mercury lamp is used as the illumination lamp.

Here, the average size of the c U particles fixed on the photocatalyst layer is about 0.004 (4 «!).

The antibacterial property test and the abrasion resistance test were performed on the multifunctional material thus produced, and the results are shown in Table 9.

(Table 9) Base material two ceramic tiles, binder two Si (h -Alz 0₃ -BaO glass frit photocatalyst two Ti (h, interstitial particles two Cu (0.004um), heat treatment 750Ό / light reduction

<td>No.</td><td>36</td><td>37</td><td>38</td><td>39</td><td>40</td>

<td>CufiXmol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td>

<td>Abrasion resistance</td><td>Ο</td><td>ο</td><td>◎</td><td>·©</td><td>◎</td>

Regarding the abrasion resistance test, it increased as the amount of Cu increased. Since the addition of 20% (mol ratio) or more, there was no scratch or change even in the 40 sliding test.

Regarding the antibacterial property test, if it is in the range of 20% or more, it is + + + as in the case of no addition. Since C ii itself has antibacterial activity, no deterioration of antibacterial properties due to a large amount of addition is seen.

However, when the added amount of Cu is small, the photocatalytic effect by the Ti() 2 particle layer is dominant. When the added amount of Cu is large, it may be considered that the effect by Cu is dominant. In the case where only the effect of Cu is expected, since Cu is slowly eluted when used in a liquid, it can be considered that the life is shorter than that in the case of no photocatalyst. In addition, if Cu

200610101461.3 The added amount of the first part increases, and the cost of this part also increases. Therefore, it is considered meaningless to set the amount of Cu too much.

According to this embodiment, it has been confirmed that not only oxides such as Sn(b, but also metals such as Cu can become particles that fill the gaps in the TiOz particle layer.

Example 1 0 On the surface of a 150 square ceramic tile base material, SiOz-AU 0₃ -BaO glass frit (softening temperature 620t) composed of an adhesive layer, on which TiOz sol aqueous solution was coated by spraying method, baked at 95°C, and coated with copper acetate on the composite member cured by Xu Que The aqueous solution is then irradiated with light containing ultraviolet rays to reduce copper ions and at the same time be fixed on the photocatalyst layer to obtain a multifunctional material.

At this time, a BLB lamp was used as the irradiation lamp, and it was irradiated for several minutes. TiOz changes from anatase type to rutile type by heat treatment process. The film thickness of Ti(h is adjusted to 0.4um during spraying.

The antibacterial property test and abrasion resistance test of the multifunctional material made in this way were carried out. Regarding the abrasion resistance test, even if it is not added, it shows good results in this temperature region. Even if Cu is added, there is no scratch or change in the 40 sliding test as in the case of no addition.

The antibacterial test is shown in Figure 18. When there is no addition, because TiOz is rutile, it is not good +. Adding Cu to it increases the antibacterial properties. And not only when the BLB lamp is irradiated, but also when there is no irradiation, if the Cu loading is 0.7Rg/cm²Above, the antibacterial activity becomes + +, if the Cu loading is 1.2HgZcm²Above, the antibacterial activity becomes + + +.

From the above point of view, in order to provide a multifunctional material with excellent antibacterial properties and abrasion resistance, the loading amount of C u can be 0.7μ_ε/οιη²Above, it can be 1.2Hg/cm better²the above.

However, after the coating of Yijun copper water soluble mask and before the BLB lamp irradiation, if it enters the drying process, the Cu loading capacity will be greatly increased. This relationship is shown in Figure 19. It is considered that this is because when drying is performed, the metal ion concentration during photoreduction is high.

200610101461.3 In addition, when the coating amount is optimized, the Cu loading amount becomes the largest (Figure 20, Figure 2 OMCu concentration is 1% (Dong amount) copper acetate example), in the case of Figure 20, In order to make the Cu loading capacity 0.7ug/cm²Above, the coating amount can be 0.2mgZ cm²Above, 2.7ng/cm²Below·In order to make the Cu loading capacity 1.2 μg/cm²Above, the coating amount of CU can be 0.3mg/cm²Above, 2.4mg/cm²the following.

Example 1 1 On the surface of a 150 square ceramic tile base material, Si(L· -Alz 0₃ -BaO glass frit (softening temperature 68 (TC) composition of the adhesive layer, after coating Ti(h sol aqueous solution) by spraying method, calcining at 95 (TC), coating on the composite member formed by cooling and solidification An aqueous silver nitrate solution is applied, dried, and then irradiated with ultraviolet light to reduce the silver ions and fix them on the photocatalyst layer at the same time to obtain a multifunctional material.

A BLB lamp is used as the irradiation lamp, and it is irradiated for several minutes. In addition, TiOz is transformed from the titanium ore type phase to the rutile type after heat treatment. The film thickness of TiOz was adjusted to 0.4 μηΐ during spraying. The antibacterial property test and the abrasion resistance test were performed on the multifunctional material prepared in this way. Regarding abrasion resistance, even if it is not added, good results are shown in this temperature region. Even if Ag was added, there was no scratch or change in the 40 sliding test as in the case of no addition.

The antibacterial properties are shown in Figure 70. When it is not added, because TiOz is rutile, it is bad+. If A g is added to it, the antibacterial properties will increase. And not only when the BLB lamp is irradiated, but also when it is not irradiated, if the A g allowance becomes 0.05 μg/cm²Above, the antibacterial activity also becomes + +, if the A g supporting amount becomes 0.1 Hg/cm²Above, the antibacterial activity becomes + + +.

Therefore, in order to provide a multifunctional material with excellent antibacterial properties and abrasion resistance, the loading amount of Ag can be 0.05ng/cm²The above, more preferably 0.1Hg/cmZ or more.

However, when the loading amount of Ag is large, the coloration changes from brown to black, and the appearance deteriorates. But the A&amp; loading capacity becomes 1 μgXcffl²Below, it will not be colored.

200610101461.3 From the above point of view, the A g load can be 0.05kg/cm²Above, 1 Rg/cm²Above, better 10.Ug/cm²Above, 1 με/οιη²the following.

Example 1 2 SiOz -AU 0 was formed on the surface of a 150 square ceramic tile base material.₃ -BaO glass frit (a binder layer composed of a softening temperature of 68 (FC), on which a TiOz sol aqueous solution is coated by spraying, then fired at 95CTC, and then a silver nitrate aqueous solution is coated on the composite member formed by cooling and solidification , Dry, and then irradiate light containing ultraviolet light to reduce silver ions, and at the same time fix it on the light-weighting agent layer to obtain a multifunctional material.

At this time, a BLB lamp was used as the irradiation lamp, and the irradiation was performed for several minutes. In addition, Ti(h is transformed from anatase-type phase to rutile-type after heat treatment.

The film thickness of Ti(b) of the multifunctional material thus produced was changed, and abrasion resistance test, antibacterial property test and stain resistance test were performed.

Regarding the abrasion test, good results were shown within the range of 2 and 01 in the test, and there was no scratch or change even in the 40 sliding test.

In the antibacterial test, when the film thickness is 0.1 μm or more, it becomes ++, and when it is 0.2 km or more, it becomes + + +. Therefore, the film thickness of TiOz may be O.Um or more, more preferably 0.2 μm or more.

Example 1 3 On the surface of a 150 square ceramic tile base material, SiOz -Alz 0₃ -BaO glass frit (a binder layer composed of a softening temperature of 62 (TC), on which a zinc chloride aqueous solution or a Ti (k sol aqueous solution) is sprayed on it, after drying, the silver nitrate aqueous solution is coated, and then irradiated containing Ultraviolet light reduces the silver ions and fixes them on the photocatalyst layer at the same time. After that, they are calcined at a temperature above 90°C and below iDD°C, and are cooled and solidified to obtain a multifunctional material.

At this time, the BLB lamp was used as the irradiation lamp, and the irradiation was performed for several minutes. In addition, TiOz is heat-treated from anatase

200610101461.3 The ore-type phase is transformed into rutile type. And the A g fixed on the surface changes from tea black to white with heat treatment, so it can be considered that it becomes silver oxide during firing. However, the attachment and fixation of Ag was completed discretely, and it was observed that there was almost no growth of Ag particles before and after firing.

The antibacterial face test and abrasion resistance test were performed on the multifunctional material made in this way.

Regarding the abrasion resistance test, it shows good results even if it is not added in this temperature zone. Even if Ag was added, it was the same as when it was not added, and there was no scratch or change in the sliding test of 40 times.

The antibacterial property test is shown in Fig. 70. When it is not added, TiOz is a rutile type, so it is not good+. If Ag is added to it, the antibacterial properties will increase.

Example 1 4 On the surface of the stem of a 150 square ceramic brick, a SiOz -Alz 0₃ -BaO glass frit (a binder layer composed of a softening temperature of 62 (TC), on which a TiOz sol water drop is coated by a spray method, and then fired at a temperature above 900°C and below 100OC, and then solidified. On the component, apply silver nitrate aqueous solution, and then irradiate light containing ultraviolet light to reduce the silver ions and fix them on the photocatalyst layer at the same time, and then apply 0.1cc/cm on it.²Coating 0.1 mol/L KI aqueous solution at a ratio of, and then irradiating it with ultraviolet light for about 5 seconds to obtain a multifunctional material. At this time, the loading capacity of A g is 2 μκΖοιη²。

Since 0 .lcc/cm²Coating 0.1mol/L KI aqueous solution at a ratio of 0.1 mol/L, and then irradiating ultraviolet light for about 5 seconds, the original tea-black multifunctional material is decolorized into white, and the appearance is improved.

Example 15 On the surface of a 150 square ceramic tile base material, an adhesive layer composed of SiOz-AG 0s-BaO glass frit (softening temperature 62 (TC)) was formed, and TiOz was sprayed on it. After the sol aqueous solution is calcined at 82VC, cooled and solidified, the obtained multifunctional material is placed obliquely, and the multifunctional material is irradiated with ultraviolet light while on the multifunctional material.

200610101461.3 The bath water collected from the public baths in the first cycle is dripped continuously to observe the changes in the bath water. In order to compare the same device, it was also placed on a substrate without a photocatalyst layer. Observed after 14 days, there is no special difference in the turbidity of the bath water under the above multifunctional material and the bath water under the substrate without the photocatalyst layer, but there is no special difference in the odor of the sewer water. have difference. The bath water dropped on the substrate without the photocatalyst layer has a strong sewage odor, and sludge-like mucus and organic precipitates are observed on the substrate. On the contrary, the dripping on the above-mentioned multifunctional material The water in the bath did not see those conditions. Through the above simulation tests, it can be considered that the multifunctional material can be used as paving stones for artificial waterfalls and fountains in water circulation methods such as parks and department stores.

As can be seen from the above description, in order to fix the photocatalyst particles by an adhesive layer composed of a material whose softening temperature is lower than that of the base material, it is particularly necessary to prevent the photocatalyst particles constituting the surface layer of the photocatalyst layer from being buried in the adhesive layer. The photocatalyst particles are substantially in a state where their surface is exposed to the outside, and can fully exhibit the photocatalytic effect. In addition, since a part of the particles constituting the lower layer of the photocatalyst layer among the photocatalyst glumes is buried in the binder layer, the holding power of the photocatalyst layer is greatly improved, and peeling and the like are less likely to occur.

FIG. 21 shows a manufacturing process diagram of another embodiment. In this embodiment, the substrate 1 uses thermoplastic materials such as inorganic glass and thermoplastic resin, and the photocatalyst layer 2 is directly formed on the surface of the thermoplastic substrate 1. As shown in the figure 2 As shown in 1(a), prepare the thermoplastic substrate 1, and then as shown in the figure

As shown in 1(b), a photocatalyst layer 2 composed of photocatalyst particles such as Ti (h particles) is formed on the surface of the thermoplastic substrate 1. Thereafter, as shown in Figure 2 1 (c), after heat treatment, the photocatalyst layer 2 The lower layer on the thermoplastic substrate side settles on the thermoplastic substrate and is solidified and buried in the thermoplastic substrate to be firmly held. In addition, the photocatalyst layer 2 constitutes the surface layer of the photochemical agent particles in contact with the air 3 Use potential energy, mutual intermolecular force or sintering combination.

200610101461.3 The preferred conditions of this embodiment are the same as those of the above-mentioned embodiment, but specific embodiments will be described below.

Example 1 6 SiOz-Α1 in 150 squares₂ 03 -Na/Kz 0 composition of the glass substrate surface, by spray coating 1 5% Ti (h sol aqueous solution, forming a film ϋΟ.δμηι of TiO₂Then, the glass substrate laminated with the TiOz layer is placed in a ceramic mold with good mold release properties, and heated and fired in a radial hearth furnace at a different gas alarm temperature depending on different examples, and then cooled and solidified to obtain Multifunctional glass.

Here, the so-called TiOz sol aqueous solution is prepared in the following manner: for example, TiCU is hydrolyzed in an autoclave under hydrothermal conditions in the range of 100-200*C to obtain titanium titania TiOz with a grain size of 0.007-0.2um. , The TiOz is dispersed in a sol state in acidic aqueous solutions such as nitric acid and hydrochloric acid or ammonia and other aqueous solutions to a few percent to tens of percent; In order to improve the dispersibility, add a surface treatment agent in the range of 0.5% or less. Organic compounds such as ethanolamine and trimethylamine, quaternary pentaerythritol, trimethylolpropane, etc. obtain the TiOz sol aqueous solution. In addition, the particle size of the TiOz sol was obtained by image processing of SEM observation, and the crystal particle size was calculated from the integrated width of powder X-ray diffraction.

In addition, although the coating method is performed by spray coating, it is expected that the same results can be obtained by dip coating and spin coating.

The antibacterial properties and abrasion resistance of the obtained multifunctional glass were evaluated.

Regarding antibacterial properties, we tested the bactericidal effect on Escherichia coli V3110. Drop 0.15ml of bacterial solution (1-5 X 10 4 CFU) on the top surface of the multifunctional glass pre-sterilized with 70 96 ethanol, and place it on the glass plate (1 0 X 10 cm) and stick it on the top surface of the substrate. Tightly serve as a sample. After irradiating with a white light (3500 Lux) for 30 minutes, wipe the irradiated sample with sterile cotton yarn and the bacterial solution of the sample kept under the shielded condition, and recover it in 10ml of physiological saline to calculate the survival rate of the bacteria. , As an evaluation indicator.

200610101461.3 Regarding the wear resistance, plastic rubber is used for sliding wear, and the appearance changes are compared and evaluated.

In the following table IQ, the use of SiOz -AU 0₃ A glass substrate composed of Na/Kz 0 changes its antibacterial and abrasion resistance with the change of its firing temperature.

(Table "0) Substrate two SiOz -AU 0₃ -Na/Kz 0 glass photocatalyst = TiOa

<td>No.</td><td>1</td><td>2</td><td>3</td><td>4</td><td>5</td>

<td>Roasting temperature (r)</td><td>700</td><td>780</td><td>880</td><td>980</td><td>1000</td>

<td>Difference with softening temperature&lt;0</td><td>20</td><td>100</td><td>200</td><td>300</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>—</td><td>—</td>

<td>Abrasion resistance</td><td>△</td><td>Ο</td><td>◎</td><td>◎</td><td>©</td>

+++: The survival rate of Escherichia coli is 10% or less ++: The survival rate of Escherichia coli is 10% or more and 30% or less ⁺ :The survival rate of Escherichia coli is 30% or more and 70% or less

-: Survival rate of Escherichia coli is 70% or more : No change to 40 cycles

O: There are scratches in 10-40 sliding times, and the photocatalyst layer (Ti0₂Film) peeling : There is a scratch in 5-10 times of sliding, the photocatalyst layer (Ti0₂Film) peeling off

X: There are scratches after sliding less than 5 times, and the photocatalyst layer (TiOz film) is peeled off. Here, SiOz-AG 0₃ The specific gravity of a glass substrate composed of Na/Kz 0 is 2.4, and the softening temperature is 680Γο In addition, in Table 10, the obtained ΉΟν, No. 1-3 is anatase type, the specific gravity is 3.9, No. 4 , 5 is a rutile type with a specific gravity of 4.2.

In Table 10, the firing temperature of No. 1 is only 2 (TC,

200610101461.3 First, since the viscosity of the glass substrate cannot be sufficiently low, the anatase-type TiOz particles constituting the lowermost layer of the photocatalyst layer are not sufficiently buried in the glass substrate. Therefore, in the abrasion resistance test, it is 5-10 times There are scratches on sliding and peeled off. In addition, because it is an anatase type with excellent photocatalytic activity; and the TG-DTA observation of TiOz sol at 30°C or higher reveals that the organic components are basically decomposed, vaporized, and surface treatment agents attached to the surface of TiOz, etc. The dispersant vaporizes, but the calcination temperature is 70°C, which is a heat treatment temperature that is considerably higher than this temperature, so the antibacterial property becomes an excellent value of ++.

Although the firing temperature of No. 3-5 was 800°C or higher and 1000°C or lower, there was no change in the wear resistance even in the sliding test of 40 times or more. It is very good. The reason can be considered to be caused by the initial firing of the Ti(h) particles on the surface. In addition, during the noor treatment, cracks occurred on the TiOz layer on the surface of the multifunctional glass taken out from the radial hearth furnace after cooling and solidification. Judging from the TMA measurement of the TiOz sample, it can be considered to be accompanied by TiO_zSignificant volume shrinkage of the particles is caused by mid-stage sintering.

The antibacterial properties of No. 4 and 5 are both -, which is poor. It can be considered that there are two reasons for this: one is that the phase of TiOz particles transforms into rutile type, and the other is that the firing temperature is 30°C higher than the softening temperature of the glass substrate, the viscosity of the glass substrate is too low, and the TiOz that constitutes the photocatalyst layer The particles are buried in the glass substrate. The reason why the phase transformation of TiOz particles into rutile type cannot be considered here. This is because even in rutile type TiOz, it is inferior to anatase type, but there is still a certain degree of Photocatalytic activity. For example, spray TiO directly on porous alumina substrate₂Sol, after calcination at 95°C, the antibacterial property of the material formed by cooling and solidification is +. Therefore, it can be explained that the firing temperature is 300 Ό higher than the softening temperature of the glass substrate, and the viscosity of the glass substrate is too low to form a photocatalyst layer. The TiOz particles are buried in the glass substrate, which is another reason.

In addition, through elemental analysis of τ i and Si (the main component of the glass substrate) of the EPMA Zun in the cross-sectional direction of the sample, observation of the layer where Ti and Si are mixed, it was confirmed that the photocatalyst particles

200610101461.3 p.

TiOz is buried.

In the above example 16, that is, when the column at least the photocatalyst is TiOz s, the glass substrate is composed of Si(h -Ala Oa -Na/Kz 0), the following facts have been confirmed.

(1) When the multifunctional glass is manufactured under the condition that the firing temperature is higher than the softening temperature of the glass substrate by 2 Ot and not higher than 300°C, the multifunctional glass can be manufactured with good antibacterial properties and durability. The reason can be considered to be that in the above temperature range, the viscosity of the glass substrate is adjusted to make Tio₂The value is moderately buried in the glass substrate.

(2) In the multifunctional glass made in (1), it has been confirmed that TiOz particles are buried in the glass substrate.

(3) When the firing temperature is above 800°C and below 100°C, the wear resistance is

There was no change in the sliding test more than 0 times, which was extremely good. It can be considered that it is caused by the formation of the necked part between the TiOz particles, resulting in a strong bond.

Example 1 7 is made of SiOz -AU 0₃ -On the surface of a 100X 100X 5 glass substrate composed of PbO, a 15% gate 0? sol aqueous solution (same as in Example 16) was sprayed to form a layer of Ti(h) with a thickness of 0.8 μm. Then, The glass substrate laminated with the TiOz layer is placed in a ceramic mold with good release properties, heated and fired in a radial hearth furnace at a different atmosphere temperature according to different examples, and then cooled and solidified to obtain a multifunctional glass.

In the following table 11, it means using SiOw -AU o₃ -In the case of a glass substrate composed of PbO, the antibacterial and abrasion resistance will change with the firing temperature.

200610101461.3 Section (Table 1 1) Substrate two SiOz -AU o₃ -PbO glass photocatalyst two TiON

<td>No.</td><td>6</td><td>7</td><td>8</td><td>9</td><td>10</td>

<td>Roasting temperature ('C)</td><td>560</td><td>580</td><td>740</td><td>840</td><td>860</td>

<td>Difference with softening temperature (0</td><td>20</td><td>40</td><td>200</td><td>300</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>+</td>

<td>Abrasion resistance</td><td>△</td><td>ο</td><td>ο</td><td>◎</td><td>◎</td>

Here, SiOz -AU o₃ -The softening temperature of the glass substrate composed of PbO is 54°C, the specific gravity is 3.8, and the crystal form of the obtained TiOz is anatase.

In the abrasion resistance test in Table 11, No. 6 has scratches and peeled after sliding less than 10 times, but No. 7 and 8 have no scratches even after sliding more than 10 times. , No. 9, 10 has good results that there is no scratches even after sliding more than 40 times.

In No. 9 and 10, there is no scratch even after 40 or more sliding times. It can be considered that because the firing temperature is 80°C or higher, necking is formed between the TiOz particles, and the Ti(b particles are firmly connected to each other. Combination's sake.

In No. 6, there are scratches and peeling when sliding less than 10 times. It can be considered that the firing temperature is only 2 Of higher than the softening temperature of the glass substrate, which cannot make the viscosity of the glass substrate low enough to form a photocatalyst. The anatase-type TiOz particles of the layer are not sufficiently buried in the glass substrate.

On the contrary, in No. 7 and No. 8, there was no scratches even after 10 or more slips. It can be considered that although the necking temperature is not reached, the firing temperature and the softening temperature of the glass substrate

200610101461.3 The difference is adjusted to the value that makes the viscosity of the glass substrate Ti(L·appropriately buried in the glass substrate.

On the other hand, in the antibacterial test of Table 11, No. 6-9 obtained good results of + + + or + +, but No. 1. Become +. It is considered that this is because the firing temperature is 32°C higher than the softening temperature of the glass substrate, the viscosity of the glass substrate is too low, and the Ti(h particles constituting the photocatalyst layer are buried in the glass substrate.

Example 18 In SiOz -AU 0₃ -On the surface of a 100X 100X 5 glass substrate composed of BaO, a 15% Ti (h sol aqueous solution (same as in Example 1) was sprayed to form a Ti(b layer) with a thickness of 0.8 nm. Then, the The glass substrate laminated with the TiDz layer is placed in a ceramic mold with good releasability, heated and fired in a sickle wire furnace at a different atmosphere temperature according to different examples, and then cooled and solidified to obtain a multifunctional glass.

Table 12 below shows the changes in antibacterial properties and abrasion resistance with changes in the firing temperature of the above-mentioned multifunctional glass.

(Table 12) Substrate two Si (h -AU 0₃ -BaO glass photocatalyst two TiO_z

<td>No.</td><td>11</td><td>12</td><td>13</td><td>14</td>

<td>Roasting temperature (*C)</td><td>640</td><td>740</td><td>840</td><td>940</td>

<td>Difference from softening temperature (9)</td><td>20</td><td>120</td><td>220</td><td>320</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>—</td>

<td>Abrasion resistance</td><td>X</td><td>ο</td><td>◎</td><td>◎</td>

Here, SiO_z -AU 0₃ -The softening temperature of the glass substrate composed of BaO is 62 (TC,

200610101461.3 The first specific gravity is 2.8. The crystal form of TiOz on multifunctional glass, No. 1 1-1 3 is anatase type, and No. 14 is rutile type.

In the abrasion resistance test of Table 12, No. 11 has scratches after 5 times of sliding and has peeled off, but No. 12 has no scratches even after sliding for more than 10 times. Nos. 13, 14 gave good results that there were no scratches even after sliding 40 times or more.

No. 1 3. 1 4 There is no scratch even after sliding more than 40 times. It can be considered that because the firing temperature is above 80 °C, necking is formed between the Ti(h particles, and the ΤΪΟζ particles are firmly bonded to each other. So upset.

No. 1 1 There are scratches and peeling after sliding less than 10 times. It can be considered that the firing temperature is only 2 (TC) higher than the softening temperature of the glass substrate (TC, the viscosity of the glass substrate is not low enough to form a photocatalyst The titanite-type Ti (k particles in the lowermost layer of the layer are not sufficiently buried in the glass substrate.

On the contrary, No. 12 has no scratches even after 10 times of sliding or more. It can be considered that the reason is that although the temperature for forming the necked part is not reached, the difference between the firing temperature and the softening temperature of the glass substrate is adjusted to make The viscosity of the glass substrate is such that Ti (h) particles are appropriately embedded in the glass substrate.

On the other hand, in the table antimicrobial test of 12, No. 1 1 ~ 1 3 + + + or + to give good + junction of results, but into a No. 1 4. This can be considered due to two reasons: one is that TiOz is rutile, and the other is that the firing temperature is 320°C higher than the softening temperature of the glass substrate. The viscosity of the glass substrate is too low, and the TiOz particles constituting the photocatalyst layer are buried in In a glass substrate.

Example 19 On the surface of a 100X 100X 5 glass substrate with different specific gravity according to different examples, a 15% Tio® sol aqueous solution was sprayed to form a gate layer with a film thickness of 0.8 μin, and then, Put the TiOz-laminated glass substrate into a ceramic mold with good releasability.

200610101461.3 In the radial hearth furnace, heat and fire at 75°C as the atmosphere temperature, and then solidify to obtain a multifunctional glass.

The following Table 13 shows the change in the specific gravity of the glass substrate of the complex functional glass, the change in antibacterial properties, and abrasion resistance.

(Table 1 3) Photocatalyst two Ti(h

<td>No.</td><td>15</td><td>16</td><td>17</td><td>18</td>

<td>Glass substrate type</td><td colspan="2">SiOrAkOj-PbO</td><td colspan="2">SiO₂-AI₂O,-PbO</td>

<td>Specific gravity of glass substrate</td><td>5.3</td><td>3.8</td><td>28</td><td>24</td>

<td>TO proportion</td><td>3.9</td><td>3.9</td><td>3.9</td><td>3.9</td>

<td>Glass substrate softening temperature (X)</td><td>480</td><td>540</td><td>620</td><td>680</td>

<td>Roasting temperature (°C)</td><td>750</td><td>750</td><td>750</td><td>750</td>

<td>Antibacterial</td><td>+ +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td>

<td>Abrasion resistance</td><td>X</td><td>ο</td><td>ο</td><td>ο</td>

Regarding the antibacterial property test, No. 15-18 all obtained good results of + + +. It can be considered that in each case, the firing temperature is higher than the softening temperature of the glass substrate by 3 or more and 30 (rc) or less. The range of the difference between the firing temperature and the softening temperature of the glass substrate is adjusted to make the glass substrate The viscosity of TiOw is the value that makes the TiOw moderately embedded in the glass substrate.

Regarding abrasion resistance, No. 15 has scratches and peeled off after sliding less than 5 times, and No. 16-18 has no scratches even after sliding more than 10 times.

The reason can be considered to be because No. 15 is different from others in that the specific gravity of the glass substrate is greater than that of Ti(L), and the anatase-type TiOz particles constituting the lowermost layer of the photocatalyst layer are not sufficiently buried in the glass substrate.

200610101461.3 So its clear that Tio₂The specific gravity of the glass substrate and the glass substrate also affect the wear resistance of the multifunctional glass. The specific gravity of the glass substrate is greater than the specific gravity of Ti(k, which deteriorates the wear resistance.

Example 2 ο Si (h -Alz o₃ -BaO composition (softening temperature 621 TC) on the glass substrate, the aqueous solution of Ti (h sol and SnOz sol mixed and stirred by spraying method, and then baked at 75 °C, and then cured, get more Functional glass.

ΤίΟ₂The sol concentration is 4-6% (weight), adjusted to pHlb with NHs aqueous solution

TiO₂The grain size of the particles is 0.01 μ®, SnO₂The grain size of the particles is 0.0035um. For the multifunctional glass produced in this way, various SnOz amounts (mol ratios) relative to Ti (the sum of h and SnOz) were tested for antibacterial properties and abrasion resistance. The results are shown in Table 14 below.

(Table 1 4) Substrate two SiOz -Al₂ 0₃ -BaO glass photocatalyst two Ti (L·, interstitial particles two SnOz (0.0035μπι)

<td>No.</td><td>19</td><td>20</td><td>21</td><td>22</td><td>23</td>

<td>SnO₂S(mol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>—</td>

<td>Abrasion resistance</td><td>Ο</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td>

Regarding the abrasion resistance test, as the amount of SnOz increased, the addition of 10% or more resulted in no scratches and no change even in the 40 sliding tests.

Regarding the antibacterial property test, if it is in the range of 2096, it will be + + + as in the case of no addition, and if it is 60%, it will be limited to +10. If it is increased further, the probability of covering the Ti(h) particles on the glass substrate and the surface becomes higher, and the antibacterial property is inferior, and it becomes -100%.

200610101461.3 Therefore, the mol ratio of the added amount of SnO? relative to the total amount of TiOz and Sn (L· is 10% or more and 60% or less, preferably 10% or more and 20% or less can provide antibacterial properties. , Multifunctional glass with excellent abrasion resistance.

Here, the abrasion resistance increases as the amount of SnON increases, which is caused by the mechanism illustrated in Figure 17.

In this way, in the composite member in which the TiOz particle layer is held on the surface of the glass substrate by the glass substrate, if the exposed TiOz particles are filled with Sn(h particles) and fired at 600 t or more, cracks will not occur. Because it can bond the neck braid between the TiOz particles, the wear resistance is improved.

Comparative example 2 1 Same as example 20, in 150 square SiOz -h\z 0₃ On the surface of a glass substrate composed of BaO (softening temperature 620*C), spray-coated an aqueous solution of TBn sol and SdOn sol mixed and stirred, and then calcined at 750°C, but solidified to obtain Multifunctional glass.

The concentration of TiOz sol is 4 to 6% (weight), adjusted to

PH 1 1, the grain size of the particles is the same as that of Example 5, which is 0.01 μιη, but the grain size of the SnO® particles is 0.008 μιη and a slightly larger diameter.

The multifunctional glass thus produced was tested for antibacterial properties and abrasion resistance, and the results of comparison with Example 5 are shown in Table 15 below.

200610101461.3 Section (Table 15) Substrate two SiOa ~ Al2 O3-BaO glass photocatalyst two TiOz, interstitial particles two SnOz (0.0080μ m). Heat treatment 75 (TC

<td>No.</td><td>24</td><td>25</td><td>26</td><td>27</td><td>28</td>

<td>SnO₂fi(mol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>—</td>

<td>Endurance</td><td>Ο</td><td>Ο</td><td>Ο</td><td>◎</td><td>◎</td>

As a result, the effect of improving the resistance of SnOz particles of 0.008 α m is greater than when SnOz particles of 0.0035 μιη are used, and when the mol ratio of the total amount of TiOz particles and Sn(L·particles) is gradually greater than 60% , Even in 40 sliding tests, there was no scratch or change.

Regarding the antibacterial test/similar to the case of using 0.0035 μm SnOz particles, if it becomes 20% of the range, it is the same as when there is no addition, and if it becomes 60% or less, it is limited to ++. If it is further increased, the probability of covering the TiOz particles on the surface of the glass substrate increases, and the antibacterial property deteriorates to 100%.

Therefore, when using 0.01 μm Ti(h particles, add 0.008 μm SnO₂Particles, it is difficult to obtain a multifunctional glass with excellent antibacterial properties and abrasion resistance. The reason can be considered to be because the evaporation pressure of SnOz particles becomes smaller as the particle size increases, and when the unvaporized remaining SnOz particles are 0.0035 μm, they exist in the gaps between the TiO? particles, which can increase the bonding strength. , In contrast, SnO₂When the particles are 0.008 μm, the distance between the particles and Ti(b particles)

200610101461.3 Compared with the first gap, Sn0₂The particles are large, so the Sz 0 particles do not enter the gap, and the probability of reaching the TiOz particles naturally increases.

It can be seen from the above that the size of the SnOz particles that should fill the gaps between the TiOz particles is ideally 4/5 or less relative to the TiOz particle size.

Example 2 2 SiOz -Alz 0 in 150 squares₃ -BaO composition (softening temperature 62 (TC) on the surface of the glass substrate, the TiOz sol aqueous solution was sprayed, and then fired at 75 °C, the composite member formed by cooling and solidification was sprayed with SnOz After the glue aqueous solution is heat-treated at 110C, the multifunctional glass is obtained. At this time, ΤίΟ₂The sol aqueous solution used the same as in Example 5, SnO₂Use 0.0035μπι for sea glue.

The antibacterial properties and purchase durability tests were performed on the multifunctional glass thus produced, and the results are shown in Table 16 below.

(Table 16) Substrate two Si (h -AG Os -BaO glass photocatalyst two TiO₂ .

Interstitial particles two SnOz (0.0035m ni), heat treatment 750Ό/110Γ

<td>No.</td><td>29</td><td>30</td><td>31</td><td>32</td><td>33</td>

<td>SnOtSCmol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ 4 +</td><td>+ + +</td><td>+ + +</td><td>+ +</td><td>—</td>

<td>Abrasion resistance</td><td>ο</td><td>ο</td><td>◎</td><td>◎</td><td>◎</td>

Regarding the abrasion resistance test, it increased with the increase in the amount of SnOz, and due to the addition of 20% (mol ratio) or more, there was no scratch or change even in the 40 sliding test.

200610101461.3 Regarding the antibacterial test, if it is within the range of 20%, it will be +/- abundance as in the case of no addition, and if it becomes 60%, it will be limited to ++. If it is increased further, the probability of covering the TiOz particles on the surface of the glass substrate increases, and the antibacterial property deteriorates, and it becomes -100%.

In this test, because Sn(h sol is heat-treated at a low temperature of u(rc, sintering caused by the vaporization-condensation mechanism shown in Example 5 does not occur. Although the wear resistance is improved, it can be considered that this The reason is that the particle size is smaller than the Ti(h particles, that is, the specific surface area becomes larger, and the Sn(k particles with good adsorption capacity fill the gaps of the Ti(h particles, thereby strengthening the bonding between the Ti(h particles).

Example 2 3 Si(h -Alz 0₃ -BaOm into (softening temperature 620*C) on the glass substrate, coating the TiOz sol aqueous solution by spraying method, and then firing at 75CTC, on the cured composite member, coating copper acetate aqueous solution, proceed After drying, it is irradiated with ultraviolet light to reduce copper ions and fix it on the photocatalyst layer at the same time to obtain a multifunctional glass. A mercury lamp is used as the illumination lamp here.

Here, the Cu particle size fixed on the photocatalyst layer is about 0.004 μm on average.

The results of the antibacterial and abrasion resistance tests on the multifunctional glass thus produced are shown in Table 17 below.

200610101461.3 Section (Table 17) Ti - S1O2 ~Al2 Oa -BaO glass purchase photocatalyst two TiOz, interstitial particles two SnOz (0.004μ m). Heat treatment 750Γ/light reduction

<td>No.</td><td>34</td><td>35</td><td>36</td><td>37</td><td>38</td>

<td>Cu amount (mol%)</td><td>0</td><td>10</td><td>20</td><td>60</td><td>100</td>

<td>Antibacterial</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ + +</td>

<td>Tolerance</td><td>ο</td><td>Ο</td><td>◎</td><td>◎</td><td>◎</td>

Regarding the wear resistance, it increases with the increase of Cui, and since the addition of 20% (mol ratio) or more, there is no scratch or change even in the sliding test of 40 times.

Regarding the antibacterial property test, if it is in the range of 20% or more, it is + + + as in the case of no addition. Since Cu itself has antibacterial activity, no deterioration of antibacterial properties due to a large amount of addition is seen.

However, it can be considered that when the addition amount of Cu is small, the photocatalytic effect caused by the Ti(h particle layer) dominates, and when the addition amount of Cu is large, the effect caused by Cu dominates. When only Cu is expected. In the case of the effect of Cu, it is believed that Cu slowly dissolves when used in a liquid, so it is considered to have a shorter life compared to the case without a photocatalyst. In addition, if the amount of Cu added is large, the cost of this part is also high. Therefore. , It can be considered that it is meaningless to set the amount of Cu excessively.

It has been confirmed by this example that not only oxides such as Sn(b, but also metals such as Cu can also become particles that fill the gaps in the TiOz particle layer.

Example 2 4 SiOz -Alz 0 in 150 square₃ -BaO composition (softening temperature 620Ό)

200610101461.3 The surface of the first glass substrate was coated with a TiOz sol aqueous solution by spraying, then fired at 95°C, and then coated with a copper acetate aqueous solution on the composite member that was cooled and solidified, and then irradiated with ultraviolet light. , Reducing copper ions and fixing them on the photocatalyst layer at the same time to obtain multifunctional glass.

At this time, a BLB lamp was used as the irradiation lamp, and it was irradiated for several minutes. TiOz changes from anatase type to rutile type by heat treatment. The film thickness of TiOz was adjusted to 0.4 μηΐ during spraying. The antibacterial and abrasion resistance tests were performed on the multifunctional glass thus produced. Regarding the abrasion resistance test, even if it is not added, it shows good results in this temperature region. Even if Cu is added, it is the same as when there is no addition, and there is no scratch or change even in 40 sliding tests.

The antibacterial test is shown in Figure 22. When it is not added, since TiOz is rutile, it is poor +. If Cu is added to it, the antibacterial properties will be improved. And not only when the BLB lamp is irradiated, but also when it is not irradiated, if the Cu loading amount becomes O^kgZcm²As described above, the antibacterial activity becomes + +, and when the Cu loading amount becomes 1.2 ug/c, the antibacterial activity becomes + + +.

It can be seen from the above that in order to provide a multifunctional glass with excellent antibacterial and blinding resistance, the amount of Cu support can be 0.7μ_ε/οιη² , Better can be 1.2μ_δ/ϋκι²。

However, if the copper acetate aqueous solution is applied and before the BLB lamp is irradiated, it enters the drying process, the Cu loading amount is drastically increased. This relationship is shown in Figure 23. It is considered that this is because the metal ion concentration during photoreduction during drying is high.

In addition, when the Cu coating amount is most suitable, the Cu loading amount becomes the largest (Figure 24, an example of copper acetate with a C ii concentration of 1% (by weight)). In Figure 24, in order to support Cu The amount is 0.7 μ-g,/cm²Above, the coating amount can be 0.2mg/cm²Above, 2.7 mg. cm 2 or less, in order to make the Cu loading amount] .2 cm²Above, the coating amount can be 0.3mg/cm² Above, 2.4mg,/cin?

200610101461.3 Example 2 5 On the surface of a glass substrate composed of 150 square SiOz -AU Os -BaO (softening temperature 68 (TC), the Ti02 sol aqueous solution was coated by spraying method, and then baked at 95 °C, The composite member formed by cooling and solidification is coated with an aqueous silver nitrate solution, dried, and then irradiated with ultraviolet light to reduce the silver ions, and at the same time, it is fixed on the photocatalyst layer to obtain a multifunctional glass.

At this time, the BLB lamp was used as the irradiation lamp, and the irradiation was performed for several minutes. In addition, Ti(h is transformed from anatase type to rutile type by heat treatment. The thickness of the TiOz film is adjusted to 0.4μm during spraying._o The antibacterial and abrasion resistance tests were performed on the multifunctional glass thus produced. Regarding abrasion resistance, even if it is not added, good results are obtained in this temperature region. Even if Ag is added, it is the same as when Ag is not added, even at 4. In the next sliding test, there was no scratch or change.

The antibacterial test is shown in Figure 25. When it is not added, Ti(h is rutile, so it is poor +. If A g is added to it, the antibacterial property is improved. And not only when the BLB lamp is taken, but also when it is not irradiated, if A g The loading capacity is 0.05μ₈/οπι²Above, the antibacterial activity becomes + +, if the A g loading is O.lugZcni² , The antibacterial property becomes + + +.

Therefore, in order to provide a multifunctional glass with excellent antibacterial properties and abrasion resistance, the loading amount of Ag can be 0.05μ₈/οιη²Above, more preferably 0.1 μ₈ζ^ζοιη²the above.

However, if there is a large amount of A g supported, it will be colored from brown to black, and the appearance will be deteriorated. However, if the Ag loading is 1 ug/cmz or less, it will not be colored.

It can be seen from the above that the loading amount of Ag can be 0.05 μg/cm²Above, 1 Ug/c* or less, preferably 0.1 μg/cm²Above, 1 μβ/οη²the following.

Example 2 6 in 150 squares made of Si0₂ -Ai₂ 0₃ - BaO composition (softening temperature 680'C) on the surface of the glass substrate, the TiX sol aqueous solution was coated by spraying method, and then at 95 (TC

200610101461.3 The first sintering is carried out, a silver nitrate aqueous solution is coated on the composite member cured by Xu Que, and dried, then light containing ultraviolet rays is irradiated to reduce the silver ions, and at the same time, it is fixed on the photochemical agent layer to obtain a multifunctional glass.

At this time, the BLB lamp was used as the irradiation lamp, and the irradiation was performed for several minutes. In addition, TiO₂After heat treatment, it changes from anatase type to rutile type.

The TiOz film thickness of the multifunctional glass thus produced was subjected to a haze resistance test, an antibacterial property test, and a stain resistance test.

Regarding the abrasion resistance test, good results were shown in the range of the test film thickness within 2 nm, and there was no scratch or change even in the sliding test of 40 times.

Regarding the antibacterial property test, it becomes + + when the film thickness is 0.1 μω or more, and becomes + + + when the film thickness is 0.2 μπι or more. Therefore, the film thickness of TWn may be 0.1 μm or more, and more preferably 0.2 μm or more.

As can be seen from the above description, because the photocatalyst particles are to be fixed on the thermoplastic substrate, especially the photocatalyst particles constituting the surface layer of the photocatalyst layer are not embedded in the thermoplastic substrate, the photocatalyst particles are substantially formed With its surface exposed to the outside, the photocatalytic effect can be fully exhibited. In addition, since a part of the particles constituting the lower layer of the photocatalyst layer among the photocatalyst particles is embedded in the thermoplastic substrate, the holding power of the photocatalyst is greatly improved, and peeling and the like are less likely to occur.

Figures 26 and 27 are conceptual diagrams of the basic distribution when observing the cross-sectional direction of the multifunctional material with EPMA (Electron Beam Microanalyzer). As shown in these figures, starting from the surface in contact with air, there is a region (A region) where the concentration of the components constituting the photocatalyst layer 2 is approximately constant, and thereafter the components constituting the photocatalyst layer decrease. In addition, the components constituting the amorphous layer (adhesive layer) are not absent or small on the surface, and the concentration increases as they enter the interior. When the mesh reaches a certain film thickness, the component concentration is approximately constant (zone B). Here, the A region is defined as the photocatalyst layer, the B region is defined as the amorphous layer, and the middle C region is defined

200610101461.3 The first is the middle layer. However, Fig. 26 is a conceptual diagram for convenience of explanation after all. In essence, as shown in Fig. 27, the concentration of a constant concentration illustrated in Fig. 26 is often accompanied by a change in concentration due to manufacturing process reasons. In this case, as shown in Figure 27, the minimum concentration of the area (A' area, B'area) corresponding to a certain area is regarded as A'area and C'area, B'area and C'respectively. The boundary of the area.

Here, the thickness of the photocatalyst layer is the thickness of the A region or the A'region, and the thickness of the intermediate layer is the thickness of the C region or the C'region.

The thickness of the intermediate layer can be changed by controlling the moving speed and possible time of the photocatalyst particles into the softened amorphous layer. The moving speed can be controlled by the difference in specific gravity between the photocatalyst particles and the amorphous layer, the calcination temperature, and the atmospheric pressure. In addition, by changing the holding time of the amorphous material at the softening temperature, the possible time of movement can be changed.

If the thickness of the intermediate layer is 1/3 or more of the thickness of the photocatalyst layer, the adhesiveness can be further increased.

The following describes specific embodiments.

Example 2 7 SiOz -Al was formed by spraying on a 1 Ocm square alumina substrate₂ Oa -Na/Core 0 system amorphous layer, after drying and firing, apply 0.01 μη) TiO by spraying method₂The sol aqueous solution was calcined at 850°C and changing the holding time to form an anatase Ti(h film of 0.2 μm, 0.5 pm, and 1 pm. Next, spraying was used on the anatase TiOz film A copper acetate aqueous solution was coated, and then photoreduction was performed (the light source was a 20-watt BLB lamp, the distance from the light source to the sample was 10 cm, and the irradiation time was 30 seconds) to obtain a sample. For the obtained sample, the cross-section of EPMA was used. Elemental analysis (T i, Si), measure film thickness, evaluate antibacterial and abrasion resistance.

For the evaluation of antibacterial properties, E. coli (Escherichia coli V3110 strain) was used as a test. Bacterial liquid was dripped on the outermost surface of the multifunctional member previously sterilized with 70 ethanol.

200610101461.3 p.

0.15ml (1 -50000 CFU), put it on a glass plate (100X100), make it closely adhere to the furthest surface of the substrate, as a sample. After irradiating with a white light (3500 Lux) for 30 minutes, wipe the irradiated sample bacterial solution with sterile gauze and recover it in 1 Ond physiological saline to obtain the bacterial survival rate as an evaluation index. The evaluation criteria are the same as those in Table 1 above.

The results are summarized in Table 18. All about antibacterial properties are + + +.

Abrasion resistance, or Ο all indicate good results. In particular, all samples whose ratio of the thickness of the intermediate layer to the thickness of the photocatalyst layer is 1/3 or more are ©.

(Table 18)

<td>TiO2 film thickness (pm)</td><td>Intermediate layer (μπηΤ</td><td>Keep it happy (hours)</td><td>Intermediate layer thickness/ΤΪΟ2 film thickness</td><td>Antibacterial</td><td>Peel resistance</td>

<td>1</td><td>0.42</td><td>16</td><td>0.42</td><td>+ + +</td><td>◎</td>

<td>1</td><td>0,33</td><td>2</td><td>0.33</td><td>+ + +</td><td>◎</td>

<td>1</td><td>0.30</td><td>1</td><td>0.30</td><td>+ + +</td><td>ο</td>

<td>0.5</td><td>0.17</td><td>2</td><td>0.34</td><td>+ + +</td><td>◎</td>

<td>0.5</td><td>0.1 3</td><td>1</td><td>0.26</td><td>+ + +</td><td>ο</td>

<td>0.2</td><td>0.08</td><td>2</td><td>0.40</td><td>+ + +</td><td>◎</td>

<td>0.2</td><td>0.05</td><td>1</td><td>0.25</td><td>+ + +</td><td>ο</td>

<td>1</td><td>0</td><td></td><td>0</td><td>+ + +</td><td>Δ</td>

Example 2 8 On a 10cm square alumina substrate, the ammonia dispersion of TiOz sol with an average particle size of 0.01 μm was sprayed by spraying, and it was fired at 85LC to form an anatase type with a film thickness of 1 um. Ti(h thin film. Next, on the anatase type TiOz thin film, a copper acetate aqueous solution was sprayed and then photoreduced (the light source is a 2 Q-watt BLB lamp, and the distance from the light source to the sample is 10 cm , Irradiate for 30 seconds) to obtain a sample. The antibacterial and abrasion resistance of the obtained sample are evaluated.

200610101461.3 As a result, the antibacterial properties are good, but the abrasion resistance is , which is not sufficient.

It can be seen from the above description that when the photocatalyst I layer is held on the surface of the substrate through the amorphous layer, the upper part of the photocatalyst layer should be exposed in contact with the air, and the photocatalyst layer has particles that bind to each other. In the multifunctional material with photocatalytic function, the amorphous layer and the photocatalyst layer should have an intermediate layer in which the component concentrations of both are continuously changed between them. This can increase the adhesion between the photocatalyst film and the substrate and improve the resistance. Peelability. Furthermore, making the thickness of the intermediate layer 1/3 or more of the thickness of the photocatalyst layer can further increase the adhesion.

The following describes the case where the photocatalyst layer 2 is formed by sintering. Figure 1 (a) is a diagram showing the state of the conventional TiOz particles before sintering, and (b) is a diagram showing the state after sintering. As shown in Figure 1 (a), the surface of the substrate 1 is coated with TiOz particles 3 Sol. If it is heat-treated (sintered) in order to increase the film strength, cracks 2a are likely to occur as shown in Fig. 1(b). The reason can be thought to be in addition to the volume consolidation (increased density) caused by the phase transition to rutile type , Ti is still before sintering (the interval between b particles 101 is Lo, but after sintering is rutile, the interval between particles becomes shorter to L due to volume diffusion to each other) (L₁ &lt;Lo), resulting in cracks.

Therefore, SnOz is made to be knitted in the necked part of the sintered bonded TiOz particles 3 to make the necked part coarse and strengthen the bonding of the TiOz particles 3 to each other, and as a result, the film strength is improved.

In order to form the photocatalyst layer 2 as described above, the Sn(h) sol is mixed and stirred in the TiCk sol, coated on the substrate 1, and heat-treated (sintered) in a predetermined temperature range.

In addition, Ti (h sol concentration is about 4-6% (weight), adjusted to PH 1 1 with NHm solution, the average primary particle size of TiCL·particles is 0.01 μ m (10 run), SnO₂The sol concentration is about 10% (weight), adjusted to pH 1 1 with NH3 solution, Sn (J₂The average primary particle size of the particles is 0.0035 μm. The average primary particle size shown here is the crystallite size (primary particle size) calculated from the half-value width of XRD (X-ray diffraction) diffraction lines.

200610101461.3 p.

grain).

Here, because SnOz has a higher affinity pressure than TiOz, the interval between TiOz particles 3 before sintering is L as shown in Fig. 17(a). However, the surface vapor pressure of the surface with the positive curvature of the titanium oxide particles 3 is high, and the surface with the negative curvature, that is, the surface vapor pressure of the necked part where the two titanium oxide particles 3 meet, becomes low. As a result, as shown in Fig. 17(b), SnOz whose vapor pressure is higher than that of titanium oxide enters the necked part, and condenses as shown in Fig. 17(c), and sinters according to the vaporization-condensation mechanism.

Moreover, if the sintering is performed according to the vaporization-condensation mechanism, the interval Lz of the Ti (h) particles after sintering is approximately equal to the interval Lo before sintering, so no cracks are generated.

As mentioned above, before and after sintering, the spacing of TiOz particles should not change substantially, and the photoactivity (Rs.) of the photocatalyst coating should be 50% or more. As shown in Fig. 28, it is necessary to make The ratio (inner ratio) of SnOw to Ti(h) is 20-70% or more.

In addition, the compounding ratio means the weight ratio of the solid content contained in each sol. In addition, the evaluation of photoactivity was performed by the decomposition of methyl mercaptan, and the removal rate (Rao) after 0 minutes of light M3 was used as an index. In detail, in a 1 1 L glass container, the 150 square material bricks with the photocatalyst coating film formed are arranged at a distance of 8 cm from the light source (BLB fluorescent lamp, 4W), and the methyl mercaptan gas is 3 -5 ppm is injected into the container, after confirming that there is no adsorption in the dark, the fluorescent lamp is turned on, and the concentration change with time is measured by gas chromatography.

Here, R 30 - (Xο~ X 30) ^z XοX 100% where Xo two initial concentration [ppm] X3. Concentration after 30 minutes [ppm] In addition, the film strength was evaluated by sliding friction using a plastic rubber to compare the change in appearance. Regarding the evaluation criteria , O, , and X are the same as the above (Table 1).

In addition, Figure 29 is a graph showing the relationship between the heat treatment temperature and the photoactivity. When organic stabilizers are added to the TiX sol, although the photoactivity is reduced, the heat treatment temperature is 300-850Ό. This is because the heat treatment temperature is less than 30 (TC). Produce activity, if super

200610101461.3 After 85 (TC, the structure of TiOz changes from anatase type to rutile type.

It can be seen from the above description that a sol containing titanium oxide particles and a substance whose vapor pressure is higher than that of titanium oxide is coated on porcelain, etc., and fired at a predetermined temperature. The coating is formed, so the interval between the titanium oxide particles before and after sintering is approximately equal, and cracking is not easy to occur. In addition, since SnOz or the like is condensed in the necked portion between the titanium oxide particles, the peel strength of the coating film becomes high.

In particular, make the addition amount (with TiO₂The internal ratio of) reaches 2 D -70%, which can meet the requirements of film strength and photoactivity. In addition, heat treatment in the range of 30°C or more and 850°C or less can obtain sufficient photoactivity.

However, using gas chromatography to determine R_3O.The measuring device is expensive, and one device can only measure one sample, so the efficiency is poor.

In addition, although it is known that metal such as P t is supported on TiOz to improve photoactivity, in a photocatalyst film with such a structure, it is difficult to determine the degree of net photoactivity due to the effect of gas adsorption due to the metal. .

In addition, if ceramic tiles are used as the wall surface, the activity of the photocatalyst thin film formed on the surface cannot be measured with a gas chromatograph once it has been installed.

In addition, as a method for evaluating the photoactivity without using a gas chromatograph, although a method of detecting the survival rate after light irradiation that kills bacteria by the action of a photocatalyst can be considered, it is more troublesome than the operation on a gas chromatograph, and it is more difficult to carry In the metal photocatalyst film, since the antibacterial activity of the metal itself also kills bacteria, it is not easy to determine the net light activity. Therefore, the following method for measuring the activity of the photocatalyst thin film can also be applied.

In the first method, a potassium halide aqueous solution such as potassium iodide or potassium chloride is applied to the surface of a photocatalyst film mainly composed of TiOz formed on the surface of the substrate, and then the dropped potassium halide aqueous solution is irradiated with ultraviolet rays for a predetermined period of time. The activity size of the photocatalyst film was judged from the difference between the pH of the potassium halide aqueous solution before the irradiation and the pH after the irradiation.

200610101461.3 The second method is on the surface of the photocatalyst film mainly composed of TiOz formed on the surface of the substrate, Urashita adds a mixture of pH indicator to the potassium iodide or potassium chloride and potassium halide aqueous solution, and then to the surface of the photocatalyst film. The vortex liquid below is irradiated with ultraviolet rays for a given period of time. Due to the color change of the mixed liquid, the activity of the photocatalyst film can be judged.

In the third method, an activity measuring film is adhered to the surface of a photocatalyst thin film mainly composed of TiOz formed on the surface of the substrate. In this state, the activity measuring film is irradiated with ultraviolet rays for a given period of time. Due to the color change of the activity measuring film, Therefore, the activity size of the photocatalyst film can be judged.

Fig. 30 illustrates the first and second activity measurement methods. The photocatalyst layer 2 mainly composed of TiOz is formed on the surface of the substrate 1. Such a photocatalyst thin film activity measurement method can be applied.

In the first method, a potassium halide aqueous solution such as potassium iodide or potassium chloride is filled on the surface of a photocatalyst film mainly composed of TiOz formed on the surface of the substrate, and then, the dripped potassium halide aqueous solution is irradiated with ultraviolet rays for a given period of time. The difference between the pH of the potassium halide aqueous solution before irradiation and the pH after irradiation determines the activity of the photocatalyst film.

In the second method, the Ti(k-based photocatalyst thin film formed on the surface of the substrate is dripped on the surface of the thin film with a pH indicator added to the potassium halide aqueous solution such as potassium iodide or potassium chloride, and then The dripped mixed liquid is irradiated with ultraviolet rays for a given period of time. Due to the color change of the mixed liquid, the activity of the photocatalyst film can be judged.

The third method is to form TiO on the surface of the substrate₂An activity measuring film is adhered to the surface of the photocatalyst film as the main body, and the activity measuring film is irradiated with ultraviolet rays for a given time in this state. As the color of the activity measuring film changes, the activity level of the photocatalyst film can be judged.

Figure 30 illustrates the first and second activity measuring methods. A photocatalyst layer 2 with Ti(h as the main body) is formed on the surface of the substrate 1. In order to detect whether the photocatalyst layer 2 is

200610101461.3 The first is photoactive, the surface of the photocatalyst layer 2 is covered with a potassium halide aqueous solution 30 such as potassium iodide or potassium chloride, and then the full potassium halide aqueous solution 30 is irradiated with ultraviolet light 40 for a given time The activity level of the photocatalyst layer 2 is judged from the difference between the pH of the potassium halide aqueous solution before the irradiation and the pH after the irradiation.

Figure 33 shows the relationship between the UV irradiation time and the change in pH. The concentration of the potassium halide aqueous solution 30 is 0.1rool/L, the ultraviolet lamp uses a 20W BLB fluorescent lamp, and the distance between the photocatalyst layer 2 and the ultraviolet lamp 40 is 20 cm, irradiation time is 60 minutes.

It can be seen from this figure that regardless of the anatase type, the metal-supported type, or the rutile type, in the photocatalyst layer 2, the UV irradiation time reaches 30 minutes, and the pH of the potassium halide aqueous solution 30 becomes higher.

In this way, the pH of the potassium halide aqueous solution 30 becomes higher due to ultraviolet irradiation, because the following oxidation reaction and reduction reaction proceed simultaneously, and OH "(hydroxide ion) is produced by the reduction reaction.

Oxidation reaction: 2 I-+ 2 h+ = I ζ Reduction reaction: On + 2 Hz 0+ 4 e^- = 4 OH~ Therefore, if the pH of the potassium halide aqueous solution 30 becomes higher due to ultraviolet irradiation, it can be said that the photocatalyst layer 2 has photoactivity.

Figure 34 shows Rs. The relationship curve with the amount of pH change. In the figure, Rg is the proportion (%) of the gas (methyl mercaptan, etc.) that decreases 30 minutes after ultraviolet irradiation. From the figure, Rs is known. There is a proportional correlation with the change of P Η. That is, the amount of change in pH serves as an index for the presence or absence of photoactivity.

In the first method above, the change in pH is measured with a pH measuring instrument or a pH measuring chip, but in the second method, a warm droplet with a pH indicator added to a potassium halide aqueous solution 30 is exposed to light. On the surface of the catalyst layer 2, next, the dripped mixed liquid is irradiated with ultraviolet rays for a given time. As the color of the mixed liquid changes, the photocatalyst layer 2 can be judged

200610101461.3 The size of the first activity.

As a pH indicator, since the pH of the potassium halide aqueous solution 30 before ultraviolet irradiation is about 4.5, and the pH after ultraviolet irradiation is 5.5-6.5, methyl red is suitable.

In addition, in the first and second methods described above, the surface of the photocatalyst layer 2 is filled with the potassium halide aqueous solution 30 or the potassium halide aqueous solution 3 Q is added with a pH indicator mixture on each substrate. The diffusion of the underlying liquid is varied, and a certain liquid thickness cannot be guaranteed. The reaction area varies with each substrate.

The method to eliminate this is the method shown in Figure 31. In this method, after the potassium halide aqueous solution 30 is filled on the surface of the photocatalyst layer 2, the potassium halide is pressed by a transparent plate 60 such as a glass plate. The aqueous solution 30 can prevent drying while forming a certain thickness.

In addition, liquids such as the potassium halide aqueous solution 30 are based on the condition that the surface of the substrate 1 is horizontal, so it is difficult to judge the activity of the photocatalyst film formed on the vertical surface of the established wall surface and the ceiling.

The method to eliminate this is the method shown in Fig. 32. In this method, an activity measuring film 70 is attached to the surface of the photocatalyst layer 2 formed on the surface of the substrate 1, and the activity is measured in this state. The film 70 is irradiated with ultraviolet rays, and since the color of the activity measuring film 70 changes, the degree of activity of the photocatalyst layer 2 can be judged.

Here, the activity measurement membrane is obtained by drying a mixture of potassium halide aqueous solutions such as potassium iodide or potassium chloride and a pH indicator on an organic binder to form a thin film.

Next, the porosity of the photocatalyst layer 2 is examined. Here, the porosity is called open porosity, and the porosity is 10% or more and 40% or less, preferably 10% or more and 30% or less.

In this case, the crystal particle diameter of the photocatalyst particles may be 0.1 μιη or less, preferably 0.04 μη. With F·, the smaller the crystal particle diameter, the larger the effective area of reaction per unit volume, so the photocatalyst layer The thickness of the film can be about 0.1 μm. In addition, make light snuggle

200610101461.3 Solid phase sintering between the particles of the first agent to form a necked part, so that in the case of increasing the strength of the layer, the grain size is increased to 0.1 μm or more, because the effective area of reaction per unit volume is reduced, so that the film The thickness is 0.5 μm or more, preferably 0.6 or more.

In addition, between the photocatalyst particles constituting the photocatalyst layer formed on the surface of the substrate, particles having a crystal particle size of 0.01um or less, preferably 0.008 μm or less may be added. By adding such particles, the gaps between the photocatalyst particles can be filled, and the particle filling rate and surface slip can be improved, thereby increasing the film strength against shear stress. Due to the improved surface smoothness, contamination can be made difficult to adhere. Although the porosity is reduced at this time, the buried porosity is below the crystal grain size of 0.01 μm, and the size of the particles below 0.008 μm enters, which is larger than the size of the gas (number &amp;). Therefore, the deodorant is not sound.

Here, the type of particles with a crystal particle size of 0.01 μm or less, preferably 0.008 μm or less, basically any type is acceptable. However, in addition to filling the gaps of the photocatalyst particles, there is a risk of covering a part of the surface. Ti(k, Sn(b, ZnO, SrTiOs&gt; Fez 0₃Oxide semiconductors such as, Biz O3, WO3, or metals such as Ag and Cd are ideal. In addition, the crystal particle size is 0.01 μm or less, and preferably, the addition method of particles having a particle size of 00 m or less can basically be any method. For example, such ultrafine particles can be generated by hydrothermal treatment, dispersed into a sol with a suitable dispersion, and the sol can be coated on the photocatalyst layer by spraying, and heat treatment can be performed at a low temperature where no particle growth occurs to make the organic The dispersant evaporates. In addition, the photocatalyst layer may be coated with a metal oxylate and an organic metal salt, heat-treated, and the diluent, organic components, etc. may be evaporated.

In addition, metal particles smaller than the pore diameter of the photocatalyst layer formed on the surface of the substrate may be fixed. By fixing the metal particles and using the electron trapping effect, the photocatalytic activity is improved and the deodorization becomes better compared with the case of a separate photocatalyst layer.

Here, the type of metal particles can be any substance that can trap electrons. For example, C ii, Ag, P t, etc. can be mentioned.

200610101461.3 The average particle size of the metal particles must be smaller than the average pore size on the surface of the photocatalyst layer. And if the average pore size of the photocatalyst layer has a porosity of 10% or more, and a sample below 40M is observed with an electron microscope, because the diameter is approximately the same as the photocatalyst particles, it is required to be smaller than the photocatalyst particles. Ideally, it can be smaller than the photocatalyst particle diameter of the starting material. The starting material of the photocatalyst layer generally uses a material below 0.0δμm, so it may be below 0.05μm.

The following are specific examples of porosity.

Example 2 8 On a 15cm square ceramic tile substrate, spraying was used to change the coating amount to coat the nitrile gel type suspension of crystal particle size O. OUmTiOz sol, at a temperature above 70 (TC, below 90 (TC) It is calcined to form a photocatalyst layer, and the obtained samples are evaluated for the crystal size of the anatase-type Ti(b) particles, the open porosity of the layer surface, deodorization, abrasion resistance, and peeling resistance.

Evaluation of deodorization by measuring R₃₀(L) Perform an evaluation. The so-called R so (L) is the removal rate after light irradiation. Specifically, in a 11-liter glass container, the surface where the sample photocatalyst film is formed is arranged at a distance of 8 cm from the light source (BLB fluorescent lamp, 4W). , The initial concentration of methyl mercaptan gas was 3 ppm, it was injected into the container, and the concentration change at 30 minutes of irradiation was measured.

The abrasion resistance evaluation uses the sliding friction of a plastic rubber to compare the changes in appearance and perform evaluation. The evaluation index is the same as the above, and is shown in the following.

: No change to 40 reciprocations

O: There are scratches in the sliding of 10 times or more and 40 times or less, and the photocatalyst layer (TiO₂Film) Peeling : Scratch occurs after 5 times or more and 10 times or less, and the photocatalyst layer (TiOz film) is peeled off

X: There are scratches after sliding less than 5 times, and the photocatalyst layer (TiOz film) is peeled off

200610101461.3 The first departure.

The peeling resistance test is a test that is more severe than the abrasion resistance test. Instead of plastic rubber, a sanding rubber with greater shear strength (LION TYPEWRITERERASER 502) is used. The specific evaluation method is to use sand rubber to uniformly force The surface of the sample was rubbed 20 times and visually compared with the standard sample in a state containing scratches. The evaluation criteria are as follows.

: No change at all

Ο: Confirm a slight change with light addition and subtraction : Confirm a slight change

X: It can be confirmed at a glance that the result of the change is shown in Fig. 35-Fig. 37.

Figure 35 shows the relationship between the porosity and the deodorization and abrasion resistance when the thickness of the photocatalyst film is made 0.5μπι. The deodorant property increases with the increase in the porosity of the house, exceeding 50% at 10%, and reaching over 80% at 30%. On the contrary, the wear resistance is at 30%, but it is Ο at 40%, and if it exceeds this, it is or X. From the above facts, it can be seen that in order to produce a member with both deodorization and abrasion resistance, the porosity of the photocatalyst film must be 10% or more and 40% or less, preferably 10% or more and 30% or less .

Fig. 36 shows the relationship between the deodorant property and the film thickness when the crystal size of the photocatalyst particles constituting the photocatalyst thin film with a porosity of 20-30% changes. The crystal size is O.Um see R_3O(L) In relation to film thickness, if it becomes thinner, the deodorization property will fall. However, the relationship with the film thickness is not seen at 0.04 μm or less, and even if the film thickness is 0.1 μm, it shows good deodorant properties. From the above facts, it can be seen that making the crystal grain size of the photocatalyst particles less than O.Um, preferably less than 0.04μηι, can make the photocatalyst thin film to a thickness of 0.1μιη and ensure good deodorization. Sex.

Figure 37 shows the relationship between deodorization and peeling resistance and film thickness when the photocatalyst particles constituting the photocatalyst thin film with a porosity of 20-30% and the bonding state are changed.

200610101461.3 The first series. If the required value of mechanical strength rises to the level of peel resistance test, the sample without necking is or X. In addition, in order to form a mechanically sufficient necking bond by solid phase sintering of the photocatalyst particles with each other, it is not enough for the photocatalyst particles to grow to 0.04 μm, and it is necessary to grow to about 0.1 μm. However, if the photocatalyst particles are grown to the level of 0.1 μm, the deodorization is already related to the film thickness. The thicker the film, the more the deodorization increases. Specifically, when the film thickness is 0.5 μm, R_3O (L) exceeds 5 Ο%, and reaches above 80% at 0.6μm. From the above results, it can be seen that the solid phase sintering of the photocatalyst particles with each other and the formation of neckings between the particles, and the growth of the particles to a crystal grain size of O.Um or more, can sufficiently improve the film strength. In this case, by increasing the crystal grain size to 0.1 μm or more, since the effective reaction area per unit volume is reduced, the film thickness must be 0.5 μm or more, preferably 0.6 μm or more.

Example 29 On a 15cm square ceramic tile substrate, sprayed coating the ammoniolytic gel suspension of TiOz gel with a crystal particle size of 0.01 um, and calcined at 75°C to form a photocatalyst film. At this stage The porosity of the TiOz film is 4 5%, Τ10₂The crystal particle size of the particles is 0.02 μηΐο, respectively, by spraying, and then coating SnOz sols with different crystal particle sizes on the particles, and then drying them at 110°C to obtain samples. The deodorization and abrasion resistance were evaluated for the obtained samples.

The results are shown in Figure 38. Regarding the deodorization property, the crystal particle size of the SnOz sol hardly changed from 0.0035 um to 0.01 μm, showing good results. Contrary to this, the effect of abrasion resistance when added 30% (heavy Dong) or more varies with the crystal particle size of Sn(b) sol. That is, in the case of adding particles of 0.008 μm or less, the effect of adding more than or Ο Improved, but no additive effect is seen at 0.01 μm. From the above results, it can be seen that by adding particles with a crystal particle size of 0.01 μm or less, preferably 0.008 μ-m or less, between the photocatalyst particles, the abrasion resistance can be improved.

200610101461.3 Example 30 On a 15cm square ceramic tile substrate, the ammoniolytic gel suspension with a crystal particle size of 0.01 μm of Ti(L·sol was coated by spraying method and varying the amount of coating, at 85(TC) After firing, a photocatalyst thin film with a thickness of 0.2 nm is formed. Next, a copper acetate aqueous solution is coated on the photocatalyst thin film by a coating method, and then photoreduction is performed (light source 20 W BLB lamp, the distance from the light source to the sample is 1 Ocm, irradiation time 10 seconds), to obtain a sample. At this time, the amount of copper supported is 2 ug/cm?, and its particle size is a few nm-10 nm. In addition, the crystal particle size of the photocatalyst particles is O. Umo evaluated the deodorant property and abrasion resistance of the obtained sample.

As a result, R ₃₀ (L) is 80%, and the abrasion resistance is therefore compared with Figure 36. Since copper is supported, R₃₀ (L) rose sharply from 1.8% to 89%.

From the above description, it can be seen that by forming a photocatalyst film with a porosity of 10% or more and 40% or less, preferably 10% or more and 30% or less, on the surface of the substrate, it can provide deodorization and abrasion resistance. Sexual components.

Next, an example in which the gap formed on the photocatalyst layer is filled with particles smaller than the gap will be described. The gap in this embodiment refers to both the gap between the separated particles and the B5 portion of the constricted portion.

In addition, if the photocatalyst layer is dense, it is excellent in terms of film strength and resistance to contamination. However, because the temperature at which the photocatalyst layer is formed generally increases, the material of the substrate is limited, so if the particles are filled in the subsequent process If desired in the gap, the porosity of the photocatalyst layer before the addition of gap particles can be 10% or more. In addition, a membrane with a porosity of 10% or less has excellent odor resistance. Therefore, by adjusting the filling amount, it is possible to provide a multifunctional material that is excellent in both law resistance and odor resistance.

The particles in the gaps that are smaller than the gaps to be filled are preferably composed of inorganic crystalline raw materials, and more preferably can be derived from TiOz and SnO with photocatalytic activity.₂, ZnO, SrTiOa, Fez 0₃, Biz 0₃, V0₃And other oxide semiconductors.

200610101461.3 The size of the particles smaller than the gap can be basically smaller than the average value of the generated pores. By reducing the gap and reducing the particles adhering to the surface of the particles with photocatalytic function, the surface smoothness and surface defects are improved, in order to achieve less adhesion of contamination and increase the film strength, specifically it can be 0.01 μ Π1 or less, preferably Small particles below 0.008 μm. However, when the Ti(h) film is anatase type and is heat-treated below 850*C and fixed on the substrate, observation with an electron microscope shows that the average pore diameter and the diameter of the TiOz particles are approximately equal to that of the TiOz particles. Small is enough. The starting material for the photocatalytically active Ti(h film) usually uses a raw material below 0.05 μm, so it can be a raw material below Ο.Οδμιη.

Here, the surface porosity of the layer with the photocatalytic function formed by filling the gaps with particles is 20% or less, making it more difficult for contamination to adhere. It is more desirable that the maximum width of the pores is 0.04|xm or less.

Here, the so-called porosity is the open porosity on the surface of the substrate. The maximum width of the open pores is the maximum distance between two adjacent particles (average value + 3 X standard) among the particles with photocatalytic function that constitute the surface of the substrate. deviation).

In addition, if a layer with a porosity of about 10% of a layer with a photocatalytic function before the particles are filled in the gap is used, although the porosity is reduced to 10% or less, the diameter of the pores buried here is crystal grains. The entry size of particles with a diameter of 0.01 μm or less is larger than the size of the gas (number A), so it does not affect the deodorization performance, and can maintain the same size as the pre-made TiOz film with a porosity of 10% or more. Deodorant properties.

In addition, the layer with the formed photocatalytic function is mainly crystalline photocatalyst particles, so that the dirt does not adhere in a firm adhesion form of the glass adhesion type, and at the same time, even if the scale adheres, it is relatively easy to wipe off. In addition, there is an effect that algae is not easily produced when water is recycled. Here, the so-called crystalline photocatalyst particles means that when the photocatalyst particles peeled off from the component are subjected to powder X-ray diffraction under the conditions of 5 OKV and 300 mA, the maximum crystallization is Peak (for example, in Ti (h particles, anatase type 2. 25.3 °, rutile type 28 27.4.)

200610101461.3 Crystallized into photocatalyst particles at the detection level.

As a method of filling particles in the above-mentioned gaps, alkoxylates, organometallic salts, sulfates, etc. are used, and they are carried out by coating, drying, and heat treatment. For example, the process of using a metal alkoxide is to mix the metal alkoxide with a suitable diluent and hydrochloric acid and coat the solution on the outermost surface of the photocatalyst layer, and then dry and heat it. The so-called diluent here is preferably alcohols such as ethanol, propanol, methanol, etc., but it is not limited to this. Can be as free as possible. If it contains water, the hydrolysis of the metal alkoxide is explosively promoted, which becomes a cause of cracks. In addition, hydrochloric acid is added to prevent cracking during drying and heat treatment. The coating method of metal alkoxide is based on the curtain coating method. But it is not limited to this. Rain coating is best carried out in dry air. If it is applied in normal air (atmosphere), the moisture in the air promotes hydrolysis, making it difficult to control the film thickness. It can be applied once or several times. This is determined by the fillability of the photocatalyst layer before coating. After that, place it in dry air for a few minutes to form a film in which the gaps of the photocatalyst layer are filled with particles.

Here, if the filler particles are preliminarily made of the same material as the layer before coating the filler particles, the thermal expansion coefficient is also the same, and it is desirable because a film with excellent mechanical strength can be formed.

As a specific example, an example of using titanium alkoxide will be described again. In the process of re-coating titanium alkoxide on the surface of the photocatalyst layer and performing drying heat treatment, the coating amount of titanium alkoxide per time, converted to TiOz, is 10 ng/cm²Above, 100ug/cm? below. If the amount is too small, the number of coatings must be increased, so the efficiency is low. On the contrary, if the amount is too large, the film thickness per coating is too thick, and cracks occur during drying and heat treatment.

In the above-mentioned dry heat treatment process, the heat treatment temperature is 40°C above, 800°C or lower, below 4°rc, amorphous TiOz does not crystallize into anatase Ti(h, rapid particle growth occurs at 80°rc, so Reduced photoactivity

In addition, the amount of hydrochloric acid relative to the titanium alkoxide in the coating liquid should be 1% (weight)

200610101461.3 above and below 10% (weight). Below 1% (weight), the crack prevention effect is insufficient. If it exceeds 10% (weight), because hydrochloric acid is usually a 3 6% aqueous solution with a large amount of water, the hydrolysis is excessively promoted and cracks are formed. When the amount of hydrochloric acid is large, the diluent may be large. Because the diluent inhibits hydrolysis. The ratio is hydrochloric acid (except water): the diluent can be about 1:100-1:1000.

Furthermore, a layer with a photocatalytic function is formed, and the gap formed on the surface of the layer is filled with particles smaller than the gap, and cu, Ag, Z η, Fe, Co, Ni can be fixed. , P d, P t at least one metal. Due to such a structure, the above-mentioned metal preliminarily occupies a highly adsorbable portion of the layer having a photocatalytic function, and alkali metals, calcium, etc. in the dirt component adhere to the portion, and the photocatalytic activity is not lost. Therefore, it is difficult to impair the antibacterial effect of the photocatalyst, and it is also possible to prevent contamination due to the adhesion of fungi. In addition, if Ag, Cu, and Zn are used as the aforementioned metals, these metals themselves have antibacterial properties, so that the adhesion of fungi can be prevented more effectively. The electron trapping effect of these metals is also used to improve the photoactivity of the photocatalyst layer.

The size of the metal to be fixed is so large that it preliminarily occupies the highly adsorbed portion of the photocatalyst layer, and it can be small to maintain high activity. From this point of view, it is best to be several nm-1 Onm.

Here, as a method of fixing the above-mentioned metal, photoreduction, heat treatment, sputtering, chemical vapor deposition, etc. can be used. However, it never requires large-scale equipment, is a relatively simple method and can be firmly fixed. , The photoreduction method is preferred. The process of photoreduction is to coat an aqueous solution containing at least one metal ion among A g. Gu, Zn, Fe, Co, Ni, Pd, and P t, and then irradiate light containing ultraviolet rays. In the aqueous solution containing at least one metal ion of Ag, Cu, Z η, Fe, Co, Ni, Pd, P t, copper acetate, silver nitrate, copper carbonate, copper sulfate, and sodium chloride Copper, copper oxide, chlorinate, chlorinated rake, nickel chloride, zinc nitrate, chlorinated cobalt, ferrous chloride, ferric chloride, etc.

200610101461.3 The coating method of these metal salts can basically be any one of the above-mentioned methods, but the spraying method or the dipping method is relatively simple. Compared with the two, the spraying method is more ideal in terms of the small amount of solution used, the uniform coating, the easy control of the film thickness, and the ability to not adhere to the back as needed. When irradiating a light source containing ultraviolet light, any light source capable of irradiating ultraviolet light may be sufficient. Specifically, any of an ultraviolet lamp, a BLB lamp, a ferment lamp, a mercury lamp, and a fluorescent lamp may be used. The method of irradiating ultraviolet light is ideal for placing the sample so that the light is vertically irradiated on the surface of the star, because the irradiation rate is the best. The irradiation time is preferably about 10 seconds to 10 minutes.

If the irradiation time is too short, the above-mentioned metals will not sufficiently adhere to the highly absorbing part of the photocatalyst layer, and therefore the framing metals, calcium, etc. in the dust component will adhere, which will cause the loss of photocatalytic activity. If the time is too long, the above-mentioned metals will adhere excessively , It is difficult for light to reach the photocatalyst layer sufficiently, thus reducing the photocatalytic activity. The distance between the sample and the light source is preferably 1 cm- 3 Ocmo. The distance is too short, the light cannot irradiate the entire sample surface with approximately uniform illuminance, and the adhesion deviation of the above-mentioned metal is likely to occur. If the distance is too long, the illuminance of the light is inversely proportional to the square of the distance. If it becomes smaller, it is difficult to attach the metal firmly.

A specific example of filling the gap formed on the photocatalyst layer with particles smaller than the gap will be given below.

Example 3 1 On a 15cm square ceramic tile substrate, sprayed coating the ammoniolytic colloidal suspension of TiOz sol with a crystal particle size of 0.01 μm, and calcined at 75°C to form an anatase TiOz film. The porosity of the TiOz film at this stage is 4 5%, and the crystal grain size of the TiOz particles is 0.02 μ ni. Next, SnO sol with different crystal grain sizes is sprayed on it, and dried in a litre to obtain a sample .Evaluation of the odor resistance, abrasion resistance, and the difficulty of adhesion of contamination were performed on the obtained samples.

The deodorant property was evaluated by measuring κ 30 (L).

Regarding the wear resistance, use plastic rubber for sliding friction, and compare the changes in appearance to evaluate

200610101461.3 The first price. The evaluation index is as follows.

: No change to 40 reciprocations

O: Scratch is caused by sliding of 10 times or more and 40 times or less, TiO₂Layer peeling Δ: Scratches in 5 or more sliding times and 10 times or less, TiOz layer peeling X: Scratches in 5 or less sliding slidings, and TίΟζ layer peeling is high.

Regarding the evaluation of the difficulty of stain adhesion, a black thick universal pen was used to draw a line on the surface of the substrate, and the stain was evaluated by wiping off the pen line with ethanol after drying. The evaluation index is shown.

: The trace disappeared completely.

Ο: A trace remains slightly.

: Gray-green traces remain.

X: A black mark remains.

The results are shown in Figure 39-Figure 46.

Figure 39 shows the difficulty of contamination adhesion relative to the addition amount of Sn(b. In this figure, the addition amount of SnOz is expressed in terms of the weight relative to the amount of TiOz and Sn(k and the weight ratio of Sn(b). When SNJn more than 3096 is added, The degree of pollution that is difficult to adhere to is increasing rapidly. The reasons for this are explained as the following three points.

The first is due to the addition of more than 30% SnOz&gt; so the porosity is reduced to less than 20% (Figure 4 0) c. The second is that due to the addition of SnOz, the pores with large pores are reduced. Figure 4 1 shows the maximum width of open pores relative to the amount of SfiOn added, SnO₂When the addition amount is more than 30%, it becomes a very small 0.04μπι_ΰThe third reason is that the addition of SnOz improves the surface finish, which also has an impact.

Fig. 42 shows the deodorant property and abrasion resistance relative to the amount of SnOz added.

Regarding deodorization, even if the crystal particle size of SMh sol changes from 0.0035μηι to

There was almost no change at 0.01 μm, showing good results. In addition, when the amount of SnOz is 5096 F, Rsq shows a good result of 80% or more. Comparing the relationship between Sn(*addition amount and porosity) in Fig. 39, it can be seen that SnO₂The addition amount is more than 40%, less than 50%

200610101461.3 At the bottom, although the porosity is 10% or less, good deodorization is formed. The result of this tendency is different from the result of the relationship between porosity and deodorization in the case of not adding the bumps of the filling gap (Figure 3 to 5). The reason can be considered as follows. In this case, although the porosity is reduced to less than 10%, compared with Figure 41, there are still pores of about 0.02μm, and the grain size of the particles in the filling gap is 0.0035μm and the size of the gas (number A) is the same. The ratio is large, so under the condition that the particles do not grow up, the path that does not generate gas is blocked.

Regarding abrasion resistance, the effect when the addition amount of SnOz is 30% or more differs depending on the crystal grain size of the SnOz sol. That is, when particles of 0.008 μm or less are added, it increases to or Ο, but the effect of addition is not seen at 0.01 μm.

It can be seen from this experiment that: (1) A TiDz film is formed on the substrate, and if particles smaller than the gap (SnOz sol) are added to the gap formed on the surface of the film, it is difficult for contamination to adhere.

(2) SnO₂If the amount of addition of TiOz and Sn (b) is 30% (heavy Dong) or more, the contamination will not be easy to adhere, and the abrasion resistance will also be improved.

(3) If the addition amount of SnOz is 50% by weight or less relative to the total weight of TiOz and Sn (h), the deodorant properties can still be maintained well.

(4) If the porosity is 20% or less and the maximum width of the open pores is 0.04 μm or less, it will be difficult for contamination to adhere.

Example 3 2 Anatase-type TiOz-forming material was installed on the side of the urinal counter where no light was seen, and a two-week field test was carried out. The result was compared with a material that does not form a normal anatase-type TiOz film. Both attach to the yellow dirt caused by fungus, kidney, bladder and other stones. However, in contrast to the normal wiping of the dirt on the toilet bowl, when a material forming an anatase-type TιΟζ film is used on the side part, the yellow color of the dirt will almost disappear significantly if it is wiped.

200610101461.3 Due to the lack of light on the side of the operator, the result is explained as the lack of the photocatalytic effect of the anatase TiOz film. It is not as good as the formation of a crystalline anatase TiOz film on the surface where dirt is difficult to adhere firmly.

Example 3 3 Coating Si (L· -Alz 0) on the surface of a 15cm square ceramic tile₃ -Na/Kz 0. Glass frit, and then spray coating on the surface of TiO with a crystal particle size of 0.01 μm₂The nitroxide colloidal suspension of the sol is calcined at 75°C for 2 hours, and made into three types of 0.2nm, 0.4um, and 0.8μπι according to the film thickness of the Ti(L·film. The porosity of the TiOz film at this stage is 4 5%, the crystal size of TiOz particles is 0.02μηι_οOn the cooled sample, dry air is used as the carrier gas, and a mixture of 10:1:400 (weight ratio) tetraethoxytitanium, 36% hydrochloric acid and ethanol is then coated by the curtain coating method, and then dry. The coating amount is 4 0-50 kg/cm in terms of TiOz² ο After that, it was fired at 50°C for 10 minutes. The titanium alkoxide coating process was performed 1 to 5 times. The obtained samples were evaluated for deodorization, antibacterial properties, abrasion resistance, and adhesion difficulty of contamination.

Regarding antibacterial properties, the test was conducted with Escherichia coli (Escherichia coli V3110 strain). Place 0.15ml (1 -50000 CFU) of bacteria liquid on the top surface of the multifunctional material pre-sterilized with 70% ethanol and place it on a glass plate (100X100) to make the sample tightly close to the top surface of the substrate. After irradiating with a white light (3500 Lux) for 30 minutes, wipe the bacterial solution of the irradiated sample with sterile gauze, and recover it in physiological saline to obtain the bacterial survival rate. About the evaluation indicators + + +, + +, +. One is the same as above.

Under any of the above conditions, deodorant R₃o (L) are all above 80%, and the antibacterial properties are all +++.

Regarding the difficulty of dirt adhesion (Figure 4 4) and wear resistance (Figure 4 5 ), it depends on the number of times of titanium alkoxide coating and the thickness of TiOz film. If the titanium alkoxide is applied more frequently, the difficulty of adhesion of contamination and the abrasion resistance increase. In addition, the thinner the TiOz film thickness, the less titanium alkoxide can be coated

200610101461.3 The number of times to improve the adhesion difficulty and abrasion resistance of pollution. One of the reasons is that the porosity of the ΉΟν layer formed by coating titanium alkoxide is reduced. In Fig. 46, the relationship between the porosity of the surface of the TiOz layer and the number of times of coating of the titanium alkoxide and the thickness of the TiOz film are shown. The more times the titanium alkoxide is applied, the more the porosity on the surface of the TiOz layer decreases, and the thinner the TiOz film thickness is. With the same titanium alkoxide coating times, TiOz₂The more the porosity of the layer surface decreases, this relationship corresponds well to the relationship between the number of times of titanium alkoxide coating, the thickness of the TiOz film, the difficulty of adhesion of contamination, and the abrasion resistance. Especially in terms of the difficulty of adhesion of pollution, it is the same as the case of Example 31. The porosity of 30% or less is the same as that of Example 3. 4 Coating Si (L· -Alz Os) on the surface of a 15cm square ceramic tile -Na/Kz 0 glass frit, and then on its surface, the ammoniolytic colloidal suspension of TiOz sol with a crystal particle size of 0.01 μm was sprayed on the surface, and then calcined at 75 °C for 2 hours. The Ti( The film thickness of the h film is 0.4μm, the porosity is 45%, and the crystal size of the TiOz particles is 0.02pm. On the cooled sample, use the shower coating method and use dry air as the planting gas to recoat 10 :1: 400 (weight ratio) of tetraethoxy titanium, 36% hydrochloric acid and ethanol mixture, and then dried. The coating amount is 4 0-50 Rg/cm based on TiOz². Then it was fired at 50°C for 10 minutes. The titanium alkoxide coating process was repeated three times. After that, a% (weight) silver nitrate aqueous solution was coated on the sample for photoreduction (the light source is a 20W BLB lamp, The distance from the light source to the sample is 10 cm. The irradiation time is 30 seconds), and the sample is obtained. Here, the amount of silver supported on the surface of the sample is 0.7%, and the average silver particle size is about 40 nm. The antibacterial properties and antibacterial properties after long-term use are measured on the obtained samples.

Regarding the antibacterial properties after long-term use, a face test was performed as follows. First, clean the surface of the obtained sample well with ethanol, etc., and dry it at 5 CTC. Next, pour the bathtub water collected in the public bath into a sterilized beaker, soak the plum sample in it, and leave it for one month. Then take out the sample, wash it with ethanol, etc., use 70% ethanol to remove the top surface of the multifunctional material

200610101461.3 Side sterilization. Next, fill 0.15ml (1 -50000 CFU) of the bacteria solution from the front of the large intestine rod (Escherichia coll 110 strain) on the top surface of the above sample, and place it on the glass plate (100X100) on the top surface of the substrate. Stick it tightly as a sample.

After irradiating with a white light (3500 Lux) for 30 minutes, wipe the bacterial solution of the irradiated sample with sterile gauze, and collect it in 10 dishes of physiological saline to obtain the survival rate of the bacteria as an evaluation index. The evaluation index is the same as the antibacterial test of Example 3.

For comparison, the samples used in Example 33 were also tested.

As a result, for the initial antibacterial properties, the samples produced in this example and the samples produced in the example? are all + + +, but there is a difference between the two in terms of antibacterial properties after one month. . That is, the antibacterial properties of the samples prepared in Example 33 deteriorated to +, while the samples prepared in this example showed a + + + value that did not change from the initial stage. This can be explained as the fact that silver occupies the highly adsorptive part on the surface of the TiOz layer, so in use, the adhesion of dust and the like is prevented in the highly adsorptive part.

From the above description, it can be seen that a layer with a photocatalytic function is formed on the surface of the substrate. Since the gaps formed on the surface of the layer are filled with particles smaller than the gaps, the number and size of gaps existing on the surface are higher than those of conventional photocatalyst thin films. It is small, and because of its good surface smoothness, it maintains deodorization while increasing the strength of the membrane. It also makes it difficult for the macromolecules, dirt, fungi and the like that constitute dirt components to adhere.

The following describes the use of materials with low melting points such as soda lime glass as substrates. That is, when a photocatalyst film is formed on the surface of a low melting point substrate, the substrate has begun to soften at the temperature at which the catalyst film is formed, and the resulting light The catalyst film has been buried in the base material, so the light cannot reach the photocatalyst layer, resulting in a disadvantage that the photocatalytic function cannot be exerted.

Therefore, in such a case, the photocatalyst particles are fixed to the substrate by a layer having a higher melting point than the substrate such as a SiCk layer. The specific embodiment is described as F.

200610101461.3 Example 35 Before coating titanium oxide on the soda lime glass, silica is coated on the surface of the soda lime glass.

The silica coating was applied to a 10 cm square soda lime glass by the following method. First, mix tetraethoxysilane, 36% hydrochloric acid, pure water and ethyl alcohol in a ratio of 6: 2: 6: 86 (weight ratio). Because of heat at this time, it was left for about 1 hour. It is coated on the soda lime glass by airflow coating.

Next, a coating solution is prepared. Mix tetraethoxy titanium and ethanol at a ratio of 1:9 (weight ratio) to form a solution, and add 10% (weight) of 36% hydrochloric acid to the tetraethoxy titanium to make a coating solution. Here, the amount of 36% hydrochloric acid added can be 1% (weight) or more, 30% (weight) or less, preferably 5% (weight) or more, 20% (weight) relative to titanium tetraethoxide. )the following. By adding an appropriate amount of hydrochloric acid, cracks can be prevented during the subsequent drying and roasting process. That is to say, if the amount of hydrochloric acid is too small, the effect of preventing cracks cannot be fully achieved. If the amount of hydrochloric acid is too much, the increase in the amount of water contained in the hydrochloric acid reagent accelerates the hydrolysis of titanium tetraethoxide, making it difficult to form a homogeneous coating. membrane.

Next, the solution was coated on the surface of the soda lime glass substrate in dry air by a curtain coating method. Here, the term "dry air does not mean air containing no moisture at all, but means air with less moisture than normal air. At this time, if the coating is performed in ordinary air without drying treatment, the moisture in the air accelerates the hydrolysis of titanium tetraethoxide, and the amount of coating film at one time is too large, and cracks are likely to occur in the subsequent drying and firing processes. In addition, due to accelerated hydrolysis, it is difficult to control the amount of coating film. In order to prevent cracks, it is ideal that the primary loading of titanium oxide is 100 Μ- g/cm²the following. This time the loading of titanium oxide is 4 5 μ₈/cm²。

Then, it is dried in dry air for 1-10 minutes to form a titanium oxide film, and the titanium oxide film is obtained according to the following principle using the process up to this point. Here, the starting material is titanium tetraethoxide, which is one of the titanium alkoxides (even if other titanium alkoxides are used in principle, they can be produced.

200610101461.3 The same effect as the first birth). It is mainly based on titanium tetraethoxide, which undergoes hydrolysis reaction with water in dry air during curtain coating to generate titanium hydroxide. Furthermore, a dehydration knitting reaction occurs during drying, and salty amorphous titanium oxide is formed on the substrate. The titanium oxide particles produced at this time are about 3-150 nm, which is of high purity. Therefore, this type of titanium oxide is characterized by low-temperature sintering compared to titanium oxide obtained by other manufacturing methods.

The composite member obtained by the above method is fired at 300-500*C to obtain a multifunctional material. If necessary, repeat the process from tetraethoxy titanium to firing to coat the titanium oxide thickly.

The samples thus obtained were evaluated for deodorization, abrasion resistance, and antibacterial properties. The results are shown in Table 19.

(Table 19)

<td>Roasting temperature (Nei).</td><td>3±1 blood X»L abrasion resistance</td><td>R 30 (L)</td><td>R 30 (D)</td><td>Antibacterial property (L)</td><td>Antibacterial property (D)</td>

<td>300</td><td>◎</td><td>0%</td><td>0%</td><td>—</td><td>One</td>

<td>400</td><td>◎</td><td>60%</td><td>0%</td><td>+</td><td>One</td>

<td>500</td><td>◎</td><td>60%</td><td>3 %</td><td>+</td><td>—</td>

Regarding the deodorization, set the sample in a cylindrical container with the initial concentration of methyl sulfide adjusted to 2 ppm, diameter 26cmX height 2 lew, and use a 4W BLB fluorescent lamp to irradiate light from 8cm away from the sample for 30 minutes. , Measure the removal rate of methyl mercaptan (R3°(L)), and measure the removal rate of methyl mercaptan (D) after 30 minutes of light shielding for evaluation.

Regarding abrasion resistance, plastic rubber was used for sliding friction, and the appearance change was compared, and no evaluation was made. The evaluation indexes , O, , and X at this time are the same as described above.

Regarding antibacterial properties, the test was performed with Escherichia coli (Escherichia col i. V3110 strain). Place 0.15ml (1 -50000 CFU) of bacterial liquid on the top surface of the multifunctional material pre-sterilized with 70 96 ethanol, and place it on a glass plate (100X100).

200610101461.3 The uppermost surface of the first substrate is attached tightly as a sample. After irradiating with a white light (5200 Lux) for 30 minutes, wipe the irradiated sample with sterile gauze and the bacterial solution of the sample kept under light-shielding conditions, and recover it in 1 Dial physiological saline to determine the survival rate of the bacteria , As an evaluation indicator. The evaluation indicators + + +, + +, +, one are the same as above.

The firing temperature is 30 (rc, which shows good results of in the sliding test, but r_3O(1) It is 0%. It is considered that this is caused by not crystallizing amorphous titanium oxide into anatase type.

Under the 40(rc) that can be verified by X-rays in synthetic experiments, the sliding test also shows good results of , but R₃o(L) is also increased to 60%. And the antibacterial property is also ten. In addition, even at 5o(rc, the sliding test also showed good results of , but R_3O (L) is also increased to 60%.

When the temperature is increased again, the soda lime glass of the 55rc substrate is deformed, and the multifunctional material cannot be manufactured.

Example 36 In order to further improve the photocatalytic properties of the samples obtained in Example 35, metal particles were supported. The photocatalyst undergoes a reduction reaction at the same time as the oxidation reaction. If the reduction reaction is not carried out, the electrons are not consumed, the particles are charged, and the oxidation reaction cannot proceed. It can be considered that in Example 1 R₃o (L) is limited to 6 (]%. In order to prevent this, metal particles are supported on titanium oxide particles to allow electrons to escape and prevent charging.

The metal particles are supported by the following method. Spread the metal salt solution on the photocatalyst and irradiate it with a 20 W BLB fluorescent lamp at a distance of 20 cm for 1 minute. In the metal salt solution, a 1% (weight) ethanol solution of copper acetate is used when supporting copper, and a 1% (weight) ethanol/water 2/1 mixed solution of silver nitrate is used when supporting silver. After irradiation, wash and dry. The metal salt wood solution is not used here, but the ethanol-containing solution is used, which makes the metal salt solution have good wettability to the sample.

200610101461.3 The sample thus obtained was evaluated for odor resistance, abrasion resistance, and antibacterial properties. The results are shown in Qiu 20. In addition, only samples obtained at a firing temperature of 50°C were used.

(Table 20)

<td>Melting temperature (9)</td><td>Abrasion resistance</td><td>R 30 (L)</td><td>R₃o(D)</td><td>Antibacterial (L)</td><td>Disturbance (D)</td>

<td>500</td><td>◎</td><td>98%</td><td>98%</td><td>+ + +</td><td>+ +</td>

The sliding test showed good results of . And R so (L) has increased dramatically to 98%. The antibacterial property is also + + +.

Comparative Example 37 Except that silica coating was not applied in Example 35, the same procedure was performed. I.e. at

Ocm square soda lime glass is coated with titanium oxide. The results are shown in Table 21. (Table 21)

<td>Temple burning temperature (°C)</td><td>Abrasion resistance</td><td>R 30(L)</td><td>R 30 (D)</td><td>Antibacterial (L)</td><td>Antibacterial (D)</td>

<td>300</td><td>◎</td><td>0%</td><td>0%</td><td>—</td><td>—</td>

<td>400</td><td>◎</td><td>0%</td><td>0%</td><td>—</td><td>—</td>

<td>500</td><td>◎</td><td>0%</td><td>0%</td><td>One</td><td>—</td>

It can be seen from Table 21 that in the case of 30 (rc, 400Ό&gt; 500Ό, the sliding test shows good results of , but Rs. (L) even if the process from tetraethoxy titanium coating to firing is repeated 10 times , Is also 0%, and the antibacterial properties are all -.

At 30°C, R 30 (L) is inferior, and it is considered that this is because titanium oxide is not crystallized from amorphous titanium oxide to anatase type.

On the other hand, in the case of 40(rc, 500Γ), the amorphous titanium oxide has been crystallized into anatase type, and the R can not be explained for the above reasons. _3O (L) Poor. It is considered that this is because the soda lime glass of the base material is softened, and the titanium oxide film is buried in the glass.

200610101461.3 Firstly, it can be seen from the above description that even a low melting point substrate can be made into a multifunctional material with deodorant and antibacterial properties by using a high melting point layer between it and the photocatalyst layer.

An example suitable for maintaining the photocatalytic effect on a surface of plastic or the like with poor heat resistance will be described below.

The base material is not limited to plastic, pottery, ceramic, glass, or composites thereof that have poor heat resistance.

The shape of the substrate can be any shape. It can be a simple shape such as a ball, a cylinder, a cylinder, a tile, a wall material, a floor plate, etc., and it can also be a sanitary ceramic or a face wash. Tables, bathtubs, sinks, toilet seats and other complex shapes, and the surface of the substrate can be porous or dense.

The type of the binder may be a thermoplastic material such as inorganic glass, thermoplastic resin, and solder, or may be a thermosetting material such as an atmosphere resin, a silicone resin, and a silicone resin. However, in view of the need to irradiate light containing ultraviolet rays in the subsequent process, a photo-corrosive material is preferable. In addition, only in the case of a heat treatment below 30 (rc), from the perspective of the usefulness of this application, it is desirable that the thermoplastic material is a softening material below 30 (rc), and the thermosetting material is a material that can be cured below 30 (rc As materials that satisfy these conditions, thermoplastic materials include boric acid-based glass, soft solder, acrylic resin, etc., and thermosetting materials include gas resin, silicone resin, and silicone resin.

As the method of coating these adhesive layers on the substrate, when using thermoplastic materials, there are spraying method, radiation coating method, dip coating method, etc., any of these methods can be used, and other methods can also be used. Its world method. In addition, the composition of the binder does not necessarily have to be the same as the composition of the binder when the component is completed. For example, when the binder is composed of inorganic vitreous, the coating material may be a suspension of an inorganic vitreous composition such as granules, glass frit, agglomerates, powder, etc., or a mixture containing constituent metal component salts. When the binder is a resin, a resin solution of this composition can be used, or other methods other than this can be used.

200610101461.3 Before coating the photocatalyst particles on the adhesive layer, dry the coated adhesive layer and evaporate water. The drying method at this time includes a method of leaving at room temperature, a method of heating together with the base material, and the like.

In addition, before coating the photocatalyst particles on the adhesive layer, the adhesive layer can be heated at a temperature lower than the softening temperature of the base material, and the adhesive layer becomes the adhesive composition when the component is completed and softened. Adhesive layer. According to this method, the formation of the photocatalyst particles on the adhesive layer is smoother than that of the previous adhesive layer, so even a small amount of the coated photocatalyst particles can exert a sufficient effect.

When using a thermosetting material, the method of mixing the binder and the curing agent and coating it on the substrate, for example, according to the method of adding a diluent to the thermosetting resin, and then adding the curing agent to the mixture. The method on the surface of the substrate.

It is desirable that the viscosity increase value is 105 poise or more and 1075 poise or less. After the high viscosity value of 105 poise or more is formed, the photocatalyst particles are coated, so that the photocatalyst particles may be buried in a state that is not completely buried in the adhesive layer. In addition, the formation of 1075 poise or less, the photocatalyst particle layer At least a part of the lowermost layer is buried in the adhesive layer.

The method of coating the above-mentioned photoburning agent particles on the surface of the adhesive layer is basically carried out according to the method of applying a material obtained by appropriately treating the starting material on the adhesive layer.

As the starting material, although a sol suspension of the photocatalyst composition is desired, a fine particle suspension of other photocatalyst compositions may also be used. In either case, in order to form a uniform coating film, it is necessary to add a surface treatment agent such as a dispersant so that the photocatalyst composition in the suspension does not aggregate. As the coating on the adhesive layer, there are spray coating, radial coating, dip coating, etc., but any of these methods may be used, or other methods other than these may be used.

The embedding thickness of the photocatalyst layer into the adhesive layer and 1/4 or more of the embedding thickness of the photocatalyst layer are satisfactory in terms of the bonding strength with the base material. The so-called photocatalyst layer thickness

200610101461.3 For the first time, it is determined from the analysis of the component elements that constitute the photocatalyst particles in the cross-sectional direction measured by EPMA, etc. It is composed of the upper layer part and the embedded part with a substantially constant amount of the component elements constituting the photocatalyst particle, and the embedded part is located at The depth at which the amount of component elements constituting the photocatalyst particles starts to decrease to the depth at which the amount of component elements constituting the binder starts to become a certain depth.

The surface treatment agent attached to the photocatalyst is mainly composed of components added to disperse the starting material sol of the photocatalyst particles. Specific examples include quaternary pentaerythritol, trimethylolpropane, triethanolamine, trimethylolamine, silicone resin, and alkylchlorosilane.

As containing 1.7mW/cm²Examples of light sources with wavelengths below 390 nm include BLB fluorescent lamps, ultraviolet lamps, germicidal lamps, aviation lamps, mercury lamps, and the like.

Must contain 1.7mV/cm²The reason for the above-mentioned light with a wavelength of 390 nm or less is that the dispersant component such as silicone resin has a certain degree of light candle resistance, and if there is no ultraviolet intensity of this degree, it does not decompose. At this time, the shorter the ultraviolet wavelength, the faster the dispersion of the dispersant, but due to the different types of binders, the binder may decompose, and it is also harmful to the human body. Therefore, it can be 250nm or more. In addition, when the illuminance reaches 3 mW/cm?, the decomposition speed increases as the illuminance increases, but even if the illuminance increases to 3 mW/cm²The above does not contribute much to the increase in the decomposition rate, so 3 cap/s 2 or less is sufficient.

The above process is schematically shown in Figure 47. On the substrate 1, the part of the lower layer of the photocatalyst layer 2 through the adhesive layer 6 is buried in the adhesive layer 6. 6a is a layer composed of a surface treatment agent that inhibits the photocatalytic activity. UV indicates that it contains 1.7 mV/cm²Light with a wavelength above 390nm and below.

The following explains about forming a layer mainly composed of photocatalyst particles 3 and thermosetting resin 6 on the surface of the substrate, and irradiating ultraviolet rays to expose the photocatalyst layer in the same way (refer to Figure 48). Thermosetting is also used in this method. The resin firmly fixes the photocatalyst particles 3 on the substrate, and irradiates light with wavelengths above 1.7 nm/cf and below 390 nm, thereby generating a photocatalytic reaction on the light-irradiated part of the photocatalyst particle surface, making it

200610101461.3 The thermosetting resin in the direction of the surface treatment agent and the light source preferentially decomposes, vaporizes, and exposes the photocatalyst particles to the air, so sufficient photocatalytic activity can be obtained.

In addition, with regard to the method of forming a layer mainly composed of photocatalyst particles and thermosetting resin, for example, the thermosetting resin, diluent, and curing agent are sequentially added to the fully dispersed photocatalyst sol float liquid to bless the mixed liquid, and the mixture is mixed. The liquid is coated on the surface of the substrate and heat-treated to form it.

Here, the crystal particle size of the sol in the photocatalyst sol suspension may be 0.01 Um or less, preferably 0.01 Um or less. This is because the smaller the crystal grain size, the higher the photocatalytic activity. It is also desirable that the sol in the sol suspension of the photochemical agent be as monodispersed as possible. The better the dispersion, the more uniform coating film can be formed.

The thermosetting resin used here preferably has photo-corrosion resistance to white light and light of normal fluorescent lamp intensity. This is because it has excellent durability during use. In this sense, silicone resins and gas resins are particularly ideal.

The diluent is used to reduce the viscosity of the mixed liquid composed of the photocatalyst sol and the thermosetting resin, so that the mixed liquid can be easily applied and added on the surface of the substrate. However, the diluent used here can basically be used as long as it is a solvent that can achieve this purpose. For example, water, ethanol, propanol, etc. can be used.

The method of applying the mixed solution to the base material includes spray coating, nap coating, dip coating, spin coating, etc., but any of these methods may be used, or other methods may be used.

Heat treatment furnaces generally use electric furnaces, gas furnaces, vacuum furnaces, pressurized furnaces, etc., but are not limited to this.

It is also possible to form a layer mainly composed of photocatalyst particles and thermosetting resin on the surface of the substrate through a thermosetting resin layer or a photocurable resin layer (intermediate layer: C) (refer to Figure 49).

200610101461.3 According to this method, even if there are irregularities on the substrate, the thermosetting resin layer or photocurable resin layer arranged between the substrate and the photocatalyst layer is used to form an extremely smooth surface before coating the photocatalyst layer. Therefore, a uniform photocatalyst layer can be easily formed. In addition, the thermosetting resin layer or the photocurable resin layer disposed between the substrate and the photocatalyst layer sufficiently forms a bond with the substrate. Therefore, even if there are irregularities on the surface of the substrate, the photocatalyst particles can be formed thinly. Together with the layer composed of thermosetting resin, the photocatalyst particles can also be concentrated near the surface of the substrate, so that the subsequent process can be completed in a shorter time. The irradiation contains 1.7mV/cm²The above light irradiation process of light with a wavelength of less than 390" m. In addition, because there is a layer composed of the above photocatalyst particles and thermosetting resin, even if it decomposes and vaporizes during the subsequent process and use, the ultraviolet rays with sufficient intensity cannot reach the middle The thermosetting resin layer or the photocurable resin layer is arranged, so the thermosetting resin for this part can be arbitrarily selected. For example, an inexpensive epoxy resin can be selected for cost reduction, and a colored resin can also be used to maintain patterning.

Here, methods for forming the thermosetting resin layer disposed between the substrate and the photocatalyst layer include, for example, coating the surface of the substrate with a mixture obtained by adding a diluent to the thermosetting resin and then adding a curing agent, and using heat treatment or Place and solidify to form. In addition, when the layer disposed in the middle of the photocatalyst is a photocurable resin layer, the heat treatment is replaced by irradiation with light containing ultraviolet rays. Here, in order to reduce the viscosity of the mixed liquid, it is easy to coat the mixed liquid on the surface of the substrate and add a diluent. Therefore, the diluent used here can basically be any solvent that can achieve this purpose. For example, water, ethanol, propanol, etc. can be used.

Furthermore, as shown in Figure 50 (a). (b), according to the above method, the gap formed on the photocatalyst layer exposed on the surface of the substrate is preferably filled with particles smaller than the gap (interstitial particles: 4) , In order to further improve the wear resistance.

The size of particles smaller than the gap can basically be smaller than the average value of the generated pore diameter or unevenness. The amount of particles smaller than the gap is preferably added to the surface of the open pores.

200610101461.3 The first rate is below 20%. Because of this, the pollution is difficult to adhere.

Specific examples are listed below.

Example 3 8 On the surface of a 1 Ocm square alumina substrate, 10% (by weight) was sequentially applied to titanium oxide sol (obtained by dispersing with an amine-based dispersant) with an average particle size of O. OUm. A mixture of siloxane resin, diluent, and curing agent was added to the mixture in sequence, and calcined at 150°C to obtain a comparative sample. The sample was irradiated with various light sources for a predetermined time to obtain a sample. The deodorant property (L) during light irradiation was evaluated for the obtained sample.

Here, the deodorization during light irradiation (L) means that the sample surface is placed in an 11-liter glass container at a distance of 8 cm from the light source (BLB fluorescent lamp, 4W), and methyl mercaptan is injected into the container with an initial concentration of 3 ppm Within, the concentration change rate after 30 minutes of light irradiation.

The results are shown in Table 22.

(Table 2 2)

<td>light source</td><td colspan="2">Ultraviolet intensity (W/crrf) for 20 nets)</td><td>Rao (L) (%)</td>

<td>Wu</td><td>—</td><td>—</td><td>30</td>

<td>BLB</td><td>0.3</td><td>7</td><td>32</td>

<td>BLB</td><td>1.69</td><td>5</td><td>52</td>

<td>ultra violet light</td><td>2.0</td><td>3</td><td>74</td>

<td>ultra violet light</td><td>3.0</td><td>1</td><td>82</td>

As a result, the UV intensity is L69mV./cin²The above deodorization is more than 5 0 96, at 2 mW cm²Above, deodorant Rr. (L) is a good result of more than 70%. Here, the UV intensity is 1.69mV/cm²The above good results can be explained as the photocatalytic reaction occurs in the light-irradiated part of the photocatalyst particle surface, and the thermosetting resin in the direction of the surface treatment agent and the light source is preferentially decomposed and vaporized, exposing the photocatalyst particle to the air.

200610101461.3 The reason for the middle.

Example 3 9 On the surface of a 10 cm square alumina substrate, a solution formed by adding a diluent and a curing agent to a silicone resin was coated, and after drying at room temperature for about 6 hours, the coating was applied to the average particle size A 0.01 μm titanium oxide sol (obtained by dispersion treatment with an amine-based dispersant) was sequentially added with a mixture of 10% by weight of siloxane resin, diluent, and curing agent, and calcined at 15°C, A comparative sample was obtained. The sample was irradiated with various light sources for a predetermined time to obtain a sample. The obtained sample was evaluated for the deodorant property R during light irradiation.₃o (L) ο The results are shown in Table 23.

(Table 2 3)

<td>light source</td><td colspan="2">Quebec machine strength (W/crrf) typical firing time (day)</td><td>R30 (L) (%)</td>

<td>no</td><td>—</td><td>—</td><td>34</td>

<td>BLB</td><td>0.3</td><td>7</td><td>38</td>

<td>BLB</td><td>1.69</td><td>5</td><td>61</td>

<td>ultra violet light</td><td>2.0</td><td>3</td><td>82</td>

<td>ultra violet light'</td><td>3.0</td><td>1</td><td>84</td>

As a result, the UV intensity is 1.69niV/cin²Above, the deodorization is more than 60%, at 2%/cm²Above, deodorant R_3o(L) is a good result exceeding 80%. Here, the reason why the ultraviolet intensity is above 1.69 nm/'cm2 shows good results, which can be explained as the photocatalytic reaction occurs in the light-irradiated part of the photocatalyst particle surface, thereby making it possible to adhere to the light that cannot be vaporized or decomposed by heat treatment. The surface treatment agent on the light-irradiated surface of the catalyst particle surface is preferentially decomposed and vaporized. As a result, the photocatalyst particle is exposed to the air.

Example 4 0 On the surface of a 10 cm square alumina substrate, a solution prepared by adding a diluent and a curing agent to a silicone resin was coated, and after drying at room temperature for about 6 hours, the coating was applied to the average particle size.

200610101461.3 Titanium oxide sol with a diameter of 0.01 μm (obtained by dispersing with an amine-based dispersant) was sequentially added with 1096 (weight) of silicone resin, diluent, and curing agent. TC is calcined. At this stage, the particle gap on the surface of the component is about 0.1-0.2μηι on average. Then, the ultraviolet intensity is 2 mV/cm²After irradiating the light (ultraviolet lamp) for 3 days, confirm R_3O(L) Zhao is over 80%, and then the surface is coated with a titanium oxide sol with an average particle size of 0.0035 μm with an average particle size of 70% (weight) relative to the titanium oxide, and dried at 11°C to obtain a sample. In this test R is also displayed in the sample₃₀(L) is a good result of 81%. In addition, a plastic rubber was used for the sliding test. The sample without tin oxide had scratches after 5 times of sliding or less, and the titanium oxide had peeled off, but the sample with tin oxide did not change even after sliding for more than 10 times. It has been confirmed from the above that by filling the gap formed on the surface of the member with tin oxide particles smaller than the gap, the wear resistance can be improved.

As can be seen from the above description, even in the case of forming a layer with photocatalytic action at 30°C or lower, a member with good photocatalytic activity can be provided.

Secondly, although the purpose of exposure is the same as that caused by ultraviolet irradiation, a different method is used to describe a method of providing a multifunctional material with sufficient photocatalysis even when firing at a temperature below 30°C.

In this method, metal particles are fixed on the surface of the titanium oxide sol before adding surface treatment agents such as a dispersant and a surfactant to the titanium oxide sol prepared by the hydrothermal method or the sulfuric acid method.

The so-called metal particles here refer to metal particles that can capture electrons when they are supported on titanium oxide by irradiating light on titanium oxide to generate electrons and holes, specifically Ag, Ca. Pt, P d, Ni, F e, C c, etc.

Among the methods of fixing metal particles on the surface of the titanium oxide sol, the photoreduction method is simple. The titanium oxide sol used here is desirably prepared by a hydrothermal method or a sulfuric acid method, but it is not limited to this. The sulfuric acid method here is a method for synthesizing titanium oxide by the procedure shown below.

200610101461.3 First, anatase is reacted with sulfuric acid to make τ i, Fe, etc., become water-soluble sulfates, and then extracted with water to prepare a sulfate solution whose main components are Ti and Fe. Next, insoluble suspended matter such as SiJ is removed. Then it cools down to 1 0-1 5 °C, precipitates iron sulfate, and separates and removes it. Then the sulfuric acid titanium oxide in the solution is hydrolyzed to produce titanium hydroxide. The resulting titanium hydroxide is obtained using pressure equipment such as an autoclave. Hydrothermal treatment is carried out in high temperature and high pressure water (generally at a saturated vapor pressure above 110'C and below 200) to crystallize to obtain titanium oxide sol C. In addition, the so-called hydrothermal method uses a pressure device such as an autoclave. A method of hydrolyzing a titanium source such as titanium tetrachloride and titanium sulfate at ii (at least rc 20 (under saturated vapor pressure below rc), and hydrolyzing it to obtain a titanium oxide sol.

The method shown below specifically explains the method of fixing metal fine particles to the surface of the titanium oxide sol by the photoreduction method.

First, make the titanium oxide suspension made by the hydrothermal method or the sulfuric acid method acidic or stiff. The isoelectric point of titanium oxide is pH 6.5, and it is easy to generalize because of its neutrality. In addition, it is better to use ammonia in order to adjust to alkalinity. Na, K and other metals are easy to adhere firmly to titanium oxide. If these metals occupy the active sites of titanium oxide first, they will reduce the photocatalytic activity and at the same time prevent the adhesion of Ag, Cu, Pt, Pd, Ni, Fe, Co, etc. On the active point of titanium oxide.

Next, the titanium oxide sol suspension and the metal salt solution with approximately the same pH are warmed to synthesize the titanium oxide sol suspension, and the metal is fixed by irradiating with ultraviolet light. If necessary, precipitate the excess metal and remove it from the solution. The so-called metal salt solution here refers to a solution consisting of a metal salt capable of capturing electrons and a solvent when light is irradiated on the titanium oxide to generate electrons and holes when it is supported on titanium oxide. More specifically, it refers to a solution consisting of a metal salt capable of capturing electrons and a solvent. A solution containing Ag, Ou. Pt, Pd, Ni, Fe, Go, etc. salt and solvent. Examples of salts containing Ag, Cu, P t, Pd, Ni, Fe, Co, etc. include silver nitrate, copper acetate, copper carbonate, copper sulfate, cuprous chloride, copper chloride, and chlorine. Clamp acid salt, nitriding target, chlorinated rubber, chlorinated drill, chlorinated

200610101461.3 No. ferrous iron, iron oxyhydrogen and so on. In addition, as the solvent, water, ethanol, propanol, etc. can be used, but the same type of solvent as the titanium oxide sol floating liquid to be formed can also be used. Add a pH adjuster to the lithium solvent as needed. As the pH adjuster on the acid side, nitric acid, sulfuric acid, and hydrochloric acid can be used. In addition, ammonia is used as a pH adjuster to the core side.

When irradiating light containing ultraviolet rays, pay attention to the points shown below. First of all, as long as the light source irradiates light containing ultraviolet light. Specific examples include ultraviolet lamps, BLB lamps, mouse lamps, mercury lamps, fluorescent lamps, and the like. There is basically no problem with the method of irradiating light containing ultraviolet rays, but first, it can be irradiated from above the container. Because there is no container to absorb ultraviolet light. Secondly, the distance between the light source and the container can be from several cni to approximately 1 Ocm. If it is too close, the heat from the light source may dry out the top of the solution. If it is too far, the illuminance will decrease. The irradiation time varies with the illuminance of the light source, and when the irradiation is for a few seconds to several tens of seconds, the metal is firmly attached to the photocatalyst particles.

Next, a thin film formed by coating the above-mentioned metal-supporting titanium oxide paste and heat-treating is formed on the surface of the substrate, thereby forming a multifunctional material with a photocatalytic effect.

The heat treatment is usually a hydrothermal treatment using roasting in the atmosphere using an electric furnace and a gas furnace or using an autoclave, but it is not limited to this. The average particle size of the titanium oxide particles in the titanium oxide film obtained by such a method is preferably 1 Jie below. When the particle size is larger than this, since the specific surface area is reduced, the photocatalytic activity is reduced.

In addition, a thin film formed by coating the sol of claim 1 on the surface of a substrate with a binder and heat-treating it is formed into a member having a photocatalytic effect. Due to the use of an adhesive, the adhesion to the substrate can be improved.

The specific method differs depending on whether the adhesive is a thermoplastic adhesive or a thermosetting adhesive. If each embodiment shown below satisfies the above configuration, it goes without saying that other methods can be used. Here, as the thermoplastic binder, specific examples include thermoplastics such as acrylic resins.

200610101461.3 Inorganic glass such as adhesive, glaze, soft solder, etc. * In addition, thermosetting adhesives include fluororesin, epoxy resin, and silicone resin.

When a thermoplastic adhesive is used, a member having a photocatalytic effect is produced in the procedure shown below. First, a thermoplastic adhesive is coated on the surface of the substrate. Next, a titanium oxide sol supporting metal particles is coated thereon, and heat treatment is performed. The heat treatment is performed at a temperature lower than the heat-resistant temperature of the base material and higher than the softening point of the thermoplastic adhesive. By performing the heat treatment at such a temperature, a part of the lower layer of the titanium oxide layer supporting the metal anion particles is buried in the adhesive layer, thereby enabling the base material and the metal particle-supporting titanium oxide thin film to be firmly bonded.

In addition, when a thermosetting adhesive is used, a member having a photocatalytic effect is produced in the procedure shown below. First, a diluent and a curing agent are sequentially added to the thermosetting adhesive to make a mixed solution, which is coated on the substrate and cured by heat treatment and other methods. Then, a mixed solution prepared by sequentially adding a thermosetting agent resin, a diluent, and a curing agent to the titanium oxide sol supporting the metal particles is coated thereon, and cured by a method such as heat treatment.

In addition, as an alternative to the thermosetting adhesive, a photocurable adhesive can also be used in the same way.

In this way, in the titanium oxide sol produced by the hydrothermal method or the sulfuric acid method, the Ag, Cu, Pt, P d, Ni, Fe are added before adding surface treatment agents such as dispersants and surfactants. , Co and other metal particles are fixed on the surface of the TiOz sol, so that the active sites of the titanium oxide sol are covered in advance with A g. Cu, Pt, Pd, Ni, Fe, Co and other metal particles, even if they are added and dispersed in the subsequent process Surface treatment agents such as surfactants, surfactants, etc., these substances are adsorbed on the active site of the titanium oxide sol and do not lose activity. Therefore, the photocatalyst sol can be stably dispersed by the action of surface treatment agents such as dispersants and surfactants, and a homogeneous film can be formed on the surface of the substrate. At the same time, the dispersion can be prevented even if calcination is performed at a low temperature below 300°C. Surfactants, surfactants, and other surfactants are adsorbed on the active site of the photocatalyst particle layer formed on the surface of the substrate, and the photocatalytic effect is reduced. At the same time, the active sites of the titanium oxide sol occupy Ag, Cu,

200610101461.3 p.

Pt, Pd, Ni, Fe, Co and other metal particles have the effect of capturing electrons and improve photocatalytic activity.

Specific examples are listed below.

Example 4 1 Water was added to titanium tetrachloride in a water bath to obtain a liquid, and the obtained liquid was subjected to hydrothermal treatment at 14°C in an autoclave to obtain anatase-type titanium oxide sol. The obtained The anatase-type titanium oxide sol is dispersed in nitric acid. The pH of the dispersion is 0.8. Add a 3-5% (by weight) copper sulfate aqueous solution with a pH of approximately 0.8 adjusted with nitric acid to the dispersion, and irradiate it from the top of the container Contains ultraviolet light. At this time, a 4W BLB lamp is used as the light source, and the solution is irradiated for 15 minutes from a distance of about 1 Ocni. A dispersant composed of organic acetate is added to the solution to stabilize the sol. The sol is coated Laid on a 15cm square ceramic tile substrate, heat-treated at 15°C to obtain a sample. The obtained sample was measured for its deodorant R under light exposure.₃₀(L) and antibacterial properties.

Deodorant R under light irradiation₃₀(L) means that the sample is placed in an 11-liter glass container at a distance of 8 cm from the light source (BLB fluorescent lamp · 4W), and methyl mercaptan gas is injected into the container. The initial concentration is 3 ppm, and the light is exposed to 3 The rate of concentration change after 0 minutes.

In addition, for the antibacterial properties, the test was performed with Escherichia coli (Escherichia coli V3110 strain). Drop 0.15ml (10000-50000 CFU) of the bacterial solution on the top surface of the above sample that was pre-sterilized with 70% ethanol, and place it on a glass plate (100&gt;100) to make it close to the top surface of the substrate. Sample. After 30 minutes of irradiation with a white light (3500 lux), the bacterial solution of the irradiated sample was wiped with sterile gauze and recovered in 10 ml of physiological saline, and the survival rate of the bacteria was determined as an evaluation index. The evaluation criteria + + +, + +, +, one are the same as above.

Result R_3O (L) shows a good result of 8 5 96, and the antibacterial property shows a good result of ten.

200610101461.3 Comparative Example 4 2 In a cold water bath, water was added to titanium tetrachloride to obtain a liquid, and the obtained liquid was subjected to hydrothermal treatment in an autoclave at i4(rc) to obtain anatase-type titanium oxide sol The obtained anatase titanium oxide sol was dispersed in nitric acid. The pH of the dispersion was 0.8. A dispersant composed of organic acetate was added to the solution to stabilize the sol, and then the sol was coated On a 15 cm square ceramic tile substrate, heat-treated at 15 VC to obtain a sample, and measure the deodorant R under light irradiation on the obtained sample_3O (L) and antibacterial properties.

Result R ₃o (L) is 5%, and the antibacterial property is one, and both are insufficient.

Example 43 In a cold water bath, water was added to the tetrahydrogen chloride to obtain a liquid, and the obtained liquid was subjected to a hydrothermal treatment in 14FC in an autoclave, thereby obtaining anatase-type titanium oxide sol. The obtained anatase-type titanium oxide sol is dispersed in nitric acid. The pH of this dispersion was 0.8. A 3-5% (by weight) copper sulfate aqueous solution whose pH is adjusted to approximately 0.8 with nitric acid is added to this solution, and light containing ultraviolet rays is irradiated from above the container. At this time, a 4W BLB lamp was used as the light source, and light was irradiated for 15 minutes from a distance of about 10 cm from the solution. A dispersant composed of organic acetate is added to the solution to stabilize the sol. Next, on the surface of a 10 cm square alumina substrate, a mixture solution formed by sequentially adding diluent propanol and curing agent to the silicone resin was applied, and then coated on the member after 1 (MTC) drying. To the sol prepared by the method, a mixture of 20% (weight, relative to the amount of titanium oxide) of siloxane resin, propanol, and curing agent was sequentially added, and the mixture was calcined at 15°C to obtain a sample. The sample was measured for deodorization R 3 under light irradiation. (L) Evaluation.

Result R ₃o (L) shows a good result of 80%.

Comparative Example 4 4 In a cold water bath, water was added to the titanium tetramer to obtain a liquid, and the obtained liquid was subjected to hydrothermal treatment in i4(rc) in an autoclave. Then transfer to anatase-type titanium oxide sol .

100

200610101461.3 Disperse the obtained anatase titanium oxide sol in nitric acid. The pH of this dispersion was 0.8. Add a dispersant composed of organic acetic acid to the solution to stabilize the sol, and then coat the surface of a 10cm square alumina substrate with a silicone resin, which is made by adding diluent propanol and curing agent in sequence. The mixed solution is coated on the component dried at 10°C and then added to the sol prepared by the above method with 20% (weight, relative to the amount of titanium oxide) of siloxane resin, propanol and curing agent. The mixed solution was calcined at i5(rc to obtain a sample, and the deodorant R under light irradiation was measured on the obtained sample₃₀(L) 0 result R₃0 (L) is 2 2%, which is not sufficient.

As can be seen from the above description, in the titanium oxide sol prepared by hydrothermal method or sulfuric acid method, before adding dispersant I, surfactant and surface treatment agent, by adding Ag, Cu, Pt, Pd, Ni , Fe, Co and other metal particles are nationally designated on the surface of titanium oxide sol. Even if they are calcined at a low temperature below 30°C, they can also provide sufficient photocatalysis on substrates that are not heat resistant, such as plastic materials. member.

The above embodiments mainly describe anatase-type TiOz, and the following description relates to rutile-type TiOz.

Figure 51 is a block diagram showing the manufacturing process of a multifunctional material using rutile TiOz. The present invention first forms a rutile Ti(h) film on the surface of a substrate such as a tile. As a method for forming a rutile TiOz film, TiOz is used as a raw material Sol, alkoxy titanium, Ti sulfate, Ti chloride solution, etc., are coated on the substrate, and then heat treated.

When using TiOz sol, because the potential point of TiOz is 6.5, which is approximately neutral, it is easy to uniformly coat the substrate with an acid or alkali-dispersed aqueous solution. When the substrate at this time is a metal, an alkali dispersion is preferable from the viewpoint of corrosion resistance. Examples of the acid include hydrochloric acid, hydrochloric acid, acetic acid, phosphoric acid, and organic acid. In the case of alkali, ammonia, hydroxides containing reduced metals, etc. can be cited. From the point of view that metal pollutants are not generated after heat treatment, ammonia is particularly

101

200610101461.3 The first ideal. Furthermore, organic acids and phosphoric acid-based dispersants, surface treatment agents, and surfactants may be added to these dispersion liquids. In addition, if the particle size is small, the initial sintering occurs at a lower temperature, and a photocatalyst film with excellent peel strength can be obtained at a low temperature. Therefore, the average particle size of the TiOz sol can be 0.05 μ rn or less, preferably 0.01 μ m or less .

As a method of coating on a substrate, compared with spray coating, dipping, radiation coating, spin coating, CVD, electron beam vapor deposition, sputtering, etc. of the above-mentioned raw materials, it is desirable that no special equipment is required and a stable coating can be formed.

The heat treatment can use air roasting using an electric furnace and a gas furnace, or hydrothermal treatment using an autoclave.

On the other hand, C u, Ag, Fe, and C are prepared in advance. , P t, Ni, Pd, Cu₂ At least one solution in 0 (metal ion-containing aqueous solution), which is coated on the rutile TiOz film. Here, when the metal salt aqueous solution is applied, the metal salt aqueous solution does not need to be transferred to the back surface of the substrate. As the solution in the metal salt solution, water, ethanol, etc. can be used. In the case of using water, as a protective oxidant, the addition of alcohol, unsaturated raw material, etc. is also effective. Furthermore, the use of ethanol solution as a solution is not harmful compared to other solvents such as gluten, acetone, methanol, etc., for example, in terms of not being a cause of rust on metal substrates and having a fast drying speed, which is desirable. .

Next, in order to improve the efficiency of supporting the metal salt aqueous solution, the metal salt was dried at room temperature to 110°C, and the metal salt was irradiated with light containing 390 nm or less to reduce the metal ions, and the metal was precipitated and fixed on the rutile TiOz film. Here, the lamp used for irradiation can be an ultraviolet lamp, a BLB lamp (near ultraviolet) lamp, a mouse lamp, a mercury lamp, a fluorescent lamp, etc. In the irradiation at this time, in order to increase the irradiation rate, the light may be irradiated vertically on the irradiation surface.

The following are specific examples. Example 4 5 On a 10cm square alumina substrate, the average particle size is 0.01 μm by spray coating.

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200610101461.3 The ammonia dispersion of the TiOz sol is fired at 90°C to form a rutile Ti(b film. Then, on the rutile TiOz film, a copper acetate aqueous solution is sprayed, and then photoreduced (the light source is 20 w BLB lamp, the distance from the light source to the sample is 10 cm, and the irradiation time is 10 seconds) to obtain a sample. The optical activity A (L) of the obtained sample is evaluated.

The optical activity A (L) represents the absolute value of the slope when the reaction curve when the gas concentration is on the Y axis and the reaction time is on the X axis is approximated to a straight line. That is, if the concentration at time t is set as Xt, then

X t twoΧο · 1 0-^A(L5t (1) Therefore, light containing ultraviolet rays passes through the irradiated photocatalyst I film, and a certain type of decomposed gas is obtained by observing the decrease in the concentration of the decomposed gas when the time t has elapsed. In this experiment, methyl mercaptan, which is a malodorous component in the decomposition gas, was used. The initial concentration of methyl mercaptan was adjusted to 2 ppm, and the sample was set in a 10-cylindrical container with a diameter of 2 6 cm and a height of 21 cm. The BLB fluorescent lamp is 8 cm away from the sample, and the decomposition gas is obtained by observing the time change of the concentration of methyl sulfuric acid when the light is irradiated.

The results obtained are shown in Figure 52 and Figure 53. Figures 52 and 53 are graphs showing the relationship between the concentration of C(1) and the photoactivity A (L) in the solution. Figure 52 shows the photoreduction of the atomized copper acetate aqueous solution after drying. Figure 53 This indicates the case where the copper acetate aqueous solution in a dry state is not subjected to photoreduction as it is atomized.

In the case of photoreduction without entering the copper acetate aqueous solution in a dry state with the atomization shown in Fig. 53 as it is, even if the Cu concentration in the solution increases from 0.001% (weight) to 0.1% (weight), A (L) It is also 3X10 ϋ degree, no change, reaching saturation.

In contrast, in the case of photoreduction after drying the atomized copper acetate aqueous solution of Fig. 52, at 0.001% (weight), it is about 2×107, which is roughly equivalent to the case without drying. The same value, but if it is increased to 0.1% (weight), it is observed that it reaches a level of 1: &lt;1 0 ϋ, and A (L) increases drastically.

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200610101461.3 Example 4 6 The same as Example 4 5 was performed, and rutile TiO was formed on floor tiles and wall tiles.₂In the film, when Cu (copper acetate aqueous solution is coated and dried) is fixed on the rutile TiOz film by photoreduction, the metal component concentration in the solution and the odor removal rate Rs. The test results of the relationship are shown in Figure 54 and Figure 55.

It can be seen from these figures that the photoreduction treatment after drying can remove malodorous components if the concentration of the metal components in the solution is large to a certain extent, even if the substrate is ceramic tiles.

Example 47 On a 15 cm square plaster tile substrate, a dispersion of TiOz sol with an average particle size of 0.01 μm was coated by spraying, and fired at different temperatures to form a rutile TiOz film. Then on the rutile Ti (h film, the copper acetate aqueous solution is sprayed on by spraying method, and then light reduction is carried out (the light source is a 20 W BLB lamp, the distance from the light source to the sample is 10 cm, and the irradiation time is 10 seconds) , A sample is obtained. The deodorant R is evaluated for the obtained sample_3Oo The results are shown in Figure 56. It is only 3 at 90 (TC (open porosity 10%). The value is better than the rutile sample without metal support. In addition, if the temperature is raised to woo-r (open porosity 30%) , The R3D value of the sample that does not support the metal is significantly reduced, and some reduction is observed even in the sample with cu. Therefore, compared with the case of 90 (rc), there are two reasons for the decrease in woor deodorization. One is As the open porosity decreases, the area of the rutile Ti(h) film of the photocatalyst that can contact the decomposition gas decreases. This is considered to be the main reason for the decrease in the deodorization of the non-supported metal sample. Another reason is that the open pores The reduction rate reduces the area where the metal particles can be deposited by the photoreduction method, because the mean free path in the movement of electrons becomes larger.

In addition, FIG. 57 shows the relationship between the A g and CU concentrations in the solution when the film is coated and the color difference. It can be seen from the figure that 0(1 is small in color difference and brightness change compared with human £, and the coloring is not obvious. In addition, the difference in coloring is in terms of c U, using ESCA

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200610101461.3 (electron beam spectroscopy for chemical analysis) and other analyses have detected the zero and monovalent substances of Cu, so it can be considered that this is the influence of monovalent components that are not easy to develop color.

Example 4 8 On a 15 cm square ceramic tile substrate, an ammonia dispersion of TiOz sol with an average particle size of 0.01 μm was coated by spraying, and then fired at different temperatures to form a rutile TiOz film. Next, an aqueous solution of silver nitrate was coated on the rutile TiOz film by spraying, and then photoreduction was performed (the light source was a 2 QW BLB lamp, the distance from the light source to the sample was 10 cm, and the irradiation time was 10 seconds) to obtain Sample. The evaluation results of the porosity, deodorization and abrasion resistance of the rutile TiOz film in the obtained samples are shown in Figure 58.

When the porosity is 10% or more, good deodorization is shown, and when the porosity is 40% or less, the abrasion resistance can be 0 or more.

Regarding the abrasion resistance, sliding friction using a plastic rubber was performed to compare appearance changes and evaluate. The evaluation index is expressed as follows.

0: Coarse to 40 times repeated without change

O: Scratches occurred in sliding of 10 times or more and 40 times or less, and the titanium oxide film peeled off. Δ: 1 in 5 times or more. Scratches and titanium oxide film peeling in sliding times less than 5 times X: Scratches in sliding sliding times less than 5 times, and titanium oxide film peeling off.

Example 4 9 On a 10 cm square alumina substrate with a glaze layer formed in advance, spraying was used to coat the ammonia dispersion of TiOz sol with an average particle size of 0.01 μm, and then fired at a temperature above 850°C and below 1000°C. , The formation of rutile TiOz film. Next, the rutile Ti (the h film was coated with an aqueous silver nitrate solution by spraying, and then photoreduced (the light source is a 20W BLB lamp, and the distance from the light source to the sample is 1 Ocbu irradiation time 10 seconds) to obtain Sample.

The antibacterial properties, abrasion resistance, peeling resistance, stain resistance, acid resistance, shock resistance, and silver coloring properties were evaluated on the obtained samples.

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200610101461.3 Regarding antibacterial properties, the test was conducted with Escherichia coli V3110 strain. Fill the outermost surface of the multifunctional material pre-sterilized with 70% ethanol with 0.15ml of bacterial solution, place it on a glass plate (100X 100), and adhere to the outermost surface of the substrate as a sample. After irradiating with a white light (3500 Lux) for 30 minutes, wipe the irradiated sample with sterile gauze and the bacterial solution that keeps the sample under light-shielding conditions, and recover the bacteria in 10 normal saline to determine the survival of the bacteria. Rate, as an evaluation indicator. The relevant evaluation indicators + + +, + +, +,-are the same as above.

The peel resistance test is a test that is more severe than the abrasion test. The sanding rubber (LION TYPEWRITER ERASER 502) with greater shear strength is used instead of the plastic rubber. The specific evaluation method is to rub the surface of the sample 20 times with a sand rubber with equal force, and visually observe the scratch state compared with the standard sample. The evaluation criteria are as follows.

: No change at all

O: Use the light addition and subtraction method to confirm the slight change

Δ: Confirm a slight change

X: Confirm the change at a glance. The so-called pollution resistance test is a test about the difficulty of dirt adhesion. The specific evaluation method is to use 0.5% methylene blue aqueous solution to create dirt on the surface of the sample, dry and wash with water, and visually observe whether there is dirt. The evaluation criteria are expressed as follows.

: Completely eliminate dirt

O: Although the color of the dirt is not clear, there is a small amount of residue

Δ: Light dirt color remains

X: Obviously remaining stain color. Regarding the acid resistance, after immersing in a 10MHC1 aqueous solution for 120 hours, the abnormal change of the A &amp; supported rutile Ti(h) thin film layer on the surface of the substrate was visually observed for evaluation. Evaluation. The benchmark is expressed as follows.

106

200610101461.3 No. : No change

O: Very slightly discolored : slightly discolored

X: Obvious discoloration. Regarding alkali resistance, immersed in a 5% NaDH aqueous solution for 120 hours, and then visually observed the abnormal change of the Ag-supported rutile TiOz thin film layer on the surface of the substrate, and evaluated it based on the evaluation criteria. as follows.

©: No change

O: Very slightly discolored ; slightly discolored

X: Remarkable and discolored. Regarding the silver colorability, it was evaluated by visual comparison with a sample not containing Ag. The evaluation criteria are expressed as follows.

©: No coloring

0: Very slightly colored : slightly colored

X: Brown colored part The above 7 evaluation results are summarized in Table 24. In addition, the effects of film thickness and firing temperature on the antibacterial properties are shown in Table 25.

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200610101461.3 Section (Table 24) The relationship between the thickness and various characteristics of the light-weighting agent

<td>Film thickness (um)</td><td>Gunworm (L)</td><td>Abrasion resistance</td><td></td><td>Stain resistance</td><td>Acid resistance</td><td>Mechanical resistance:</td><td>Ag colorability</td>

<td>0.1</td><td>+ + +</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td>

<td>Q2</td><td>+ + +</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td>

<td>0.3</td><td>+ + +</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td>

<td>Q4</td><td>+ + +</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td><td>◎</td>

<td>0.5</td><td>+ + +</td><td>©</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td>

<td>0.6</td><td>+ + +</td><td>©</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td>

<td>0.7</td><td>K+ +</td><td>◎</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td>

<td>0.8</td><td>+ + +</td><td>◎</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td>

<td>0.9</td><td>+ + +</td><td>◎</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td><td>ο</td>

<td>1.0</td><td>+ + +</td><td>©</td><td>X</td><td>X</td><td>0</td><td>0</td><td>X</td>

<td>W</td><td></td><td>Δ</td><td colspan="4"></td><td></td>

(Table 2 5) The influence of film thickness and calcination temperature on the antibacterial properties of the photocatalyst film

<td>\iSflE film</td><td>880 nil</td><td>900*t</td><td>920 nil</td><td>940£</td><td>960¾</td><td>980t</td>

<td>0.1 pm</td><td></td><td>+ + +</td><td></td><td>+ +</td><td></td><td>+ +</td>

<td>0.2 pm</td><td></td><td></td><td></td><td>+ + +</td><td></td><td>+ +</td>

<td>0.3 μ m</td><td>+ + +</td><td>+ + +</td><td></td><td>+ + +</td><td>+ +</td><td></td>

<td>0.4 μ m</td><td></td><td>+ + +</td><td>+ + +</td><td></td><td>+ + +</td><td></td>

<td>0.5 pm</td><td></td><td></td><td>+ + +</td><td>+ + +</td><td>+ + +</td><td>+ +</td>

<td>0.6 μ m</td><td>+ + +</td><td></td><td>+ + +</td><td></td><td>+ + +</td><td></td>

<td>0.7 μ m</td><td>+ + +</td><td></td><td>+ + +</td><td>+ + +</td><td></td><td>+ + + ·</td>

<td>0.8 μ m</td><td></td><td>+ + +</td><td></td><td></td><td>+ten+</td><td>+ + +</td>

<td>0.9 pm</td><td>+ + +</td><td></td><td>+ + +</td><td>+ +card</td><td></td><td></td>

<td>1.0ym</td><td></td><td></td><td></td><td>+ + +</td><td></td><td></td>

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200610101461.3 Regarding antibacterial properties, the photocatalyst film produced in this example has a film thickness of 0.1 μm or more and 1 μm or less, and if the firing temperature is appropriate, it shows a good result of + + +. However, as shown in Table 24, if the film thickness is 0.2μm or less, the antibacterial property of the sample calcined at a high temperature of 98 (TC) is + +. A tendency to decrease the antibacterial property is seen. It is considered that this is due to the glaze layer The softening of the photocatalyst film is partially buried in the scratch layer. In addition, although Ag itself also has antibacterial activity, the antibacterial property depends on the baking temperature, and the antibacterial activity of the composite member made according to the method of the present application is still low. It is shown that the rutile type Ti other than the antibacterial effect of Ag is related to the characteristics of the h film (because Ag is supported after calcination as described above).

In addition, it can be considered that in all samples, as the glaze layer is softened, a certain degree of sinking of the photocatalyst thin food into the glaze layer has occurred. However, this example has confirmed that if the firing temperature is appropriate, it can be made at least 0.1 μm or more. The photocatalyst film is kept on the surface layer of the glaze layer.

Regarding the abrasion resistant cinnamon, the film thickness of the photocatalyst thin film produced in this example showed good results of in the range of O.Um or more and 1pm or less. This result is different from the sample prepared by the same manufacturing method without passing the glaze in the middle for comparison, and it is a very good result. It is believed that this is because the glaze is interposed in the middle, and part of the lower layer of the photocatalyst film is buried in the glaze layer due to the softening of the glaze during firing.

On the contrary, for the peel resistance test, when O.lum or more and 0.4μm or less, it is , 0.4 μm or more and 0.9 μm or less, it is Ο, and it is X at 1 pm. Films with the photocatalyst film are observed Thickness increases and tends to become worse. It is considered that this is because the ratio of the buried thickness to the film thickness in the glaze layer increases, and it is not easy to peel off. In addition, those who are not abnormal in the abrasion resistance test are poor in the peel resistance test, which is caused by the difference in the magnitude of the shearing force.

Regarding contamination resistance, when the photocatalyst film thickness is more than O.Uim and less than 0.4 um, it is , when it is 0.4 μm or more and 0.9 μm or less, it is O, and when it is 1 μm;

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200610101461.3 As the thickness of the photocatalyst film increases, there is a tendency for deterioration.

Regarding the acid resistance, the photocatalyst thin film produced in this example had a film thickness in the range of O.Um or more and 1 μm or less, and all showed good results. However, when it is 0.4 μm or more and 1 ni or less, it is 0, and when it is 0.1 μm or more and 0.4 μm or less, it is , and those with a thin film thickness show satisfactory values.

Regarding the shock resistance, the photocatalyst thin film produced in this example showed good results within the range of 0.1 μm or more and 1 μm or less. However, when it is 0.4 μm or more and 1 pm or less, it is 0, and when it is 0.1 μm or more and 0.4 pm or less, it is , and those with a thin film thickness show satisfactory values. Regarding the Ag colorability, when the photocatalyst film thickness is 0.1 μm or more and 0.4 μm or less, it is , 0.4 μm or more and 0.9 μm or less, it is Ο, and 1 ixm is X. The photocatalyst film is observed As the film thickness increases, there is a tendency to deteriorate. This tendency is consistent with stain resistance.

It can be seen from the above 7 tests that the thickness of the photocatalyst film is 0.1 μm or more and 0.9 μm or less, preferably O. Um or more and 0.4 μm or less. In addition, it can be seen that the photocatalyst film is fixed on the substrate through the glaze layer to improve the abrasion resistance.

In addition, the characteristics of the design are also changed by the film thickness. That is, above 0.2μ m and below 0.4» m, the interference of visible light and the photocatalyst film is used to produce iridescent stripes, giving a special impression in appearance. On the contrary, at 0.2 μm or less, 0.4 μm or more, and 0.9 μm or less, the above-mentioned iridescent stripe pattern does not occur. The color of the base material, the color, pattern, or the appearance related to the combination of the glaze can be used as it is.

Example 50 On a 15 cm square ceramic tile substrate, an ammonia dispersion of TiOz sol with an average particle size of 0.01 μni was coated by spraying, and fired at 90 °C to form a rutile-type TίΟζ film with a thickness of 0.8 μm. Next, change the coating amount of copper acetate aqueous solution (solution concentration 0.296 (weight), 0.5% (weight), 1 96 (weight)) on the surface of the tile, and spray

110

200610101461.3 The second method is to apply copper acetate aqueous solution, and then perform photoreduction (the light source is a 20W BLB lamp, the distance from the light source to the sample is 10 cm, and the irradiation time is 10 seconds) to obtain a sample. The antibacterial properties of the obtained samples were evaluated. The residual aqueous solution after the irradiation was recovered, and the Cu supported amount was calculated from the difference between the initial copper amount and the recovered copper amount.

The relationship between the Cu loading amount and the bacterial survival rate during light irradiation (L) and dark time (D) is shown in FIG. 59. From this figure, the following facts can be known.

First, use the support of Cu to improve antibacterial properties. Secondly, when light irradiation (L) is less than dark (D), when there is less Cu, the antibacterial property is higher. This is because when light is irradiated (L), the photocatalytic action of the rutile-type TiOz film that restores the photoactivity due to the Cu loading is effective. It can be seen from this figure that the addition of 0.12ug/cin2 or more is + +, and the addition of 0.3 Rg/cm2 or more increases to +++.

It is known that Cu itself has an antibacterial effect. Therefore, when the copper load is increased in the dark, it can be seen that the antibacterial property improves. At this time, the supporting amount is 0.7μ g/cm²Above is + +, the load is 1.2 μg/cm² , Increase to + + +.

Therefore, it is 0.12ug/cm2 or more and 0.7yg/cin2 or less according to the ++ level, and 0.3 μcm according to the + + + level evaluation²The Cu loadings above and below have good antibacterial properties when light is irradiated (L ), which can be considered to be the special effect produced by the combination of Cu and rutile Ti thin film, due to the rutile TiO₂The film exists. The amount of Cu support can be small. In this way, the amount of Cu loading can be reduced, which is especially important when the composite member is used around water. It is used in an environment where copper can be dissolved in water, such as use on sinks in washstands and sanitary ceramics. It can also inhibit the amount of dissolution.

In addition, in the case of Cu, the same effect is obtained in the form of B'0. This is because on the surface during photoreduction, the 1-valent C u is detected by ESCA, although C ii₂Part of it becomes C u+, but the effect of restoring photoactivity is observed.

111

200610101461.3 On the other hand, by setting the loading amount of C ii at 0.7ng/cni²Above, 1.2 Ug/cm is best²As described above, good antibacterial properties can be obtained regardless of the presence or absence of light irradiation.

In addition, Figure 60 shows the relationship between the Cu coating amount and the Cu loading amount when the Cu concentration in the solution is 1% (weight). It can be seen from this graph that even if the Cu coating amount is simply increased, the Cu The supporting amount does not increase. In order to make the supporting amount of copper be 0·7ug/cm2 or more, the coating amount of Cu can be 0.2mg/citt2 or more, 2.7mg/cm²Below, in order to make the loading capacity of CU 1.2 Kg/cn)²Above, the coating amount of Cu can be 0.3mg/cm² Above, 2.4mg/cm² the following.

Example 5 1 On a 15 cm square ceramic tile substrate, a spray coating method was used to coat Ti(h sol ammonia dispersion liquid with an average particle size of 0.01 μm, and fired at 90°C to form a rutile type with a thickness of ο.δμτη Ti0₂film. Next, on the surface of the tile, change the coating amount of the silver nitrate aqueous solution (solution concentration 0.2% (weight), 0.5% (weight), 1% (weight)), apply the solution by spraying, and then perform photoreduction (The light source is a 20W BLB lamp, the distance from the light source to the sample is 10cm, and the irradiation time is 10 seconds) to obtain the sample. The antibacterial properties of the obtained samples were evaluated. The residual aqueous solution after the irradiation was recovered, and the A g supported amount was calculated from the difference between the initial amount of silver and the amount of recovered silver.

Fig. 61 shows the relationship between the A g loading amount and the bacterial survival rate during light irradiation (L) and dark time (D ). The following facts can be clear from this figure.

First of all, unlike the case of C ii, the survival rate curves of bacteria during light exposure (L) and dark time (D) overlap. This is not so much that the case of A g does not produce different effects from the case of C u. It is better to say that the antibacterial activity of A g is much greater than that of Cu, and the effect is produced with a very small amount of loading, so it can be considered as light irradiation. The difference in the necessary load between time (L) and dark time (D) is included in the results of the experimental error range.

In addition, it can be seen from the figure that by setting the loading amount of A g at 0.05Hg,/cm²the above,

112

200610101461.3 The best is 0.1 μ₈ζcm²As described above, good antibacterial properties can be obtained regardless of the presence or absence of light irradiation.

In addition, FIG. 62 shows the relationship between the loading amount of silver and the color difference of a sample that does not support silver. If the loading amount of silver exceeds 1 μ₈/οιη² , The chromatic aberration increases sharply, exceeding 2. Generally, if the color difference is 2 or more, the difference in color is significant. If silver is attached, it changes from brown to black, so the appearance is ugly and undesirable. Therefore, it is ideal to control the chromatic aberration to 2 or less. For this reason, the loading amount of silver should be 1 Ug/cm2. In addition, the color difference was measured with a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd.).

However, in the above-mentioned embodiments, in order to prevent the active part of the photocatalyst from being covered by some molecular substances and dust with the surface treatment agent, and to reduce the chemical ability or restore the activity, it has been described that silver, copper, and tongs are used. Metal particles such as, button, gold, sickle, iron, diamond, zinc, etc. cover the active points of the particles with photocatalytic activity. However, because such metals are non-ferrous metals, if they are coated in large quantities, they will be inherently attached to the surface of the substrate. Color, damage the color, pattern and other patterns of the substrate.

Therefore, the following describes a decolorization method that maintains high photocatalytic activity without damaging the color, pattern, and other patterns of the substrate.

As a basic method, there are two processes: the process of fixing metal particles on the particles with photocatalytic activity, the process of reacting the above-mentioned metal particles with aqueous solution or gas, and at least forming a colorless or white salt on the surface of the metal particles. Manufacture of catalysts containing metal particles.

The order in which the above two processes are carried out is different, but they can be carried out from anywhere. That is, after fixing the non-ferrous metal particles on the photocatalytically active particles, the above-mentioned metal particles can be reacted with an aqueous solution or gas to at least form a colorless or white salt on the surface of the metal particles, or the non-ferrous metal particles can be combined with an aqueous solution or The gas reacts, at least after forming a colorless or white salt on the surface of the metal particles, it is fixed on the particles with photocatalytic activity.

In addition, the particles with photocatalytic activity can also be mixed with non-ferrous metal particles and then fixed on the substrate. In this case, for example, the following process is carried out in sequence, that is, mixed with light

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200610101461.3 The process of stiffening active particles and non-ferrous metal particles, the process of coating the above-mentioned mixture on the substrate, and the process of ocher burning the above-mentioned mixture on the substrate, reacting with the gas, and forming at least on the surface of the metal particles The process of colorless or white salt.

Furthermore, the process of baking to fix the above-mentioned mixture on the surface of the substrate and the process of reacting with the gas to form a colorless or white salt on the surface of at least the metal particles may be performed simultaneously.

The so-called non-ferrous metal particles refer to silver, copper, tongs, loquat, gold, standard, drill, drill, and zinc metal particles that have a low plasma tendency and are easily reducible by themselves.

When a colorless or white salt is formed by the reaction of an aqueous solution, or when a metal particle-containing catalyst is used in a liquid, the colorless or white salt formed may be poorly soluble or insoluble.

When the catalyst containing metal particles is fixed on the substrate for use, the particles with photocatalytic activity can be pre-fixed on the substrate and then made into a catalyst containing metal particles, or it can be made into a catalyst containing metal particles. , Fixed on the substrate.

In the case of preparing a metal particle-containing catalyst by fixing particles with photocatalytic activity on a substrate in advance, it can be carried out in the following order, that is, the process of forming a layer of particles with photocatalytic activity on the substrate. The process of fixing non-ferrous metal particles on it is a process of covering the above-mentioned non-ferrous metal particles to form a colorless or white salt.

The process of covering the non-ferrous metal particles to form a colorless or white salt, for example, is carried out by reacting with the above-mentioned non-ferrous gold particles to form a colorless or white salt solution at least on the surface of the metal particles and contacting the metal particles, or The reaction with the aforementioned non-ferrous metal particles is carried out by contacting the metal particles with a reaction gas capable of forming a colorless or white salt at least on the surface of the metal particles.

The white or colorless salt in the salt of the aforementioned non-ferrous metal particles is preferably a poorly soluble or insoluble salt. Therefore, it is easy to form a salt on the surface of the metal particles by reacting with an aqueous solution, and it can be used stably in an environment with water.

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200610101461.3 The white or colorless salt in the above-mentioned non-ferrous metal particulate salt, for example, silver chloride, silver bromide, silver iodide, silver leatherate, silver thiosulfate, organic silver, silver thiochloride, chlorinated silver Cuprous, Australian cuprous, sulphurized cuprous, cuprous oxide, zinc phosphate, zinc oxalate, zinc chloride, loquat chloride, zinc sulfide, zinc carbonate, ferrous carbonate, zinc oxide, etc. . A solution capable of forming the above-mentioned salt, for example, in the case of silver chloride, potassium chloride solution, sodium chloride solution, money chloride solution, ferrous chloride solution, etc. can be cited, and in the case of silver iodide, Potassium iodide solution, sodium iodide solution, ferrous iodide solution, hydrogen peroxide water, ozone water, etc., but not limited to these, any soluble salt solution containing various salt anions can be widely used.

In addition, if the reaction gas capable of forming the above-mentioned salt also contains anion elements of various salts, it can also be widely used. For example, if the above-mentioned salt is an oxide such as zinc oxide and cuprous oxide, it can be heated in the air, oxygen, water vaporization, or reacted with other oxidants to oxidize the surface of the metal particles, and an oxide layer can be formed on the surface. .

Specific examples are listed below. Example 5 2 On the surface of a 15cm square ceramic tile substrate, a titanium oxide sol with an average particle size of Olum is coated, and then heat-treated at 90°C to form a rutile titanium oxide Thin film: The sample formed up to this stage is referred to as Comparative Sample 1.

After that, the silver nitrate aqueous solution was coated by spraying, and irradiated with a 20W BLB lamp as a light source for 10 minutes to fix the silver on the rutile titanium oxide film. At this time, the loading amount of silver is 1.2 g/c*, showing a brown color. The sample formed up to this stage was used as the comparative sample 2.

After that, with 0.lcc/^cm²The ratio of 0.1 mol/L potassium iodide aqueous solution was applied to the comparative sample 2 ±&gt; to make it react. As a result, the surface of the sample changed to yellowish white, and the whiteness was considered to be due to the formation of a silver iodide layer. This sample was used as Example Sample 1.

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200610101461.3 These samples were evaluated for color difference, light activity, deodorization and antibacterial properties.

The color pad was measured with a spectrophotometer (manufactured by Tokyo Denshoku Co., Ltd.). At this time, the standard sample is used as the calibration sample 1. The results are shown in Figure 63. As a result, the color difference of Comparative Sample 2 was 3.5. On the contrary, due to the treatment with potassium iodide aqueous solution, the color difference of Example Sample 1 was reduced to 1, and the degree of color development was reduced.

Regarding the photoactivity, it was evaluated by ApH test face. The results of photoactivity and deodorization are shown in Fig. 64. By comparing samples 1 and 2, the photoactivity of comparative sample 2 is restored, ApH and Rs due to the support of silver. (L) Both show good results. In addition, the example sample 1 and the comparative sample 2 are relatively known, ApH and R_3O (L) are all approximately the same value, and even with the decolorization treatment, the photoactivity does not change, and good characteristics can be maintained.

In addition, for the antibacterial properties, the face test was performed with Escherichia coli (Escherichia coli V3110 strain). Place 0.15ml (2 X 1 o) on the top surface of the sample pre-sterilized with 70% ethanol⁴ CFU) Bacterial liquid, placed on a glass plate (100X100), closely attached to the top surface of the substrate, as a sample. Wipe it with sterile gauze, irradiate the sample (L) with a white light (3500 Lux) for a given time and keep the sample (D) in a darkened condition, and recover the bacteria solution in 10ml of normal saline to detect the number of bacteria. Make an evaluation.

The results of antibacterial properties are shown in Fig. 65. Since the comparative sample 1 does not support silver, the antibacterial effect in the dark time (D) is not seen. On the contrary, in Example 1, although the surface of silver was changed into a compound by decolorization treatment, the antibacterial effect in dark time (D) was also seen. In addition, a stronger antibacterial effect was observed during light exposure (L), not only the antibacterial effect of silver was observed, but also the photocatalytic activity recovery effect of the rutile titanium oxide film was observed.

Example 5 3 After coating the glaze on a 15cm square sanitary ceramics blank, it was fired at 1100-1200Γ, and then anatase-type titanium oxide sol with an average particle size of 0.01 μm was fired at 900woor. The rutile titanium oxide film is fixed on the base material of the sanitary ceramic shaped blank.

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200610101461.3 After that, a silver nitrate aqueous solution was coated on it, and ultraviolet rays were irradiated to precipitate silver on the titanium oxide film. Then apply an aqueous solution of ferrous chloride on it, irradiate it with ultraviolet rays to decolorize, and reduce the color difference from 3 to 0.3. In addition, the antibacterial property was in contact with the sample for 30 minutes when irradiated with light and in the dark, and it was confirmed that the number of live bacteria was less than 10% of the original bacteria count, showing good results.

Example 5 4 After coating the glaze on the 15cm square sanitary ceramics shaped blank, it was fired at 1100-1200°C, and then coated with anatase-type titanium oxide sol with an average particle size of 0.01 μm, and fired at 9001000°C. The rutile titanium oxide film is fixed on the base material of the sanitary ceramic shaped blank.

After that, a silver nitrate aqueous solution was coated thereon, and ultraviolet rays were irradiated to make silver on the titanium oxide film. Then the sample was placed in a desiccator with an ozone generator (ozone concentration 10ppm) for about 2 hours, and no decolorization occurred. It was confirmed that the living bacteria were only less than 10% of the original bacteria count, showing good results.

Example 5 5 After coating the glaze on a 15cm square sanitary ceramic shaped blank, it was fired at 1100-1200-C, and then anatase with an average particle size of 0.01 μm dispersed in an aqueous nitric acid solution was coated on it. The inclusion compound of type titanium oxide sol and silver nitrate aqueous solution is then calcined to fix the titanium oxide film on the sanitary ceramic shaped bad substrate. At this time, if it is fired at 70°C or less, it will appear brown, but if it is fired at 70°C or higher, it will be decolorized. This can be explained by the reaction of the silver surface with the components in the atmosphere. In addition, it is suitable for firing at 85°C, which is used in sanitary ceramics. The sample with anatase-type titanium oxide film fixed on the substrate was tested for antibacterial properties. When exposed to light and dark for 3 hours, it was confirmed that the number of living bacteria was only 1 0 96 or less of the original number, showing good results. .

Example 5 6 After coating the glaze on a 15cm square sanitary ceramics shaped blank, it was fired at 1100-1200°C, and then coated with anatase-type oxide sol with an average particle size of U.Olnm, at a temperature of 900- 1000Γ roasting, fix rutile titanium oxide thin on the sanitary ceramic forming bad substrate

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200610101461.3 The first film.

Then, an aqueous silver nitrate solution was coated on it, and ultraviolet rays were irradiated to precipitate silver on the titanium oxide film. Then apply hydrogen peroxide water on it to decolorize it. In addition, the antibacterial property was exposed to the sample for 3 hours during light irradiation and in the dark, and it was confirmed that the number of living bacteria was only 10% or less of the original number of bacteria, showing good results.

Next, the problem of mixing rutile-type TiOz particles and tin oxide in order to improve the compactness and adhesion of the photocatalyst film and at the same time increase the activity will be described.

As a method of forming the photocatalyst thin film, either of the following two methods can be used.

One is a method of mixing TiOz sol and tin oxide sol in advance and coating them on the surface of the substrate for baking.

The mixing of TiOz sol and tin oxide sol is carried out in a mildew aqueous solution. Both of them showed good dispersion because of the alkaline side from the electrochemical point of view. Examples of the aqueous solution include ammonia and hydroxides containing reduced metals or earthy metals, but ammonia is particularly preferable in terms of not generating metal contaminants after heat treatment. In addition, an organic type, phosphoric acid type dispersant, surface treatment agent, and surfactant may be further added to these dispersion liquids.

As the coating method, there are methods of forming a coating film by spraying, dipping, radial coating, spin coating, CVD, electron beam evaporation, sputtering, etc. of the above-mentioned mixed solution, but it may be any of these methods, or it may be Other methods besides this. However, spray coating, dipping, and radiation coating have the advantage of not requiring special equipment and forming coating films at low cost compared to CVD, electron beam evaporation, and sputtering.

After coating, the film can be dried before firing. Drying can be carried out at room temperature-about 10°C.

The calcination is carried out at a temperature sufficient to produce rutile. This temperature is 83 (rc or more) when coexisting with tin oxide under normal pressure.

It is not necessary to form a solid solution of TiOz and tin oxide: in order to form a solid solution of TiOz and tin oxide

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200610101461.3 The first solid solution needs to be kept at high temperature for a long time, so the production efficiency becomes low.

Another method is to form a rutile TiOz film, and then add tin oxide sol to it, and then calcinate it.

In this method, a starting material containing τ i is first coated on a substrate. Here, TiOz sol, titanium alkoxide, τi sulfate, τi chloride solution, etc. are used as starting materials. When using TiOz sol, TiO₂Its isoelectric point is PH6.5, which is roughly neutral, so it is easy to coat evenly by using acid or a dispersed aqueous solution to coat it on the substrate. In this case, when the base material is a metal, from the standpoint of candle resistance, the Gan dispersion liquid is ideal. In the case of ceramics, tiles, ceramics, etc., any dispersion of acid or alkali can be used. Examples of the acid include nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, and organic acids. Examples of the reducing aqueous solution include ammonia, hydroxides containing a metal or an earth metal type metal, but ammonia is particularly preferable from the viewpoint that metal contaminants are not generated after heat treatment. In addition, organic or phosphoric acid-based dispersants, surface treatment agents, and surfactants may be further added to these dispersion liquids. In addition, the average particle size of the starting material TiOz sol may be 0.05 μm or less, preferably 0.01 μm or less. If the particle size is small, initial sintering occurs at a lower temperature, so a photocatalyst film with excellent peel strength can be produced at a low temperature. The method of coating on the substrate can be spraying, dipping, radial coating, spin coating, CVD, electron beam evaporation, sputtering and other methods to coat these dispersions. It can be any of these methods, or it can be Other methods besides this. However, spraying, dipping, and radiation coating have the advantage of not requiring special equipment compared with CVD, electron beam evaporation, sputtering, etc., and the coating film can be formed inexpensively. After coating, it can be dried before firing. Drying can be carried out at around room temperature-10°C.

The coated composite member is then fired. Roasting is carried out at a temperature at which rutile is formed. The temperature is above 90 (rc) under normal pressure.

After that, the cooled and solidified composite member is coated with the starting material that becomes the Sη source and fired. As a starting material that becomes the source of s η, there are tin oxide sol and the like. Soluble in tin oxide

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200610101461.3 Aqueous solution can be used in the first glue. Because tin oxide sol is stable from the electrochemical point of view. Examples of the alkaline aqueous solution include nitrogen, a hydroxide of a metal containing a metal, or a metal of the earth, but ammonia is particularly preferable from the viewpoint that metal contaminants are not generated after the heat treatment. In addition, an organic or phosphoric dispersant, a surface treatment agent, and a surfactant may be further added to these dispersion liquids. The method of coating on the substrate can be spraying, dipping, radial coating, spin coating, CVD, electron beam evaporation, sputtering, etc. to apply these dispersions to form a coating film, and it can be any of them. , It can also be other methods besides this. However, spraying, dipping, and radiation coating have the advantages of not requiring special equipment and being able to form coating films at low cost compared with CVD, electron beam evaporation, and sputtering. After coating, it can be dried before firing. Drying is preferably carried out at room temperature-10°C or so. The firing temperature can be the temperature at which organic additives are evaporated from tin oxide. The temperature is 30°C or more under normal pressure. In addition, it is not necessary to form TiON and tin oxide. ?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? In order to form a solid solution of TBn and tin oxide, it needs to be kept at a high temperature for a long time, so the production efficiency becomes low.

In addition, a thin film composed of a mixture of rutile TiOz and tin oxide with a crystal particle size of 0.01 μ. rn or less is formed on the surface of the substrate, and Cti, Ag, Pt, Fe, Co, Ni, P can be fixed on it. d. Cu₂ At least one metal in 0.

These metals have an electron-trapping effect, and use this to improve the photocatalytic activity of a thin film composed of rutile-type Ti (h and tin oxide with a crystal particle size of 0.01 μη or less).

In particular, Cu and Ag themselves have antibacterial activity and can impart dark activity related to antibacterial properties, so it is possible to maintain a certain degree of antibacterial activity even if they are not irradiated. At least one metal of Cu, Ag, Pt, Fe, C α, Ni, P d, and Cuz 0 is fixed. The method is to coat at least one metal salt aqueous solution in these metals, and then fix it by photoreduction or heat treatment.

In the metal salt aqueous solution, the metal can basically be dissolved as a cation. Specific examples include copper acetate, silver nitrate, copper carbonate, copper sulfate, cuprous chloride, copper chloride, chloric acid,

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200610101461.3 No. chlorinated passivation, zinc chloride, cobalt chloride, ferrous chloride, ferric chloride, etc.

The coating method of metal salt aqueous solution includes spraying method or dip coating method. However, the spraying method is more ideal because it can achieve a small amount of use, uniform coating, easy control of film thickness, and non-sticking on the back as needed.

In the case of the photoreduction method, light containing ultraviolet rays is then irradiated to reduce metal ions, and CU, Ag, Pt, and Fe are fixed on a thin film composed of a mixture of rutile TiOz and tin oxide with a crystal particle size of 0.01 μm or less. , Co, Ni, P d. Cu₂ At least one metal in 0.

The light source that irradiates the ultraviolet light may be a light source capable of irradiating ultraviolet light, and specifically may be any of an ultraviolet lamp, a BLB lamp, a ferment lamp, a mercury lamp, a fluorescent lamp, and the like. In the method of irradiating ultraviolet light, it is desirable to arrange the sample so that the light is perpendicular to the irradiated surface. Because the irradiation efficiency is the best. The ideal distance from the light source to the sample is 1 cm-30 cm. If the distance is too short, the light cannot be irradiated with approximately equal illuminance on the entire sample surface. The adhesion of the above-mentioned metal species is prone to deviation, and the distance is too long because the illuminance of the irradiated light decreases inversely proportional to the square of the distance. Therefore, it is difficult to firmly adhere the metal species.

In the heat treatment method, in order to fix the metal thereafter, it is heated to a sufficient temperature for fixation. The temperature is preferably higher than io (rc. However, for example, when the treatment is performed at a so-called high temperature above 80 (rc), the metal is oxidized. In this case, it is limited to those that do not lose the electron trapping effect or lose their antibacterial properties even if they are oxidized. metal. That should be limited to a g, Cue in Ag, Cu case, since i.e. so that the high temperature firing or not the loss of an electron-trapping effect of the antibacterial, the manufacturing method shown below may be used. That is premixed TiOz oxide sol and Tin sol is coated on the surface of the substrate, followed by coating the metal salt aqueous solution and then firing. According to this method, the firing process can be completed at one time, which has the effect of improving productivity and reducing manufacturing costs.

Specific examples are given below

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200610101461.3 Example 5 5 A TiOz sol with a crystal particle size of 0.01 μm was added at 4 to 6% by weight to the ammonia solution adjusted to pH 11 to prepare suspension A. In another container, 10% by weight of tin oxide sol with a crystal particle size of 0.0035 pm was added to the ammonia solution adjusted to pH II to prepare suspension B. After mixing Suspension A and Suspension B in a given ratio, they were sprayed on the surface of a 15 cm square ceramic tile substrate, dried and fired at 85°C for 2 hours to obtain a sample. The crystal type of Ti(b) in the sample is rutile. In addition, the lattice constant was measured by powder X-ray diffraction, and no tin oxide was found to be solid-dissolved in the TiOz lattice. The photoactivity and abrasion resistance of the obtained sample were evaluated.

Regarding the photoactivity, a potassium iodide aqueous solution was applied to the surface of the sample, and then the dripped iodine potassium aqueous solution was irradiated with ultraviolet rays for 30 minutes, and the difference between the pH of the potassium iodide aqueous solution before irradiation and the pH of the potassium iodide aqueous solution after the irradiation was evaluated. That is, according to this method, if the photoactivity of the sample surface increases, the oxidation-reduction reaction shown below proceeds more easily, so the pH after irradiation is higher than the pH before irradiation.

Oxidation reaction: 2 I ^- + 2 h+ = I ₃ Reduction reaction: 4-2 Η Z 0+4 e ~ = 4 0 Η In addition, plastic rubber is used for sliding friction for abrasion resistance, and the changes in appearance are compared and evaluated. The evaluation indexes , Ο, , and X are the same as above.

Fig. 66 shows the endurance change with respect to the tin oxide-to-dung ratio in the thin film. Regardless of the presence or absence of tin oxide, the abrasion resistance showed good results, being or Ο. It is considered that the sintering occurs due to the so-called high temperature of 850°C, and the particles in the film are firmly bonded to each other.

In particular, when tin oxide exceeds 30%, it is because the strength-to-diameter ratio of the starting material TiJ sol (crystal grain volume 041 μm pi and tin oxide (crystal grain size 0.0035 μm)) is 2 or more, and the fine tin oxide particles Fill the gaps of Ti (b particles, improve filling performance, film

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200610101461.3 The first is more dense.

Figure 67 shows the change in light activity relative to the weight of vaporized tin in the film. For comparison, it also shows the ApH of the rutile Ti (a sample with Cu supported on h (60% at Rs.) showing good antibacterial and deodorizing properties, and the sharp showing very good antibacterial and deodorizing properties. The ApH of the titanium ore-type TiOz sample (in R3. 9 7%). The ApH of rutile-type Ti (h) with tin oxide can not catch up with the anatase-type Ti (L·, the added weight ratio of tin oxide exceeds 10%, 80% or less or 20% or more, 70% or less, in rutile TiO₂The ApH of the sample on which Cu is loaded shows a larger value and has good photoactivity.

Even adding tin oxide with an average particle size of 0.01 um or more does not increase the photocatalytic activity. This is because the position of the conductive band is not moved up enough due to the micronization of tin oxide, and the tin oxide particles do not have a band gap sufficient to generate active oxygen. In addition, if it does not exceed 10%, sufficient photoactivity will not be produced, which is caused by the insufficient amount of tin oxide particles. On the other hand, at 80% or more, the effect is weak. This is because the probability of adjacent presence of tin oxide in the photocatalyst layer increases. Therefore, it is estimated that the frequency of particles growing to an average particle diameter of 0.01 μm or more during heat treatment increases.

Comparative Example 5 6 A 4-6% (by weight) TiOz sol with a crystal particle size of 0.01 μm was added to an aqueous ammonia solution adjusted to pH 1 1. Prepare suspension A. In another container, 10% (weight) of tin oxide sol with a crystal particle size of 0.01 um was added to the ammonia solution adjusted to pH 11 to prepare suspension B. After mixing Suspension A and Suspension B in a given ratio, they were sprayed on the surface of a 15 cm square camp brick substrate, dried, and fired at 85°C for 2 hours to obtain a sample. The crystalline type of TiOz in the sample is rutile. The TiOz lattice baking number was measured by powder X-ray diffraction, and no tin oxide was found to dissolve into the ΤίΟζ lattice: The photoactivity and abrasion resistance of this sample were evaluated.

Fig. 68 shows the change in wear resistance relative to the weight ratio of tin oxide in the film. Do not

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200610101461.3 The first tube has tin oxide or not, and the wear resistance shows good results, which is O. It is believed that the so-called high temperature of 85 °C caused sintering, and the particles in the film were firmly bonded to each other. However, even if the addition amount of tin oxide was increased this time, the wear resistance could not be improved. The particle size ratio of the starting material TiOw sol (crystal particle size 0.01 μ 111) and tin oxide sol (crystal particle size 0.01 μ m) is approximately the same.

Fig. 69 shows the change in photoactivity relative to the weight ratio of tin oxide in the thin film. For comparison, it is also shown that the rutile type Ti0 exhibits good antibacterial and deodorant properties.₂The Ap Η of the sample on which CU is supported and the Ap H of the anatase TiOz sample showing very good antibacterial properties and deodorization properties. The Ap H of the rutile TiOz added with tin oxide is far inferior to the ApH of the anatase TiOw sample this time, and it is also far worse than the Z\pH of the sample that supports Cu on the rutile TiOz.

Example 5 7 Add 4-6% (weight) of crystal grain size to the nitrogen aqueous solution adjusted to PH11

A 0.01 μm TiOz sol was made into suspension A. In another container, 10% by weight of tin oxide sol with a crystal particle size of 0.0035 μm was added to the nitrogen aqueous solution adjusted to pH 11 to prepare suspension B. After mixing Suspension A and Suspension B in a given ratio, they were sprayed on the surface of a 15cm square ceramic tile substrate, dried and fired at 85°C for 2 hours to obtain a composite component. In the resulting composite component The middle TiOz crystal type is rutile. And the weight ratio of tin oxide in the film is 6 OHo. In addition, the lattice constant of Ti(h) was measured by powder X-ray diffraction, and no solid solution of tin oxide into the crystal lattice was observed. The composite member was coated with a 5% (weight) copper acetate aqueous solution by spraying method, dried, and then subjected to light reduction (the light source is a 20W BLB lamp, the distance from the light source to the sample is IOcid, and the irradiation time is 1 Minutes) to obtain a sample. The deodorant R^ is evaluated for the obtained sample.

Here, use the test shown below to find R 3θο Use methyl mercaptan in the decomposition gas, the sample is set at the initial concentration of methyl sulfuric acid and adjusted to 2 ppm, diameter 2 6 cmX height 21 cm

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200610101461.3 The first cylindrical container. Place a 4 W BLB fluorescent lamp 8 cm away from the sample and irradiate it with light for 30 minutes. Calculate the concentration reduction rate of methyl mercaptan and obtain the deodorant R during light irradiation.₃o( L ). In addition, the concentration reduction rate of methyl mercaptan after 30 minutes has passed without light irradiation is calculated, and the deodorant property R in the dark is obtained_3O(D). The results are shown in Table 26. For comparison, the samples prepared in Example 55 and Comparative Example 56 (the weight ratio of tin oxide is 60%) were tested simultaneously. It can be clearly seen from Table 26 that due to the addition of Cu, there are the following effects.

(Table 2 6)

<td>Sample</td><td>r_3O(l)</td><td>R30 (D)</td>

<td>Example 1</td><td>82</td><td>0</td>

<td>Example 2</td><td>97</td><td>92</td>

<td>Comparative example</td><td>32</td><td>0</td>

(SnO₂The weight ratio is 60%) It can be seen from Table 26 that compared with the sample of Example 53, R so (L) has some improvement. It can be considered that this is caused by the electron capture effect of Cu. In addition, compared with Example 5 3 and Comparative Example 5 4, R_3o (D) Significantly improved. This increase in dark activity can be explained by the catalytic effect of copper.

It can be seen from the above description that in the member that forms the photocatalyst film on the surface of the substrate, the TiO₂The composition is processed at the calcination temperature at which the composition becomes rutile, and sufficient compactness and TiOz film strength can be maintained. At this time, in addition to rutile TiOz, if tin oxide with a crystal particle size of 0.01 μm or less is present, the photocatalytic activity of the photocatalyst thin film can be improved.

Then fix at least one metal among Cu, Ag, Pt, Fe, Co, Ni, Pd on the photocatalyst film, and use the electron trapping effect to further improve the photocatalysis

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200610101461.3 The first activity.

Industrial Applicability As described above, the multifunctional material of the present invention with antibacterial, antifouling, deodorizing and photocatalytic functions for decomposing harmful substances such as ΝΟχ is suitable for wall materials, tiles, glass, mirrors, and as a circulating filter device. For example, artificial waterfalls and water-spraying stones used for paving stones, or sanitary ceramics such as toilets and washstands, hospital equipment used to prevent bacterial infections such as MRSA, residential equipment, anti-fungal equipment, and anti-viral infection equipment Wait.

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