Amorphous titanium peroxide particle, hydrophilic coating material, hydrophilic coating film layer, and building material

The present invention relates to amorphous titanium peroxide particles having suppressed organic matter resolution, a hydrophilic coating material using the same, a hydrophilic coating layer formed by using the hydrophilic coating material, and a building material having the hydrophilic coating layer. ..

As shown in FIG. 3, a photocatalyst such as crystalline titanium oxide is excited to generate electrons and holes when irradiated with ultraviolet light having an energy equal to or higher than the bandgap, and these act on water molecules to generate OH. Since radicals are generated, it has organic matter resolution.

When forming a hydrophilic coating layer on a base material, if the base material is an inorganic base material, an amorphous metal oxide is applied to the base material and fired to crystallize the amorphous metal oxide. It is possible to change it to a photocatalyst and bind it to the base material, but in the case of an organic base material, the base material deteriorates due to firing, so the photocatalyst that has been crystallized in advance is included in the paint, etc. It is necessary to apply it to the base material.

Since the photocatalyst itself has low binding force to the base material and has organic matter resolution, viscous inorganic and amorphous metal oxide particles are used as a binder to form a layer containing the photocatalyst on the organic base material. In many cases. Amorphous titanium peroxide particles are known as such a binder.

When the hydrophilic coating layer is provided on an organic base material, a hydrophilic paint containing a photocatalyst and a binder may be applied directly to the base material, but amorphous peroxide is used to prevent decomposition of the organic base material by the photocatalyst. A layer of titanium particles may be interposed between the hydrophilic coating layer and the organic base material as a decomposition prevention film (see, for example, Patent Document 1).

Amorphous titanium peroxide particles are in contact with the organic base material regardless of whether the hydrophilic paint is directly applied to the base material or intervened as a decomposition prevention film. Since the photocatalyst is crystalline, it has organic matter resolution, but since this amorphous titanium peroxide is amorphous, it is suitably used as a binder that does not decompose organic matter.

<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 9-262481</text></patcit></p>

<p><nplcit num="1"><text>Hiromichi Ichinose, Improvement of Titanium Oxide Coating Agent and Application to Environmental Purification, [online], 3. Research Report P.85-89 2002 Research Report, Saga Ceramics Technology Center, [September 3, 2009 Day search], Internet &lt;URL: http://www.scrl.gr.jp/research/reports/h14/h14titancoat.pdf&gt;</text></nplcit></p>

<p> However, even at a low temperature of around 40 ° C, for example, the amorphous titanium peroxide contained in the binder and the decomposition prevention film partially changes to crystalline over time, and the decomposition prevention film and the binder itself gradually become organic decomposing. Although there is a difference in temperature depending on the temperature, there is a problem that unintended deterioration of the organic base material is promoted even in the temperature environment of -15 to 40 ° C, which is assumed as the housing environment in Japan.</p><p> The present invention has been made in view of the above problems, and an object of the present invention is to provide amorphous titanium peroxide particles in which decomposition of the organic base material is unlikely to occur even if they are crystallized. Another object is a hydrophilic paint in which the organic base material is not easily decomposed even when applied to an organic base material, a hydrophilic coating layer formed by using the hydrophilic paint, and a building material having the hydrophilic paint layer. The purpose is to provide.</p>

<p> In order to solve the above problems, the amorphous metal oxide according to the present invention is an amorphous metal oxide that becomes capable of having organic matter resolution by crystallization, and is another one that suppresses the organic matter resolution. It is characterized by containing a metal.</p><p> When the amorphous metal oxide is amorphous titanium peroxide particles, the other metal is one or more metals selected from the group formed by W, V, Nb, Mo, Cu and Fe. There may be.</p><p> The above-mentioned inclusion may be carried out by doping, and when the other metal is vanadium (V), this doping is carried out by adding an oxidizing agent to an aqueous solution containing the respective hydroxides of titanium and vanadium in a predetermined ratio, and by this addition. It may be carried out by the reaction that occurs.</p><p> Further, vanadium may be 1 to 10 mol% based on the total molar amount of titanium and vanadium used for the above-mentioned content.</p><p> Further, the hydrophilic coating material according to the present invention is applied to an organic base material, and is characterized by containing the amorphous titanium peroxide particles. Further, the hydrophilic coating film layer according to the present invention is a hydrophilic coating film layer formed on an organic base material using this hydrophilic coating material. Further, the building material according to the present invention has an organic base material and a hydrophilic coating film layer containing the amorphous titanium oxide particles formed on the surface thereof.</p><p> The base material refers to a material to which a hydrophilic paint containing amorphous titanium peroxide particles is applied.</p>

<p> Since the amorphous titanium peroxide particles according to the present invention contain vanadium in a predetermined ratio, even if a part of the amorphous titanium peroxide particles crystallizes with the passage of time, the resolution of the organic matter developed by the crystallization is suppressed by the vanadium.</p><p> Therefore, even if a hydrophilic coating film containing the amorphous titanium peroxide particles as a binder component is applied to an organic base material to form a hydrophilic coating film layer, the organic base material using the hydrophilic coating film layer can be used. Decomposition is unlikely to occur.</p><p> Further, if the inclusion is carried out by doping, vanadium is uniformly scattered in the amorphous titanium peroxide particles, which is preferable from the viewpoint of suppressing the decomposition of the expressed organic matter.</p><p> Further, if the vanadium content is 1 to 10 mol% with respect to the total molar amount of titanium and vanadium, the effect of sufficiently suppressing the organic matter resolution can be obtained.</p><p> Since the hydrophilic coating film layer according to the present invention is a hydrophilic coating film layer containing the above-mentioned amorphous titanium peroxide formed by coating on an organic base material, the organic base material is not easily decomposed.</p><p> Since the building material according to the present invention is a building material having an organic base material and a hydrophilic coating layer containing the amorphous titanium peroxide formed on the surface thereof, the building material is hydrophilic in contact with the organic base material. Even if the amorphous titanium peroxide in the coating layer is crystallized, the organic base material is less likely to deteriorate, the life of the building material is less likely to be shortened due to this deterioration, and the appearance of the building material is less likely to be deteriorated. ..</p>

<figref num="1A">It is a figure which showed the steps 1 and 2 of the method of preparing a hydrophilic paint which concerns on embodiment of this invention in the order of steps.</figref><figref num="1B">It is a figure which showed the steps 3 and 4 of the method of preparing a hydrophilic paint which concerns on embodiment of this invention in the order of steps.</figref><figref num="1C">It is a figure which showed the steps 5 and 6 of the method of preparing a hydrophilic paint which concerns on embodiment of this invention in the order of steps.</figref><figref num="2">(A) It is explanatory drawing which shows the movement of an electron and a hole when vanadium (V) is not contained. (B) It is explanatory drawing which shows the movement of an electron and a hole when vanadium (V) is contained.</figref><figref num="3">It is a figure which showed the band cap energy, hydrophilicity and organic matter resolution of each metal oxide.</figref><figref num="4">(A) It is a table showing the organic matter resolution of the amorphous titanium peroxide layer formed by using the amorphous titanium peroxide solution (with or without vanadium) incubated at a temperature (40 ° C) for a predetermined period (day). .. (B) The line graph of the table in (A) is shown.</figref><figref num="5">(A) It is a table showing the hydrophilicity of a hydrophilic coating film layer formed by using a hydrophilic coating material having an amorphous titanium peroxide solution (with or without vanadium) as a binder composition in FIG. 4 (A). (B) The line graph of the table in (A) is shown.</figref><figref num="6">(A) A table showing the organic matter resolution of the hydrophilic coating layer formed by changing the solid content ratio of the anatase solution (ANA) / amorphous titanium peroxide solution (AMO) with and without vanadium. Is. (B) The line graph of the table in (A) is shown.</figref><figref num="7">(A) A table showing the hydrophilicity of the hydrophilic coating film formed by changing the solid content ratio of the anatase solution (ANA) / amorphous titanium peroxide solution (AMO) with and without vanadium. Is. (B) The line graph of the table in (A) is shown.</figref>

The amorphous metal oxide according to the present invention is an amorphous metal oxide having an organic matter resolution when the metal oxide crystallizes to become a photocatalyst, and is another one that suppresses the organic matter resolution. Contains elements such as metals. This amorphous metal oxide gradually crystallizes under the temperature environment condition of -15 ° C to 40 ° C, which is assumed as the residential environment in Japan, for example.

Specifically, ZnO, TiO₂, ZnS, Co₃O₄, NiO, Ag, ZnTiO₃, MnO₂, Cr₂O₃, La₂O₃, Fe₂O₃, SiO₂, MoO₃, BaTiO₃Amorphous metal oxides such as, etc. can be mentioned.

Other elements such as metals are elements such as metals that are contained in amorphous metal oxides and suppress the resolution of organic substances exhibited when the amorphous metal oxides crystallize. Normally, a photocatalyst is excited by light of a specific wavelength, but when it contains other metals, the wavelength of the excited light changes.

For example, in the case of crystalline titanium oxide, it is excited by ultraviolet light, but when other metals are contained, it is often excited not only in the wavelength range of ultraviolet light but also in the visible light range. Therefore, the other metal is an element that suppresses the organic matter resolution comprehensively even if the amorphous metal oxide crystallizes and is excited in another wavelength region.

If the amorphous metal oxide is titanium oxide, other metals include vanadium (V), tungsten (W), niobium (Nb), molybdenum (Mo), chromium (Cr), copper (Cu) and iron ( Fe) and the like. Elements other than metals that can suppress the resolution of organic substances can be used.

By incorporating these elements such as metals into amorphous metal oxides by doping or inclusion, for example, amorphous under the temperature environment condition of -15 ° C to 40 ° C, which is assumed as the residential environment in Japan. Even if the quality metal oxide is unintentionally partially crystallized, the resolution of the expressed organic matter can be suppressed.

For example, when an amorphous metal oxide is contained in the above by doping with an aqueous phase, an aqueous solution of a metal salt serving as a metal source for the photocatalyst (for example, an aqueous solution of titanium tetrachloride when the photocatalyst is titanium oxide) is prepared. By dissolving oxides of other metals in this aqueous solution and adjusting the pH of the aqueous solution, a precipitate (gel) of metal oxides containing both metals can be produced and contained as described above. In this case, the precipitate (gel) is dissolved with an oxidizing agent to prepare a solution of an amorphous metal oxide.

When the other metal is vanadium, a vanadium compound such as vanadium chloride, vanadium hydroxide, vanadium sulfide, or vanadium iodide can be used as the vanadium source.

Further, when the other metal is tungsten, it is tungsten oxide, when it is niobium, it is niobium oxide, when it is molybdenum, it is molybdenum oxide, when it is copper, it is copper oxide, and when it is iron, it is iron oxide.

The photocatalyst applicable to the present invention may be any photocatalyst that is excited to generate electrons and holes when irradiated with light having an energy equal to or higher than the band cap energy of the photocatalyst.₂, ZnS, Co₃O₄, NiO, Ag, ZnTiO₃, MnO₂, Cr₂O₃, La₂O₃, Fe₂O₃, SiO₂, MoO₃, BaTiO₃Etc. can be used. These may be commercially available.

Hereinafter, with respect to the embodiment of the amorphous metal oxide particles according to the present invention, titanium oxide is selected as the metal oxide and vanadium is selected as the metal that suppresses the resolution of organic substances, with reference to the drawings. This will be described in more detail. &lt;Amorphous titanium peroxide particles&gt; The amorphous titanium peroxide according to the present invention is an amorphous metal oxide, and as described above, when a predetermined amount of vanadium is contained, even if the amorphous titanium peroxide partially crystallizes and exhibits organic matter resolution, It can be suppressed by vanadium containing this organic matter resolution. Amorphous titanium peroxide can be a binder component of a hydrophilic coating material applied to an organic base material.

For example, when a hydrophilic coating layer is formed on the surface of an organic base material with a hydrophilic paint containing amorphous titanium peroxide particles, the amorphous titanium peroxide particles functioning as a binder component are fixed in contact with the base material. Therefore, when the amorphous titanium peroxide particles are partially crystallized with the passage of time and then photoexcited, unnecessary decomposition of the base material occurs at the contacted portion.

However, since the amorphous titanium peroxide particles according to the present invention contain vanadium, even if the amorphous titanium peroxide particles are partially crystallized and changed to crystalline material such as anatase, the organic matter decomposition activity is suppressed. It is possible to suppress unnecessary decomposition of the organic base material.

When the surface of the organic base material is decomposed, fine irregularities are generated on the surface of the base material, and the light reflection on the surface of the organic base material is not uniform, so that the appearance of the organic base material is deteriorated. By containing vanadium in the mixture, decomposition of the surface of the base material can be suppressed, and deterioration of the appearance of the organic base material can be prevented.

Further, since the decomposition of the surface of the organic base material is suppressed, the peeling of the hydrophilic coating film layer formed on the surface can be suppressed.

Regarding the amount of vanadium mixed, it is desirable that the amorphous titanium peroxide particles are contained in a molar amount of 1 to 10 mol% with respect to the total molar amount of titanium and vanadium used for forming the amorphous titanium peroxide particles. ..

When the molar amount of vanadium is less than 1 mol%, the effect of suppressing the organic matter resolution when the amorphous titanium peroxide particles are partially crystallized becomes low. Further, when it is more than 10 mol%, the effect of suppressing the organic matter resolution is low for the amount of vanadium applied, and the correlation between the vanadium amount and the organic matter resolution suppressing effect is low. Further, since the brown color of the hydrophilic coating film layer is increased, the color reproducibility of the base layer (including the portion other than the organic base material) is lowered.

When vanadium in an amount in the range of more than 10 mol% is mixed with the titanium oxide particles, a higher effect of suppressing the organic matter resolution of titanium oxide is obtained and the color is very tinted. In this case, the amount of vanadium mixed is It is also possible to obtain an acceptable color by reducing the thickness of the hydrophilic coating layer and applying it extremely thinly. &lt;Hydrophilic paint&gt; The hydrophilic coating material according to the present invention is a coating material containing at least a metal oxide such as the above-mentioned amorphous titanium peroxide particles. For example, when the hydrophilic paint contains an organic paint component, the amorphous titanium peroxide crystallizes over time while the hydrophilic paint is stored, and then crystallizes by some irradiation light. Even if the formed titanium oxide particles are excited, the organic matter resolution of the titanium oxide particles is suppressed by vanadium as described above, so that the organic paint component contained in the hydrophilic paint is not easily decomposed. Therefore, the paint components are less likely to deteriorate in quality, and the quality of the paint is less likely to deteriorate.

When amorphous titanium peroxide is included as a binder component in the hydrophilic paint, it can be a general composition such as 0.01 to 0.50% by weight in the paint composition. &lt;Hydrophilic coating layer&gt; The hydrophilic coating film layer according to the present invention is characterized in that it is formed on the surface of an organic base material using the above hydrophilic coating material.

Therefore, in the hydrophilic coating layer according to the present invention, even if the amorphous titanium peroxide particles are in contact with the surface of the organic base material, the organic matter resolution of the titanium oxide particles themselves is suppressed, so that the organic base material is suppressed. Erosion is suppressed. Therefore, as described above, deterioration of the appearance of the base material due to erosion and peeling of the hydrophilic coating film layer are less likely to occur, and the hydrophilic coating film layer becomes stronger than the conventional product.

Since the building material according to the present invention is a building material containing the hydrophilic coating film layer, the life of the building material is not shortened or the appearance is not deteriorated due to the problem of erosion of the base material.

Even in the state of hydrophilic paint or hydrophilic coating layer, after about 30 days under the temperature environment condition of around 40 ° C, amorphous titanium peroxide particles crystallize and have about 5 times the organic matter resolution. (Comparative Examples 1 to 3 described later), when 5 mol% of vanadium is mixed as described above, the methylene blue decomposition rate can be suppressed to a low level.

&lt;Organic base material&gt; Examples of the organic base material to which the amorphous titanium peroxide according to the present invention is applied can be used as a building material, and examples thereof include a base material containing an organic polymer. For example, organic polymers such as acrylic silicon-based, acrylic urethane-based, polyolefin-based, polyether-based, and fluorine-based can be used.

As the organic base material, if it is hydrophilic to the extent that the formation of striped droplets is prevented on the surface of the base material when the hydrophilic paint is applied, it is preferable because it can be applied more evenly. However, any material may be used as long as it can be applied uniformly. Further, in the case of an inorganic base material, any material may be used without particular limitation. &lt;Additives&gt; If a surfactant is added to the hydrophilic paint, the surface tension is lowered, so that the hydrophilic paint is less likely to be repelled on the surface of the organic base material when it is applied, and the hydrophilic paint can be applied evenly and evenly.

The surfactant may be any water-soluble solvent, and anionic, cationic ionic molecules, nonionic nonionic molecules and the like can be used. For example, monoalcohols such as methanol, ethanol and propanol, and dialcohols such as ethylene glycol, propylene glycol and propylene glycol can be used. In addition, methyl cellosolve, cellosolve, and butyl cellosolve cellosolves can also be used.

Further, since the hydrophilic paint has an almost inorganic composition, when it is applied to an organic base material, a coupling agent is added to the hydrophilic paint in order to improve the adhesion of the formed hydrophilic coating film layer to the base material. You may. As the coupling agent, for example, a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent can be used. The formed substantially inorganic hydrophilic coating film layer is more firmly bonded to the surface of the organic base material by this coupling agent.

Further, a matting agent may be added to the hydrophilic coating film in order to matte the hydrophilic coating film layer and improve the appearance. As the matting agent, extender pigments such as kaolin, talcite, alumina, hydrotalcite, benton, barium sulfate, and calcium carbonate and clays can be used. &lt;Manufacturing of amorphous titanium peroxide particles and hydrophilic paint containing them, formation of hydrophilic coating film layer&gt; Methods for incorporating other metals into amorphous metal oxide particles include doping and inclusion, but the specific procedure for doping in the aqueous phase is described in [Step 1] to [Step 6] below. It can be exemplified.

Of these, [Step 1] to [Step 4] are methods for preparing amorphous titanium peroxide particles mixed with vanadium. Hydrogen peroxide solution is added to an aqueous solution containing the respective hydroxides of titanium and vanadium in a predetermined ratio. Such as an oxidizing agent is added, and the reaction caused by this addition forms amorphous titanium peroxide particles containing the titanium and the vanadium in the same molecule. Each step will be described below in order, but the specific numerical values in the description are also examples and are not limited thereto.

[Process 1]: Raw material preparation With reference to FIG. 1A, a titanium source, a vanadium source, or the like is prepared as a raw material used in step 2 and subsequent steps described later.

First, the volume of the finally prepared amorphous titanium peroxide solution or anatase solution is determined, and the final concentration of titanium contained in the solution (for example, 0.5% by weight) and the molar amount of titanium (for example, 0.1 mol) are determined. A titanium chloride aqueous solution containing the molar amount of titanium is prepared as a titanium source. It is easier to prepare the hydrophilic paint later if the molar amount of titanium is the same in both the case of preparing the amorphous titanium peroxide solution and the case of preparing the anatase solution.

Further, for example, vanadium oxide (about 0.0005 to 0.005 mol) containing a molar amount of vanadium (about 0.001 to 0.01 mol of vanadium in the above example) which is about 1 to 10 mol% with respect to the total molar amount of titanium and vanadium described above. ) Is prepared.

In addition, ammonia water for neutralization and ammonia water for preparing a vanadium solution are prepared. The molar amount of ammonia in the ammonia water for preparing the vanadium solution is less than or equal to the molar amount of ammonia finally used for neutralization, and an arbitrary molar amount is added to set the pH at the start of pH adjustment. Can be done.

Then, as shown in FIG. 1A, a compound containing vanadium (vanadium oxide in the above example) is dissolved in aqueous ammonia for preparing a vanadium solution and appropriately diluted with distilled water (in the above example, the vanadium oxide concentration is 0.9% by weight). %) To obtain a vanadium solution.

Further, since titanium chloride is strongly acidic, distilled water may be mixed with the titanium chloride aqueous solution to dilute it.

A hydrolyzate of titanium alkoxide can also be used instead of the titanium chloride. Examples of the titanium alkoxide in this case include tetraethoxytitanium, tetraisopropoxytitanium, tetranormalpropoxytitanium, and tetranormalbutoxytitanium. [Step 2]: Precipitation In step 2, each solution prepared in step 1 is mixed to form a precipitate (gel).

First, the vanadium solution and the aqueous ammonia for neutralization are mixed, and the entire amount of this solution is gradually added to the titanium chloride aqueous solution (or titanium alkoxide aqueous solution). After that, the pH is further adjusted with aqueous ammonia, but when preparing high-viscosity amorphous titanium peroxide particles, the pH is preferably 2 to 6.

As a result, a precipitate (gel) in which titanium hydroxide and vanadium hydroxide are mixed is obtained (see [Step 2] in FIG. 1).

Here, the amount of vanadium contained can be adjusted by adjusting the amount of the vanadium oxide solution to be mixed when the vanadium solution and the ammonia water are mixed. [Step 3]: Removal of unnecessary ions (cleaning) With reference to FIG. 1B, to the weight of the precipitate (gel), add the amount of water required to reach the final solution concentration (Ti about 0.5% by weight in the example) and remove the supernatant (not shown). .. By repeating these operations, the precipitate (gel) is washed until the supernatant has a conductivity of 10 μs / cm or less. [Step 4]: Dissolution of precipitate (gel) (preparation of amorphous titanium peroxide solution) To the precipitate (gel) of step 3 with water added, an oxidizing agent such as hydrogen peroxide, which has a molar amount 10 times the molar amount of titanium, is added. Amorphous titanium peroxide can be produced by adding a precipitate (gel) of an oxidizing agent such as hydrogen peroxide.

In this case, the heat of fusion of the precipitate (gel) may promote the crystallization of the generated amorphous titanium peroxide particles. Therefore, the reaction solution may be dissolved at a low temperature in a constant temperature bath such as ice water. desirable.

As a result, an amorphous titanium peroxide solution (in the above example, a solution of amorphous titanium peroxide particles presumed to contain 0.1 mol of titanium and 0.001 to 0.01 mol of vanadium) is obtained.

[Step 5]: Preparation of hydrophilic paint Next, referring to FIG. 1C, a hydrophilic paint is prepared from amorphous titanium peroxide, water, (optionally a photocatalyst, an additive, etc.). When a photocatalyst is included, the hydrophilic coating material is prepared in consideration of the solid content ratio of the amorphous titanium peroxide solution. The total weight% of the photocatalyst and the binder in the hydrophilic coating material can be a general composition and can be changed arbitrarily. [Step 6]: Coating The hydrophilic coating film layer according to the present invention is a coating film formed on an organic base material using a hydrophilic coating film, and the thickness of the hydrophilic coating film layer is preferably less than 20 μm. It is not preferable to apply a thick coat of 20 μm or more because it will be colored and will be noticeable when cracks occur.

Also, it can be applied as thinly as possible. The range that can be applied thinly depends on the hydrophilicity of the organic base material on which the hydrophilic coating film is formed, and also changes depending on the material of the organic base material. Substrate is preferred.

As a method of applying the hydrophilic paint to the organic base material, a method such as spray coating, dipping, spin coating, brush coating, and bell coating can be used. (Drying of hydrophilic coating layer) Regarding the drying of the hydrophilic coating film layer after coating, if it is a drying method that does not adversely affect the hydrophilic coating film layer or the organic base material, such as a temperature range that does not deteriorate the base material in the case of an organic base material. , Any drying method may be used. (Organic matter resolution / hydrophilicity evaluation) The organic matter resolution of the hydrophilic coating film layer can be evaluated according to the "Photocatalyst Product Technology Council Regulations / Regulations and Test Method June 2005". Further, the hydrophilicity is meaningful to be evaluated because it serves as an index of the resolution of organic matter, and the evaluation method follows the method of Example 1 described later.

Regarding the investigation of the decomposition of the organic base material at the interface between the organic base material and the hydrophilic coating layer, the surface of the hydrophilic coating layer also has the interface with the organic base material of the hydrophilic coating layer. Since some of the amorphous titanium peroxide particles are exposed at the same frequency, the organic matter resolution of the amorphous titanium peroxide at the interface can be known by examining the organic matter resolution on the surface of the hydrophilic coating layer. ..

Here, to be more precise, mW / cm at the interface and the surface depends on the parameters (film thickness and haze value) of the hydrophilic coating film to be formed.²To create a correction coefficient, which may correct the evaluation value of the organic matter resolution on the surface.

<p> Examples and comparative examples according to the present invention are shown below, and the present invention will be described in more detail with reference to FIGS. 4 to 7, but the present invention is not limited to these examples and the like. In FIGS. 4 to 7, the vanadium mixed amount (V mixed amount, mol%) is the molar amount of vanadium (mol) used with respect to the total molar amount of titanium and vanadium used for forming the amorphous titanium peroxide particles. %) Is shown. [Example 1] In Example 1, 1 mol% of vanadium was mixed with the total molar amount of titanium and vanadium used for forming the amorphous titanium peroxide particles, and the effect of suppressing the decomposition of organic substances developed by the crystallization of amorphous titanium peroxide was obtained. evaluated. I prepared the following items. [Process 1] (A) Titanium chloride aqueous solution (titanium source) (Made by Wako Junyakusha, TiCl₄Contains 16.5 ± 0.5% by weight of aqueous solution and titanium (Ti)) (B) Ammonia water (ammonia source) (Made by Wako Junyakusha, NH₄OH aqueous solution, ammonia (NH₃) Containing 25 ~ 27.9 ± 0.5% by weight) (C) Vanadium solution (vanadium source) (Contains 95% by weight or more of vanadium oxide) (D) Hydrogen peroxide solution (hydrogen peroxide source) (Manufactured by Wako Pure Chemical Industries, hydrogen peroxide aqueous solution, 30.0 to 35.5% by weight) (E) Vanadium solution (vanadium oxide approx. 0.9% by weight) Regarding (E) vanadium solution, vanadium solution (C) (manufactured by Wako Pure Chemical Industries, Ltd., V)₂O₅(Contains 95% by weight or more) 3.6 g (about 0.02 mol as vanadium) and (B) ammonia water (Wako Pure Chemicals NH₄OH aqueous solution, NH₃18.0 g (about 0.02 mol as ammonium ion) and 378.4 g of distilled water were mixed to prepare a mixture containing about 0.9% by weight of vanadium oxide. [Step 2]: Formation of precipitate (gel) In a 3 L beaker, 30 g of titanium chloride solution (A) (about 0.1 mol as titanium) and 60 g of distilled water were mixed. Separately, aqueous ammonia (B) was diluted with distilled water (about 140 g) to a concentration of 2.5% by weight. Diluted aqueous ammonia (about 0.074 mol) was mixed with about 10.54 g (about 0.001 mol) of vanadium solution (E). The entire mixed solution of this aqueous ammonia and vanadium solution was mixed with a 3 L beaker of titanium chloride solution.</p><p> Furthermore, the pH was measured with a pH meter (HANNAHI 98129 COMBO1) every time 20 g of ammonia water (B) was added to a 3 L beaker. The pH was adjusted to 4 to form a precipitate (gel). [Step 3]: Removal of unnecessary ions (cleaning) Distilled water was added to each solution containing the precipitate (about 400 g each) at the end of step 2 to make 3 L, and the conductivity of the supernatant at this time was measured with a pH meter (HANNAHI 98129 COMBO1 or HORIBA, Ltd. B-173), and the supernatant was measured. Was removed. These operations were repeated until the conductivity of the supernatant of each solution became 10 μS / cm or less. [Step 4]: Preparation of amorphous titanium peroxide solution The supernatant of each solution in step 3 was discarded, the weight of the precipitate (gel) was measured, and about 118 g (about 1 mol) of hydrogen peroxide solution (D) was prepared. Further, distilled water was added to the precipitate (gel) in consideration of the weight of the precipitate (gel) and the weight of hydrogen peroxide so that the titanium weight concentration became about 0.5%.</p><p> To prepare a solution of amorphous titanium peroxide particles, boil this solution in a constant temperature bath at about 40 ° C, and when the solution temperature reaches approximately 40 ° C, add hydrogen peroxide solution (D) to the above solution. About 118 g (about 1 mol) was added to the solution to make about 1 L of the solution having a titanium concentration of about 0.5% by weight.</p><p> Then, the mixture was stirred until it became a transparent orange to yellow solution, taken out from a constant temperature bath and left at room temperature to obtain a jelly-like, highly viscous amorphous titanium peroxide solution (AMO). [Step 5]: Preparation of hydrophilic paint In this Example 1, since it is investigated that the amorphous titanium peroxide particles crystallize when immersed in warm water at 40 ° C. as described above, only the amorphous titanium peroxide solution is used as the hydrophilic paint, and other additives and the like are used. Did not include. [Step 6]: Coating After spreading 2 ml of the above hydrophilic paint on a commercially available slide glass (Matsunami Glass Industry Co., Ltd. S-1111 (length 76 mm x width 26 mm x thickness 0.8 to 1.0 mm)), spin coating method (500 r.pm 5 seconds) , 1,500 rpm for 10 seconds). The slide glass was dried at room temperature. Coating and drying were repeated twice in total to form a hydrophilic coating layer. (Evaluation of organic matter resolution) Ultraviolet rays (1.0 mW / cm) for 3 hours on the hydrophilic coating layer of this slide glass²) Is irradiated to prepare a test piece, and the photocatalyst performance evaluation test method I (liquid phase film adhesion method, 2001 version) described in "Photocatalyst Product Technical Regulations / Regulations and Test Method (June 2005)" is used. The organic matter resolution of the hydrophilic coating film was evaluated (see Fig. 4).</p><p> The values in the table shown in FIG. 4 represent the decomposition rate [%] of methylene blue when the substrate solution of methylene blue immediately after preparation is used as a blank (decomposition rate 0%). (Evaluation of hydrophilicity) Five slide glasses having a hydrophilic coating film formed by the above coating were prepared, and these were left in a constant temperature and humidity chamber (dark place) at a humidity of 65% and a temperature of 23 ° C for 8 hours or more. Then, the slide glass left unattended was taken out from this constant temperature and humidity chamber. 1 μl of distilled water was dropped onto the hydrophilic coating film layer of each slide glass with a micropipettor or the like, and the contact angle between the hydrophilic coating film layer and water was measured. The hydrophilicity of the hydrophilic coating film layer was evaluated by taking the average of each measured value.</p><p> Kyowa Interface Science Co., Ltd. DM300 was used to measure the contact angle. This result was used as the contact angle of the hydrophilic coating film layer in a dark place (not irradiated) (see Fig. 5).</p><p> On the other hand, 5 other slide glasses (same as above) having a hydrophilic coating film formed by the above coating were prepared in the same manner, and ultraviolet rays (1.0 mW / cm) were applied to the hydrophilic coating layer in a dark place for 3 hours.²) Was irradiated. Then, 1 μl of distilled water was dropped onto the irradiated hydrophilic coating film layer with a micropipettor or the like, and the contact angle between the hydrophilic coating film layer and water was measured. Regarding the measurement of the contact angle, the average of the measured values of each slide glass was taken and evaluated as the hydrophilicity of the hydrophilic coating film layer. Kyowa Interface Science Co., Ltd. DM300 was used for this measurement in the same manner as described above. This result was used as the contact angle of the hydrophilic coating film layer after irradiation (see Fig. 5). [Example 2, Example 3] When the amorphous titanium peroxide solution was prepared in step 4 of Example 1, the solution was prepared for 27 days (Example 2) and 60 days (Example 3), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Example 1 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). [Example 4] Coating, organic resolution and hydrophilicity as in Example 1 except that the amount of vanadium solution (E) mixed in step 2 of Example 1 was adjusted to about 31.6 g (containing about 0.003 mol of vanadium). Was evaluated (see Figures 4 and 5). [Examples 5 and 6] When the amorphous titanium peroxide solution was prepared in step 4 of Example 4, the solution was prepared for 27 days (Example 5) and 60 days (Example 6), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Example 4 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). [Example 7] Coating, organic resolution and hydrophilicity, as in Example 1, except that the amount of vanadium solution (E) mixed in step 2 of Example 1 was adjusted to about 52.7 g (containing about 0.005 mol of vanadium). Noh was evaluated (see Figures 4 and 5). [Examples 8 and 9] When the amorphous titanium peroxide solution was prepared in step 4 of Example 7, the solution was prepared for 27 days (Example 8) and 60 days (Example 9), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Example 7 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). [Example 10] Coating, organic resolution and hydrophilicity as in Example 1 except that the amount of vanadium solution (E) mixed in step 2 of Example 1 was adjusted to about 73.8 g (containing about 0.007 mol of vanadium). Was evaluated (see Figures 4 and 5). [Examples 11 and 12] When the amorphous titanium peroxide solution was prepared in step 4 of Example 10, the solution was prepared for 27 days (Example 11) and 60 days (Example 12), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Example 10 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). [Example 13] Coating, organic resolution and hydrophilicity as in Example 1 except that the amount of vanadium solution (E) mixed in step 2 of Example 1 was adjusted to about 105.5 g (containing about 0.01 mol of vanadium). Was evaluated (see Figures 4 and 5). [Examples 14 and 15] When the amorphous titanium peroxide solution was prepared in step 4 of Example 13, the solution was prepared for 27 days (Example 14) and 60 days (Example 15), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Example 13 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). [Comparative example 1] The coating, organic matter resolution, and hydrophilicity were evaluated in the same manner as in Example 1 except that the same amount of pure water was added instead of the vanadium solution (E) in step 2 of Example 1 (Figs. 4 and 5). reference). [Comparative Examples 2 and 3] When the amorphous titanium peroxide solution was prepared in step 4 of Comparative Example 1, the solution was prepared for 27 days (Comparative Example 2) and 60 days (Comparative Example 3), respectively, from the time when the temperature of the solution reached approximately 40 ° C. The coating, organic resolution and hydrophilicity were evaluated in the same manner as in Comparative Example 1 except that the temperature was maintained at 40 ° C (see FIGS. 4 and 5). (Organic resolution of hydrophilic coating layer composed of amorphous titanium peroxide particles) As shown in Fig. 4, the amorphous titanium peroxide 27 to 60 days after the start of hot water immersion at 40 ° C was partially crystallized and the organic matter resolution was increased by about 5 times (Comparative Examples 1 to 3). However, when 1 to 10 mol% of vanadium was mixed, the organic matter resolution was suppressed to a low level, and even after 27 to 60 days, the organic matter resolution was about the same as 0 days (Examples 1 to 15).</p><p> In each of the above Examples and Comparative Examples, the degree of partial crystallization of amorphous titanium peroxide at 40 ° C was evaluated, but this partial crystallization is likely to occur even at a temperature of less than 40 ° C. Even if amorphous titanium peroxide is partially crystallized under the temperature environment condition of -15 ° C or more and less than 40 ° C, which is assumed as a residential environment in Japan, the resolution of the expressed organic matter can be suppressed if vanadium is mixed. .. (Hydrophilicity of hydrophilic coating layer composed of amorphous titanium peroxide particles) Hydrophilicity is meaningful to evaluate because it is proportional to the amount of radicals that cause organic matter resolution.</p><p> With reference to Fig. 5, in the case where 0 days have passed since the start of immersion in warm water at 40 ° C (Comparative Example 1), the effect of partial crystallization is small because it is immediately after the preparation of the amorphous titanium peroxide solution, and the water after irradiation. Although the contact angle with is high, the contact angle after irradiation is 39.6 ° because it still partially crystallizes in a short 40 ° C immersion time and slightly develops organic matter resolution and does not contain vanadium that suppresses this organic matter resolution. It is a little low (slightly high in hydrophilicity).</p><p> When this amorphous solution (Comparative Example 1) elapses for 27 to 60 days under a temperature condition of 40 ° C, it further partially crystallizes, and the contact angle with water after irradiation becomes 0 ° (Comparative Examples 2 and 3), and organic substances Comes to have resolution.</p><p> On the other hand, in each group after 0-day, 27-day, and 60-day irradiation in which the amount of vanadium mixed was 1 to 10 mol% (Examples 1 to 15), each comparative example 1 to 3 was uniformly applied. It can be seen that the hydrophilicity was further reduced (see the comparison between Examples and Comparative Examples), and the organic matter resolution was suppressed by the mixing of vanadium. (Ability to suppress organic matter decomposition when using hydrophilic paint or hydrophilic coating film layer) Next, in Examples 16 to 20 and Comparative Examples 4 to 8, hydrophilicity was obtained by changing the solid content ratio of the anatase solution (photocatalyst): amorphous titanium peroxide solution in each of the cases where vanadium was contained and the case where vanadium was not contained. It was evaluated how the organic matter resolution changes when a sex coating film is used.</p><p> In Examples 16 to 20, it was shown from the results of Examples 1 to 15 (see FIG. 4) that the amorphous titanium peroxide of Example 7 in which 5 mol% of vanadium was mixed suppressed the organic matter resolution most efficiently. Therefore, the one mixed with vanadium at 5 mol% was used.</p><p> In the following sentences, the molar% of vanadium in parentheses in the sentences in each example and comparative example is the vanadium used for the total molar amount of titanium and vanadium used for particle formation of amorphous titanium peroxide. The molar amount of is shown as a ratio.</p><p> When a hydrophilic coating material containing an amorphous titanium peroxide solution and an anatase solution is applied to a base material to form a hydrophilic coating layer, a hydrophilic coating layer mainly containing amorphous titanium peroxide particles and anatase particles (photocatalyst) is formed. Therefore, the proportion of amorphous titanium peroxide particles in the coating layer in contact with the organic substrate changes depending on the solid content ratio.</p><p> In addition, vanadium in the amorphous titanium peroxide particles can also serve as an electron-hole recombination site generated from anatase particles (photocatalyst) charged into the hydrophilic paint from the beginning.</p><p> Therefore, the ratio of each solid content affects the organic matter resolution at the interface between the organic base material and the hydrophilic coating film layer, and it is meaningful to investigate this. Since the organic matter resolution for the interface cannot be measured, the measurement was performed by regarding the surface of the hydrophilic coating film layer similar to the interface as the interface.</p><p> [Example 16] In Example 16, the solid content ratio (ANA: AMO) of the anatase solution (mixed with ANA, V5 mol%): amorphous titanium peroxide solution (mixed with AMO, V5 mol%) was set to about 50:50, and other compositions. Prepared a hydrophilic paint made of water. Other than that, the coating, organic matter resolution and hydrophilicity were evaluated in the same manner as in Example 1. As the amorphous titanium peroxide solution, the solution at the end of step 4 of Example 7 was used. Anatase solution (ANA) is prepared by the method described later. (Composition of hydrophilic paint) (F) Anatase solution (ANA) (Ti about 0.5% by weight, molar ratio Ti: V = about 0.95: 0.05) ... 0.25% by weight (G) Amorphous titanium peroxide solution (AMO) (Ti about 0.5% by weight, molar ratio Ti: V = about 0.95: 0.05) ... 0.25% by weight (H) Water ... 99.5% by weight The compositions (F) to (H) were mixed with a stirrer to prepare 100 g of a hydrophilic coating material having an anatase solution (F): amorphous titanium peroxide solution (G) having a solid content ratio (ANA: AMO) of 50:50.</p><p> Using this hydrophilic coating material, a hydrophilic coating film layer was formed by coating in the same manner as in Example 1, and the organic matter resolution evaluation and the hydrophilicity evaluation were performed.</p><p> The anatase solution (ANA) used as a photocatalyst was prepared by maintaining the liquid temperature at about 4 ° C in a constant temperature bath when preparing the amorphous titanium peroxide solution (AMO) in step 4 of Example 7, and hydrogen peroxide. To prepare an amorphous titanium peroxide solution, set a 1 L flask of this solution in the mantle heater, put the amorphous titanium peroxide solution from step 4 in this flask, and constantly adjust the amount of heat that the solution boils. The amorphous titanium peroxide solution was refluxed for 1 hour or more to prepare.</p><p> [Examples 17 to 20] In Examples 17 to 20, the solid content ratio (ANA: AMO) of the anatase solution: amorphous titanium peroxide solution of Example 16 was about 0: 100 (Example 17) and about 25:75 (Example 18), respectively. , Approximately 75:25 (Example 19) and approximately 100: 0 (Example 20). Other than that, coating, organic matter resolution and hydrophilicity were evaluated in the same manner as in Example 16.</p><p> [Comparative example 4] In Comparative Example 4, each particle containing no vanadium (anatase particles, amorphous titanium peroxide particles) was used, and anatase solution (ANA, V0 mol% mixed): amorphous titanium peroxide solution (AMO, V0 mol% mixed). The solid content ratio (ANA: AMO) was set to about 50:50, and other than that, the coating, organic matter resolution, and hydrophilicity were evaluated in the same manner as in Example 16.</p><p> The amorphous titanium peroxide solution and anatase solution of Comparative Example 1 were used in order to use one containing no vanadium. Specifically, as the amorphous titanium peroxide solution, the solution at the end of step 4 of Comparative Example 1 containing no vanadium was used. The anatase solution (mixed with ANA, V0 mol%) was prepared in the same manner as in Example 16 using the solution at the end of step 3 of Comparative Example 1. [Comparative Examples 5 to 8] In Comparative Examples 5 to 8, each particle (anatase particle, amorphous particle) containing no vanadium was used, and an anatase solution (ANA, V0 mol% mixed): an amorphous titanium peroxide solution (AMO, V0 mol% mixed) was used. The solid content ratio (ANA: AMO) is mixed so as to be 0: 100 (Comparative Example 5), 25:75 (Comparative Example 6), 75:25 (Comparative Example 7), 100: 0 (Comparative Example 8). Other than that, the coating, organic matter resolution and hydrophilicity were evaluated in the same manner as in the amorphous solution of Example 16. (Organic matter resolution) With reference to FIG. 6, for Examples 16 to 20, when the solid content ratio (ANA: AMO) is 25:75 to 100: 0, the organic matter resolution of the hydrophilic coating film layer is uniform regardless of the solid content ratio. There were (Examples 16, 18 to 20). That is, it was shown that the organic matter resolution was sufficiently suppressed in the above solid content ratio range regardless of the solid content ratio.</p><p> On the other hand, Comparative Examples 4 to 8 showed high organic matter resolution because they did not contain vanadium, and had a uniform organic matter resolution with a solid content ratio of 25:75 to 100: 0 as in Examples 16 to 20. (Comparative examples 4, 6 to 8). (Hydrophilicity) Hydrophilicity is meaningful to evaluate because it is proportional to the amount of radicals that cause organic matter resolution.</p><p> With reference to FIG. 7, in both Comparative Examples 4 to 8 and Examples 16 to 20, the water in the hydrophilic coating layer after irradiation was determined according to the amount of anatase solution (ANA) in the solid content ratio (ANA: AMO). The contact angle with was reduced.</p><p> In the range of solid content ratio (ANA: AMO) 25:75 to 100: 0, in each of Examples 16 to 20, the contact angle after irradiation was higher than that of Comparative Examples 4 to 8 due to the mixing of vanadium into each particle. It can be seen that the organic matter resolution was suppressed.</p><p> When the solid content ratio (ANA: AMO) is 0: 100, as shown in Examples 1 to 16, the effect of suppressing organic substances by mixing vanadium into the amorphous titanium peroxide particles can be seen.</p><p> This hydrophilicity is reduced by the inclusion of vanadium, but it is within the range where sufficient self-cleaning ability can be obtained.</p><p> In Examples 16 to 20, unlike the commercially available products, the anatase particles used as the photocatalyst are also mixed with vanadium at an amount of 5 mol%, so that the organic matter resolution is lower than that of the commercially available anatase solution, but like the commercially available products. Even when the hydrophilic coating layer of Examples 16 to 20 is formed by changing the solid content ratio as described above using anatase particles containing no vanadium, the solid content ratio can be changed only by changing the contact angle. There is no change in being able to change and use it.</p><p> Further, it is clear that even when vanadium is contained only in the amorphous titanium peroxide, it has an effect of suppressing the organic matter resolution of the photocatalyst and the partially crystallized amorphous titanium peroxide that are added to the hydrophilic paint from the beginning.</p><p> Therefore, when anatase particles that do not contain vanadium are used, each performance of the hydrophilic coating layer (organic resolution, hydrophilicity, etc.) can be adjusted by adjusting the amount of vanadium mixed in the amorphous titanium peroxide particles and the solid content ratio. ) Can be set. For example, the performance may be as shown in the above embodiment.</p><p> Although the present invention has been described above with reference to Examples and Comparative Examples, the present invention is not limited to each of the above Examples, and as described in the embodiments, it is amorphous in the above temperature range. The present invention can be applied as long as the metal oxide of the above is of a type that partially crystallizes and exhibits organic matter resolution.</p>