JP2016120483A - Titanium oxide-containing composition, method for producing titanium oxide-containing composition, and photocatalyst structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To turn the hue of a titanium oxide-containing composition comprising a divalent copper oxide into one close to white.SOLUTION: A titanium oxide-containing composition comprises a titanium oxide compound, a divalent copper oxide, and a binder as a solid content, and a solvent for suspending them. The titanium oxide-containing composition also comprises sulfonic acid in an amount corresponding to 0.5-25 mass% of the solid content.SELECTED DRAWING: Figure 1

Description

  The present invention mainly relates to a titanium oxide-containing composition which is a composition containing titanium oxide having a photocatalytic function and at least one of antibacterial and antiviral functions, and its application.

Photocatalysts using titanium oxide are widely used as photocatalysts because they are inexpensive, excellent in chemical stability, have high photocatalytic activity (decomposability of organic compounds, antibacterial properties, etc.) and are harmless to the human body. .
Further, it is known that a titanium oxide-containing composition obtained by mixing copper metal or a copper compound with titanium oxide has an excellent photocatalytic function and antibacterial / antiviral properties.

  For example, Patent Document 1 discloses a titanium oxide-containing composition as a microorganism inactivating agent that contains a photocatalytic substance together with a monovalent copper compound, and discloses that a titanium oxide catalyst can be used as the photocatalytic substance. Yes. Furthermore, Patent Document 1 describes that a monovalent copper compound has a much stronger inactivation effect on microorganisms than a divalent copper compound.

However, monovalent copper compounds are easily oxidized. For example, when Cu ₂ O (red), which is a monovalent copper oxide, is oxidized to change to CuO (black), which is a divalent copper oxide, etc. Color unevenness and deterioration of antibacterial and antiviral properties may occur.
In general, the titanium oxide-containing composition is applied to the surface of a predetermined base material (for example, a film material) and dried to fix the solid content mainly on the surface of the base material. However, if the above-described color unevenness occurs on the surface of the photocatalyst layer formed on the surface of the substrate by applying the titanium oxide-containing composition, the design properties are inferior.

In order to improve such a point, Patent Document 2 discloses that a divalent copper compound is used. There are various kinds of divalent copper compounds, but it is convenient to use divalent copper oxide as the copper compound from the viewpoint of its price and availability.
However, for example, when divalent copper oxide (CuO) is used as the divalent copper compound, the color of the titanium oxide-containing composition becomes blackish as a whole.

JP 2011-190192 A Japanese Patent No. 5343176

If the titanium oxide-containing composition has a blackish color, the application of using it on a substrate may be limited. For example, a titanium oxide-containing composition using divalent copper oxide often has darkening due to ultraviolet irradiation outdoors and the like, and thus its use is limited. Furthermore, under mainly visible light irradiation environments such as indoors, the titanium oxide-containing composition would be best transparent as long as its function is guaranteed, but it should be at least as white as possible. It is preferable because of the wide range of application.
In addition, a titanium oxide-containing composition using divalent copper oxide is used in a case where the composition is applied to the surface of a substrate and used in comparison with a titanium oxide-containing composition using monovalent copper oxide. However, it is unlikely that color unevenness occurs on the surface, but it is still a composition containing titanium oxide, for example, in a high humidity atmosphere such as indoors, or in an environment where light exists where titanium oxide produces a photocatalytic effect. When a human hand comes into contact with the surface of a film on which an object has been applied or an organic substance adheres to it, color unevenness may occur on the surface of the photocatalyst layer made using a titanium oxide-containing composition. sell. The occurrence of such color unevenness causes a problem in design rather than the color of the photocatalyst layer formed by applying the titanium oxide-containing composition on the surface of the base material is uniformly black as a whole. Probability is high.

  The present invention has an antibacterial and antiviral property, and the titanium oxide-containing composition containing a divalent copper oxide is close to white in color and is easily maintained. The problem is to widen the application range of and provide the application.

In order to solve the above-mentioned problems, the present inventor proposes the following invention.
The present invention is a titanium oxide-containing composition containing a titanium oxide compound, divalent copper oxide, and a binder as a solid content, and a solvent for suspending the same. A titanium oxide-containing composition comprising an amount of sulfonic acid corresponding to 5 to 25% by mass.
Here, the sulfonic acid in the present invention is an alkyl sulfonic acid or an alkenyl sulfonic acid represented by the formula (1).
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkyl group which may have a substituent. And a C3-10 cycloalkenyl group which may have a substituent, or a C6-10 aryl group which may have a substituent.
Examples of the sulfonic acid represented by the above formula (1) are vinyl sulfonic acid or methane sulfonic acid.
The titanium oxide-containing composition containing a titanium oxide compound, divalent copper oxide, and a binder as a solid content and containing a solvent for suspending them is generally the titanium oxide-containing composition described in the prior art (Patent Document 2). It is the same as a thing. The inventor of the present application added a sulfonic acid represented by the above formula (1) in an amount corresponding to 0.5 to 25% by mass to the solid content. In addition, the present inventors have found that the occurrence of discoloration and color unevenness in use is small, and that the effect of reducing the antibacterial and antiviral properties in the use environment is small.
The mechanism by which the titanium oxide-containing composition obtained by adding the sulfonic acid represented by the above formula (1) to the conventional titanium oxide-containing composition has a color close to white is unknown. According to the consideration of the present inventor, divalent copper oxide and the sulfonic acid represented by the above formula (1) react with the former as a base and the latter as an acid (for example, CuO + 2HOSO ₂ R ₁ → Cu (Taking a reaction like (OSO ₂ R ₁ ) ₂ + H ₂ O) may be the reason why the titanium oxide-containing composition has a color close to white.
In addition, the inventor of the present application is also unclear in detail about the mechanism that the titanium oxide-containing composition according to the present invention easily maintains a white color, but with the above-described reason that the titanium oxide-containing composition becomes white We anticipate that this will be the same mechanism.
Furthermore, the present invention has a remarkable effect that darkening is hardly caused by ultraviolet irradiation. And the mechanism that produces this effect is unknown in detail. In the titanium oxide-containing composition, darkening is thought to be due to the reduction of at least one of divalent copper oxide and tetravalent titanium oxide. It is difficult to explain only with the reaction with the base, and it is presumed that there is an effect unique to the sulfonic acid represented by the above formula (1).
The same applies to the titanium oxide-containing composition described below. For example, the application of the titanium oxide-containing composition in the present application may be a photocatalyst, or the application may be an antibacterial or antiviral agent.
In addition, the solvent in this application suspends the titanium oxide compound as a solid substance, bivalent copper oxide, and a binder. Usually, the term “suspension” means that a solid is not dissolved but is dispersed in a solvent. For example, when the solvent is an alcohol and the binder is a silica binder having a low molecular weight, The silica binder may be dissolved in the solvent. In view of such points, the term “suspension” as used in the present application includes a case where a part of the solid is dissolved in the solvent, but the rest of the solid is dispersed in the solution as a solid.

The titanium oxide compound may be anatase-type titanium oxide, rutile-type titanium oxide, or a mixture thereof. The crystal structure of titanium oxide includes an anatase type, a rutile type, and a brookite type. Among these, as the titanium oxide of the present invention, anatase type titanium oxide and rutile type titanium oxide can be used. Anatase-type titanium oxide and rutile-type titanium oxide generally have a higher function as a photocatalyst under ultraviolet irradiation, but they may be mixed.
The titanium oxide compound may have a molar ratio of rutile titanium oxide to titanium oxide of 50% or more. By using such a titanium oxide compound, the photocatalytic action that produces the titanium oxide compound and the antibacterial and antiviral properties can be further increased.

At least a part of the copper oxide may be a reaction product with the sulfonic acid represented by the above formula (1).
Such a reaction product may be generated only by adding the sulfonic acid represented by the above formula (1) to a conventional titanium oxide-containing composition, or promotes a reaction for generating such a reaction product in the manufacturing process. In some cases, it is obtained by performing a process for performing the process (the process will be described later). The reactants referred to in the present application include both those that are generated after the treatment for promoting the generation of the reactants as described above and those that are not.

The binder in the present invention is obtained by applying the titanium oxide-containing composition to the surface of a predetermined substrate and drying it at the time of use of the titanium oxide-containing composition. What is necessary is just what can fix a titanium oxide with respect to a base material in fixing. In any case, known binders can be used.
The binder in the present invention may have a hydroxyl group on the binder surface. In the case of such a binder, when the sulfonic acid represented by the above formula (1) is alkenyl sulfonic acid which is a vinyl sulfonic acid having a double bond, the binder hydroxyl group and alkenyl sulfonic acid Reaction with a heavy bond becomes possible, and free (single) sulfonic acid is reduced. Thereby, the titanium oxide-containing composition in which a sulfonic acid having a double bond as described above is selected is obtained from the coating film when the coating film made using the composition comes into contact with a high humidity environment or hot water. Since less sulfonic acid (alkenyl sulfonic acid) elutes, the durability can be expected to improve. The sulfonic acid in this case is a part of the sulfonic acid represented by the above formula (1), and is a sulfonic acid represented by the following formula (2).
R ₂ —SO ₂ OH (2)
(In the formula, R ₂ represents a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkenyl group which may have a substituent.)
An example of the sulfonic acid represented by the above formula (2) is vinyl sulfonic acid.
The binder is a metal oxide gel or metal hydroxide gel, and the specific surface area thereof is preferably 50 m ² / g or more after drying at 150 ° C., more preferably 100 m ² / g or more. If it has such a specific surface area, adhesiveness will improve more and a catalyst activity will also improve. Here, as a metal component, the oxide gel or hydroxide gel of metals, such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, can be illustrated preferably. In addition, the binder includes a reaction product of an oxide gel or hydroxide gel of metal such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, and the sulfonic acid of the above formula (2). It may be included.

A solvent is a liquid which suspends the solid content contained in a titanium oxide containing composition, and can use a well-known thing as much as possible.
The solvent may be one of water, alcohols, and ketones, or a mixture of two or more thereof.
Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture thereof. Examples of ketones include acetone, acetylacetone, methyl ethyl ketone, or a mixture thereof. Can be mentioned.

The titanium oxide-containing composition of the present invention can be obtained by mixing a titanium oxide compound, divalent copper oxide, a binder, the above-mentioned amount of the sulfonic acid represented by the above formula (1), and a solvent. .
However, in order to better obtain the effect of the present invention that the color of the titanium oxide-containing composition is close to white, the divalent copper oxide is reacted with the sulfonic acid represented by the above formula (1). Thus, it should promote the production of a reaction product of copper oxide and the sulfonic acid represented by the above formula (1).

As described above, R ₁ contained in the sulfonic acid represented by the formula (1) in the present invention is a C1-10 alkyl group which may have a substituent, or a C2-10 alkenyl group which may have a substituent. A C3-10 cycloalkyl group which may have a substituent, a C3-10 cycloalkenyl group which may have a substituent, or a C6-10 aryl group which may have a substituent.
The C1-10 alkyl group or C2-10 alkenyl group represented by R ₁ may have a linear or branched structure. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, vinyl group, methylvinyl group, 1-propenyl group, allyl group, methallyl A group, 1-methylallyl group, 1-butylenyl group, 2-butylenyl group, isobutylenyl group, 1,3-butadiene-1-yl group and the like.
Specific examples of the C3-10 cycloalkyl group or the C3-10 cycloalkenyl group represented by R ₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-cyclopentenyl group. , 3-cyclohexenyl group and the like.
Examples of the C6-10 aryl group represented by R ₁ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
R ₁ is a C2-10 alkenyl group that may have a substituent, or a C3-10 cycloalkenyl group that may have a substituent, that is, R ₁ is R ₂ , or It is preferable that the sulfonic acid represented by the formula (1) is an alkenyl sulfonic acid represented by the formula (2).
Specifically, the sulfonic acid represented by the above formula (2) in the present invention is more preferably vinyl sulfonic acid.
Alkenyl sulfonic acids can be reacted with binders, particularly with ultraviolet light. Therefore, as described below, when R ₁ is R ₂ , in other words, when the sulfonic acid represented by formula (1) is the sulfonic acid represented by formula (2), As a method for producing a titanium oxide-containing composition, any of the A-3 method, B-1 method, and B-2 method described later is employed, or a method C-2 is employed as a method for producing a photocatalyst structure. It is preferable to employ them. In particular, when a reaction between the binder and the sulfonic acid is required, the sulfonic acid represented by the above formula (2) is an alkenyl sulfonic acid whose R ₂ is a C2-10 alkenyl group that may have a substituent. A vinyl sulfonic acid is more preferable.
The above “may have a substituent” means that one or a plurality of hydrogen atoms contained in a group represented by R ₁ (which is naturally the same in the case of R ₂ which is a subordinate concept of R ₁ ) is represented by Means that it may be substituted by a substituent. The substituent on R ₁ may further have a substituent. The “substituent” is not particularly limited, but is preferably a group exemplified for R ₁ , a C1-4 alkoxy group, a C1-4 alkenyloxy group, a carboxyl group, a C1-4 acyl group, a C1-4 acyloxy. Group, C1-4 alkoxycarbonyl group, halogen group such as chloro group, fluoro group, bromo group, nitro group, cyano group, C1-4 alkyl group or amino group which may be substituted with C1-4 acyl group, sulfone An acid group etc. can be mentioned.

The addition amount of the sulfonic acid represented by the above formula (1) in the present invention is based on the solid content or the total mass of the titanium oxide compound, the divalent copper oxide, and the binder. , An amount corresponding to 0.5 to 25% by mass.
The added amount is preferably 0.8% by mass or more in order to exhibit a more reliable effect. Further, if at least 10% by mass of the sulfonic acid represented by the formula (1) is present, a sufficient effect can be obtained. Therefore, if the addition amount is 10% by mass or less and a slight margin is observed, 20% by mass. % Or less is preferable.

The titanium oxide-containing composition may be produced by the method described below.
(Method A)
The solid content includes a titanium oxide compound, divalent copper oxide, and a binder, a solvent that suspends them, and an amount corresponding to 0.5 to 25% by mass with respect to the solid content. A method for producing a titanium oxide-containing composition by stirring and mixing a suspension comprising a sulfonic acid represented by formula (1), and preferably performing the following treatment on the suspension To produce a titanium oxide-containing composition. Method A includes the following 1-3.
1. A method of adding the sulfonic acid represented by the above formula (1) to the suspension and stirring and mixing at room temperature (referred to as method A-1).
2. A method of adding the sulfonic acid represented by the above formula (1) to the suspension and stirring and mixing with heating (referred to as method A-2).
3. A method of adding the sulfonic acid represented by the above formula (1) to the suspension, heating the mixture under ultraviolet irradiation, and stirring and mixing (referred to as method A-3).
(Method B)
The reaction product obtained by adding and reacting the sulfonic acid represented by the above formula (2) to the binder contains a titanium oxide compound and divalent copper oxide, and a suspension containing a solvent for suspending them. By adding and stirring and mixing the suspension, the above formula (2) in an amount corresponding to 0.5 to 25% by mass with respect to the titanium oxide compound as a solid content, divalent copper oxide, and binder is added. ) And a method for producing a titanium oxide-containing composition by performing the following treatment on the suspension. The method B includes the following 1 and 2.
1. After adding the sulfonic acid represented by the above formula (2) to the binder and preferably stirring and mixing under heating to obtain the reaction product 1, as a solid content, a titanium oxide compound and a divalent The reaction product 1 is added to a suspension containing copper oxide, and the mixture is stirred and mixed preferably while warming. (Referred to as B-1 method)
2. After adding the sulfonic acid represented by the above formula (2) to the binder, preferably heating under ultraviolet irradiation, stirring and mixing to obtain the reaction product 2, the titanium oxide compound as a solid content is obtained. The reaction product 2 is added to a suspension containing divalent copper oxide and stirred and mixed while preferably heating. (Referred to as B-2 method)

In the method A-1, the reaction conditions are not particularly limited. The time for stirring and mixing, that is, the reaction time, is preferably until the color of the titanium oxide-containing composition becomes white or after uniform mixing, the stirring is stopped and the mixture is left to stand so that the color of the titanium oxide-containing composition becomes white. That's all you need to do.
According to this method, the neutralization reaction between divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid represented by the above formula (1) seems to proceed mainly.
In the method A-2, the reaction conditions are not particularly limited. The reaction temperature is not particularly limited, but can be 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. Although reaction time changes with reaction temperature and the addition amount of the sulfonic acid represented by said Formula (1), what is necessary is just to stir until the color of a titanium oxide containing composition turns white.
According to this method, the neutralization reaction of divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid represented by the above formula (1) proceeds, and in particular, the sulfonic acid is vinyl sulfonic acid or the like. In the case of the alkenyl sulfonic acid represented by the formula (2), it is considered that the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds in parallel.
In the method A-3, the reaction conditions are not particularly limited. The reaction temperature is not particularly limited, but can be 50 ° C. or higher and 150 ° C. or lower. The wavelength and intensity of ultraviolet light can be UVA (400 to 315 nm) and UVB (315 to 280 nm), and the ultraviolet intensity can be 0.5 to ⁵ mw / cm ² . The reaction time varies depending on the reaction temperature, the intensity of ultraviolet light, and the amount of sulfonic acid added, but it is sufficient to stir at least until the color of the titanium oxide-containing composition becomes white.
According to this method, the neutralization reaction of the divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid proceeds, and in particular, the alkenyl represented by the above formula (2) such as vinyl sulfonic acid. In the case of a sulfonic acid, the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds in parallel, and the ratio of the reaction with the double bond increases from the A-2 method. It is thought that a photocatalytic reaction also occurs in the inside.

In the method B-1, the synthesis conditions for the reaction product 1 are not particularly limited. The reaction temperature can be, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 60 ° C. or higher and 150 ° C. or lower. The reaction time is preferably 1 hour or more and 24 hours or less.
According to this method, particularly when the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid, the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds, and The sulfonic acid group of the alkenyl sulfonic acid bonded to the binder is free, and it seems that there is also a free alkenyl sulfonic acid that does not bind to the binder.
In the method B-1, the conditions for mixing the suspension after adding the reaction product 1 are not particularly limited. The reaction temperature is 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. The reaction time may be stirred until the color of the titanium oxide-containing composition becomes white.
In the method B-2, the synthesis conditions for the reaction product 2 are not particularly limited. The reaction temperature can be, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 60 ° C. or higher and 150 ° C. or lower. The wavelength and intensity of the ultraviolet light can be UVA (400 to 315 nm) or UVB (315 to 280 nm), and the ultraviolet intensity can be 1 to 10 mw / cm ² . The reaction time is preferably 1 hour or more and 24 hours or less.
According to this method, in particular, when the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid, the reaction product 2 is obtained from the reaction product 1 with the hydroxyl group of the binder. The reaction of double bonds of alkenyl sulfonic acid is more advanced, and it is considered that the content of free alkenyl sulfonic acid is reduced. In the method B-2, conditions for mixing the suspension after the addition of the reaction product 2 are not particularly limited. The reaction temperature is, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. The reaction time may be stirred until the color of the titanium oxide-containing composition becomes white.

As an application of the titanium oxide-containing composition of the present invention, the present inventor also proposes the following photocatalyst structure as one aspect of the present invention.
An example of the photocatalyst structure includes a base material, and a photocatalyst layer including a titanium oxide compound, divalent copper oxide, a binder, and a sulfonic acid represented by the above formula (1) provided on the surface of the base material. The amount of the sulfonic acid represented by the formula (1) is 0.5 to 25 based on the total mass of the titanium oxide compound, the divalent copper oxide, and the binder. This is a photocatalyst structure corresponding to mass%.
Such a photocatalyst structure can be produced by applying any of the above-described titanium oxide-containing compositions according to the present invention to the surface of a substrate and drying it to evaporate the solvent contained therein.
The photocatalyst structure as described above has a photocatalytic function and antibacterial / antiviral properties of titanium oxide and divalent copper oxide on the surface of the base material, and a titanium oxide-containing composition on the surface of the base material Since the layer formed by an object can be made into a color close to white, it is excellent in terms of design. Moreover, with this photocatalyst structure, the layer formed of the titanium oxide-containing composition is likely to remain white, and is not easily darkened even when irradiated with ultraviolet rays.

The photocatalyst structure can be produced, for example, by the following (Method C) using any titanium oxide-containing composition in the present invention.
(Method C)
A photocatalyst structure manufacturing method for manufacturing a photocatalyst structure by applying any of the titanium oxide-containing compositions according to the present invention described above to the surface of a substrate and evaporating the solvent contained therein by drying. And after apply | coating a titanium oxide containing composition, it is the method of manufacturing a photocatalyst structure by performing the following processes. The C method is the following two types.
1 A method for producing a photocatalyst structure by applying any of the titanium oxide-containing compositions of the present application to a substrate, followed by drying and curing at a temperature of 150 ° C. or lower. (Referred to as C-1 method)
2 A method for producing a photocatalyst structure by applying any of the titanium oxide-containing compositions of the present application to a substrate, followed by drying and curing at a temperature of 150 ° C. or less under ultraviolet irradiation. (Referred to as C-2 method)
According to these production methods, the bond between the coating film and the substrate is strengthened by drying the coating film, and in particular, the sulfonic acid contained in the titanium oxide-containing composition is the above formula (2 In the coating film, it can be expected that the alkenyl sulfonic acid is immobilized by promoting the reaction between the double bond of the alkenyl sulfonic acid and the hydroxyl group of the binder. By preventing the alkenyl sulfonic acid from flowing out, it is considered that the function derived from the alkenyl sulfonic acid contained in the photocatalyst structure is better maintained. From this point, in the method C-2, it is particularly preferable to use the alkenyl sulfonic acid represented by the above formula (2) as the sulfonic acid.

Although the said base material can be selected suitably, it can be set as a sheet | seat, for example. The sheet may be a polymer resin molding or a textile fabric. Examples of the sheet that is a molded article of a polymer resin are molded articles such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and ABS resin.
Specific examples are shown below. The sheet used in the present invention is not particularly limited as long as it contains a polymer resin. For example, polyethylene terephthalate resin, polycarbonate resin, polyacrylate resin, Methyl methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene fluoride resin, fluorinated ethylene-propylene copolymer resin, fluorinated ethylene-ethylene copolymer resin, etc. A substrate can be formed. Further, as the sheet base material, one containing 1% by mass or more and 80% by mass or less plasticizer, preferably 5% by mass or more and 80% by mass or less plasticizer is used, and the titanium oxide-containing composition according to the present invention is applied thereto. In this case, the photocatalytic function is remarkably improved as compared with the photocatalyst structure obtained by the conventional method.
The shape of the substrate used in the present invention may be any shape such as a film shape, a plate shape, a tubular shape, a fiber shape, and a net shape. Moreover, if the magnitude | size is 10 micrometers or more, a photocatalyst can be carry | supported firmly.
More specifically, a light transmissive material made of a film material such as a tent canvas, a curtain, or a wallpaper, a polyethylene terephthalate resin, a polyacrylate resin, or the like can be preferably exemplified.
In order to improve the adhesion between the base material made of the polymer resin, the photocatalyst layer, and the adhesive layer, a sheet base material that has been subjected to discharge treatment, primer treatment, or the like on its surface can also be used. In addition, depending on the use such as construction materials, home appliances, and glasses that have already been constructed, the processed polymer resin molded body existing as a product is treated by the method for producing a photocatalyst structure of the present invention. It can also be set as a photocatalyst structure. In any case, the application range of such a photocatalyst structure can be said to be extremely wide.
In particular, when the method of the present invention is applied to a film material, in particular, a tented canvas, a remarkable effect appears as compared with the case of manufacturing by a conventional method. As the tent place canvas, any existing kind of tent place canvas can be used. A base fabric woven with a fiber made of resin such as polyester, a vinyl impregnated base fabric processed by coating and impregnating vinyl chloride resin on the base fabric, and a surface treatment in which the surface of the PVC impregnated base fabric is coated with acrylic, fluororesin, etc. It can be applied to everything called as tent canvas, such as PVC-impregnated base fabric, but it is particularly preferable for widely used B-type tent canvas, C-type tent canvas, and membrane materials for warehouses. Can be used.
The photocatalyst-supported tent canvas according to the present invention is widely used as a general building material, for example, roofs of tent warehouses, hoods of transport equipment such as truck seats, field stacks, decorative tents for shops, sunshades for shops, etc. , Various arcade roofs, roofs and side covers of exhibition pavilions, gas station roofs and side covers, waterproof protective sheets, snowproof sheets, air domes, pool covers, inner films of quick shelters, various architectural films Maintain a beautiful surface for a long period of time by utilizing its excellent antifouling, antibacterial, and antifungal properties in ceilings, partitions, windows, etc. that require antifouling, antibacterial, and antifungal effects Therefore, it can be particularly preferably used.
Among them, it is preferable to use the antibacterial / antiviral effect in medical facilities including a medical tent, a food factory, a food warehouse, a plant factory, etc., particularly in the inside thereof.

Table 1 showing the test results. Table 2 showing the test results. Table 3 showing the test results. Table 4 showing the test results. Table 5 and graph 5 which show a test result. Table 6 and graph 6 which show a test result. Table 7 and graph 7 which show a test result. Table 8 and graph 8 which show a test result. Table 9 and graph 9 which show a test result. Table 10 showing the test results. Table 11 showing the test results.

  Hereinafter, embodiments of the present invention will be described.

[Production of titanium oxide-containing composition]
In this embodiment, a titanium oxide-containing composition is produced as follows.
The titanium oxide-containing composition finally obtained contains a titanium oxide compound, divalent copper oxide, and a binder as a solid content, a solvent for suspending them, and a solid content of 0.001. The sulfonic acid represented by the following formula (1) is contained in an amount corresponding to 5 to 25% by mass (preferably 0.8% by mass or more and 20% by mass or less with respect to the solid content).
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, a C3-10 cycloalkyl group which may have a substituent, C3-10 cycloalkenyl group which may have a substituent, or C6-10 aryl group which may have a substituent.
Here, the C1-10 alkyl group or the C2-10 alkenyl group which is R ₁ contained in the sulfonic acid represented by the formula (1) may have either a linear or branched structure. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, vinyl group, methylvinyl group, 1-propenyl group, allyl group, methallyl A group, 1-methylallyl group, 1-butylenyl group, 2-butylenyl group, isobutylenyl group, 1,3-butadiene-1-yl group and the like.
Specific examples of the C3-10 cycloalkyl group or the C3-10 cycloalkenyl group represented by R ₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a 2-cyclopentenyl group. , 3-cyclohexenyl group and the like.
Examples of the C6-10 aryl group represented by R ₁ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
R ₁ is a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkenyl group which may have a substituent, that is, a sulfonic acid represented by the above formula (1) Is preferably an alkenyl sulfonic acid represented by the following formula (2).
R ₂ —SO ₂ OH (2)
(In the formula, R ₂ represents a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkenyl group which may have a substituent.)

The method for producing a titanium oxide-containing composition includes, for example, a titanium oxide compound, a divalent copper oxide, a binder, the above-mentioned amount of the sulfonic acid represented by the above formula (1), and a solvent. They are mixed at a mass ratio and stirred as necessary.
Moreover, what was carry | supported by the titanium oxide compound is also used suitably for bivalent copper oxide. A method of supporting divalent copper oxide on a titanium oxide compound is known, and a titanium oxide compound supporting divalent copper oxide can be obtained by this method.
As an example of the method, a method of executing “Manufacturing Method 3” in Paragraph [0029] following the method according to “Manufacturing Method 1” in Paragraph [0021] of Patent Document 2 (Japanese Patent No. 5343176). Can be mentioned. That is, a mixture of titanium oxide containing crystalline rutile-type titanium oxide, a divalent copper compound raw material (for example, CuCl ₂ · 2H ₂ O), water, and an alkaline substance is stirred and then dehydrated, whereby copper and A titanium-containing composition (Cu ₂ (OH) ₂ Cl / TiO ₂ ) can be obtained.
Next, the copper and titanium-containing composition obtained by the production method 1 can be further heat-treated to obtain a divalent copper oxide / titanium oxide compound (showing the CuO / TiO ₂ carrier of the present invention). . By this heat treatment, the divalent copper compound is firmly bonded to the titanium oxide.
As another example of a method for supporting divalent copper oxide on a titanium oxide compound, “Manufacturing Method 3” in Paragraph [0029] is executed following the method in accordance with “Manufacturing Method 2” in Paragraph [0029]. The method of doing can be mentioned. Copper and titanium-containing composition ((Cu ₂ Cl ₂ ) is obtained by dry-mixing or wet-mixing titanium oxide containing crystalline rutile-type titanium oxide and a divalent copper compound raw material (for example, CuCl ₂ .2H ₂ O). · _{2H 2} O / TiO 2) can be obtained.
Next, the copper and titanium-containing composition obtained by Production Method 2 can be further heat-treated to obtain a divalent copper oxide / titanium oxide compound (showing the CuO / TiO ₂ carrier of the present invention). . By this heat treatment, the divalent copper compound is firmly bonded to the titanium oxide.
However, considering that the color of the titanium oxide-containing composition is close to white, the reaction between the divalent copper oxide and the sulfonic acid represented by the above formula (1) is promoted, and copper oxide and More reaction product with sulfonic acid should be produced. The detailed method is as follows.

(Method A)
The solid content includes a titanium oxide compound, divalent copper oxide, and a binder, a solvent that suspends them, and an amount corresponding to 0.5 to 25% by mass with respect to the solid content. A method for producing a titanium oxide-containing composition by stirring and mixing a suspension comprising a sulfonic acid represented by formula (1), and preferably performing the following treatment on the suspension To produce a titanium oxide-containing composition. Method A includes the following 1-3.
1. A method of adding the sulfonic acid represented by the above formula (1) in the present invention to the suspension and stirring and mixing at room temperature (referred to as method A-1).
2. A method of adding the sulfonic acid represented by the above formula (1) to the suspension and stirring and mixing with heating (referred to as method A-2).
3. A method of adding the sulfonic acid represented by the above formula (1) to the suspension, heating the mixture under ultraviolet irradiation, and stirring and mixing (referred to as method A-3).

In the method A-1, the reaction conditions are not particularly limited. The time for stirring and mixing, that is, the reaction time, is preferably until the color of the titanium oxide-containing composition becomes white or after uniform mixing, the stirring is stopped and the mixture is left to stand so that the color of the titanium oxide-containing composition becomes white. That's all you need to do.
According to this method, the neutralization reaction between divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid represented by the above formula (1) seems to proceed mainly.
In the method A-2, the reaction conditions are not particularly limited. The reaction temperature is not particularly limited, but can be 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. Although reaction time changes with reaction temperature and the addition amount of the sulfonic acid represented by said Formula (1), what is necessary is just to stir until the color of a titanium oxide containing composition turns white.
According to this method, the neutralization reaction of divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid proceeds, and in particular, the alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid. In this case, it is considered that the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds in parallel.
In the method A-3, the reaction conditions are not particularly limited. The reaction temperature is not particularly limited, but can be 50 ° C. or higher and 150 ° C. or lower. The wavelength and intensity of ultraviolet light can be UVA (400 to 315 nm) and UVB (315 to 280 nm), and the ultraviolet intensity can be 0.5 to ⁵ mw / cm ² . The reaction time varies depending on the reaction temperature, the ultraviolet intensity, and the amount of the sulfonic acid represented by the above formula (1), but it may be stirred at least until the color of the titanium oxide-containing composition becomes white.
According to this method, the neutralization reaction of divalent copper oxide (CuO) and the sulfonic acid group of the sulfonic acid proceeds, and in particular, the alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid. In this case, the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds in parallel, and the ratio of the reaction with the double bond increases from the A-2 method. The photocatalytic reaction is expected to occur.

(Method B)
The reaction product obtained by adding the sulfonic acid represented by the above formula (2) in the present invention to the binder and reacting the suspension contains a titanium oxide compound and divalent copper oxide, and a suspension containing a solvent for suspending them. By adding to the suspension and stirring and mixing the suspension, the amount of the above corresponding to 0.5 to 25% by mass with respect to the titanium oxide compound, divalent copper oxide, and binder as solid content A method for producing a titanium oxide-containing composition comprising a sulfonic acid represented by formula (2), preferably a method for producing a titanium oxide-containing composition by subjecting a suspension to the following treatment: is there. The method B includes the following 1 and 2.
1. After adding the sulfonic acid represented by the above formula (2) to the binder and preferably stirring and mixing under heating to obtain the reaction product 1, as a solid content, a titanium oxide compound and a divalent The reaction product 1 is added to a suspension containing copper oxide, and the mixture is stirred and mixed preferably while warming. (Referred to as B-1 method)
2. After adding the sulfonic acid represented by the above formula (2) to the binder, preferably heating under ultraviolet irradiation, stirring and mixing to obtain the reaction product 2, the titanium oxide compound as a solid content is obtained. The reaction product 2 is added to a suspension containing divalent copper oxide and stirred and mixed while preferably heating. (Referred to as B-2 method)

In the method B-1, the synthesis conditions for the reaction product 1 are not particularly limited. The reaction temperature can be, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 60 ° C. or higher and 150 ° C. or lower. The reaction time is preferably 1 hour or more and 24 hours or less.
According to this method, particularly when the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid, the reaction of the double bond between the hydroxyl group of the binder and the alkenyl sulfonic acid proceeds, and The sulfonic acid group of the alkenyl sulfonic acid bonded to the binder is free, and it seems that there is also a free alkenyl sulfonic acid that does not bind to the binder.
In the method B-1, the conditions for mixing the suspension after adding the reaction product 1 are not particularly limited. The reaction temperature is 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. The reaction time may be stirred until the color of the titanium oxide-containing composition becomes white.
In the method B-2, the synthesis conditions for the reaction product 2 are not particularly limited. The reaction temperature can be, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 60 ° C. or higher and 150 ° C. or lower. The wavelength and intensity of the ultraviolet light can be UVA (400 to 315 nm) or UVB (315 to 280 nm), and the ultraviolet intensity can be 1 to 10 mw / cm ² . The reaction time is preferably 1 hour or more and 24 hours or less.
According to this method, particularly when the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid, the reaction product 2 is obtained from the reaction product 1 by the hydroxyl group and alkenyl of the binder. It seems that the reaction of the double bond of sulfonic acid proceeds more and the content of free alkenyl sulfonic acid is reduced.
In the method B-2, conditions for mixing the suspension after the addition of the reaction product 2 are not particularly limited. The reaction temperature is, for example, 50 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 150 ° C. or lower. The reaction time may be stirred until the color of the titanium oxide-containing composition becomes white.

The titanium oxide that can be used in the production method of this embodiment may be a known one, specifically, rutile type or anatase type titanium oxide, or a combination thereof. The titanium oxide in this embodiment is such that the rutile-type titanium oxide contained in the titanium oxide exceeds 50% in molar ratio.
The divalent copper oxide may be supported on titanium oxide as described above.
The divalent copper oxide may also contain a reaction product of the sulfonic acid represented by the above formula (1), particularly the sulfonic acid represented by the above formula (2), as described below.

The binder that can be used in the production method of this embodiment can be selected from the following, and may include two or more of the following.
The binder in the present invention is obtained by applying the titanium oxide-containing composition to the surface of a predetermined substrate and drying it at the time of use of the titanium oxide-containing composition. What is necessary is just what can fix a titanium oxide with respect to a base material in fixing. The binder in the present invention has a hydroxyl group on the binder surface, and when the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid, the hydroxyl group and the alkenyl sulfonic acid are mixed. It can be capable of reacting with a heavy bond. In any case, known binders can be used.
The binder is a metal oxide gel or metal hydroxide gel, and the specific surface area thereof is preferably 50 m ² / g or more after drying at 150 ° C., more preferably 100 m ² / g or more. If it has such a specific surface area, adhesiveness will become stronger and catalytic activity will also improve. Here, as a metal component, the oxide gel or hydroxide gel of metals, such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, can be illustrated preferably.
The binder is made of an oxide gel or hydroxide gel of a metal such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, and the sulfonic acid represented by the above formula (2). It may contain a reactant.

The solvent that can be used in the production method of this embodiment can be selected from the following, and may include two or more of the following.
The solvent can be selected from, for example, water, alcohols, and ketones.
Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture thereof. Examples of ketones include acetone, acetylacetone, methyl ethyl ketone, or a mixture thereof. Can be mentioned.

For example, the titanium oxide-containing composition described above may be used as a photocatalyst or may be used as an antibacterial or antiviral agent.
In addition, the titanium oxide-containing composition described above is applied to, for example, the entire surface (at least one surface) of a base material (for example, a sheet) and dried to evaporate the solvent. The solid content is fixed to the surface of the glass. But as a base material, it can select suitably from what was variously quoted in the column of the means for solving a subject.
When the base material is a sheet, the sheet may be a polymer resin molded product, a fabric made of fibers, or a sheet coated with a polymer resin using a fiber fabric as a core material. Examples of the sheet that is a molded article of a polymer resin are molded articles such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and ABS resin. Examples of the textile fabric are a polyester fiber fabric and a glass fiber fabric. Examples of a sheet coated with a polymer resin using a fiber fabric as a core material are a vinyl chloride tent base material using a polyester fiber fabric or a glass fiber fabric as a core material, and a fluororesin tent base material using a glass fiber fabric as a core material. is there.
The surface of the base material to which the titanium oxide-containing composition is applied has both a photocatalytic function of titanium oxide and divalent copper oxide and antibacterial and antiviral properties.

When manufacturing a photocatalyst structure using the titanium oxide containing composition in the above, the following (Method C) can be used, for example.
(Method C)
A method for producing a photocatalyst structure, which comprises applying the titanium oxide-containing composition described above to the surface of a substrate and drying to evaporate a solvent contained therein, which contains titanium oxide. This is a method for producing a photocatalyst structure by performing the following treatment after applying the composition. The C method is the following two types.
1 A method for producing a photocatalyst structure by applying any of the titanium oxide-containing compositions of the present application to a substrate, followed by drying and curing at a temperature of 150 ° C. or lower. (Referred to as C-1 method)
2 A method for producing a photocatalyst structure by applying any of the titanium oxide-containing compositions of the present application to a substrate, followed by drying and curing at a temperature of 150 ° C. or less under ultraviolet irradiation. (Referred to as C-2 method)
According to these production methods, the coating film and the substrate are firmly bonded by drying the coating film, and the sulfonic acid is an alkenyl sulfonic acid represented by the above formula (2) such as vinyl sulfonic acid. In this case, since the reaction between the double bond of alkenyl sulfonic acid and the hydroxyl group of the binder is promoted, it can be expected that the alkenyl sulfonic acid is immobilized. It is considered that the function derived from the alkenyl sulfonic acid contained in the photocatalyst structure is better maintained.

Hereinafter, the Example of the manufacturing method of the titanium oxide containing composition in this embodiment is demonstrated.
<Production of sample liquid A3> (heating and mixing)
To 1000 g of distilled water, 60 g (100 parts by mass) of rutile type titanium oxide A as a titanium oxide compound (BET value (10 m ² / g), rutile ratio (95.9 mol%), anatase ratio (4.1) Mol%), full width at half maximum (0.18 degree), primary particle size (150 nm): Showa Titanium Co., Ltd.) and 4.979 g (3.1 parts by mass, 3.0% by mass in terms of copper) ) CuCl ₂ · 2H ₂ O (manufactured by Kanto Chemical Co., Inc.) was added and stirred for 10 minutes.
Next, a 1 mol / L sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) aqueous solution was added so that the pH was 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry.
Next, the slurry was filtered, and the obtained powder was washed with pure water, dried at 80 ° C., and crushed with a mixer to obtain a sample. The obtained sample was heat-treated in the atmosphere at 450 ° C. for 3 hours to obtain Sample 1.
The sample 1 was heated and dissolved in a hydrofluoric acid solution, and the extract was quantified by ICP emission spectroscopic analysis. As a result, the copper ion was 3.1 parts by mass with respect to 100 parts by mass of titanium oxide. (3.0% by mass). That is, it was found that the total amount of the copper ions derived from the above-described CuCl ₂ · 2H ₂ O used to make Sample 1 was supported on the surface of titanium oxide as a copper compound. Furthermore, this copper compound was confirmed to be CuO from the waveform separation of ESCA (Electron Spectroscopy for Chemical Analysis: X-ray photoelectron spectroscopy).
Next, the sample 1 and the surfactant described above were added to 186.9 g of distilled water as a solvent, mixed by stirring, and slurry 1 that was a slurry adjusted to have a solid content of 25% by mass was obtained. Obtained.
Next, 50 g of slurry 1 and 1.5 g of a surfactant were added to and suspended in 148.5 g of ethyl alcohol, and 50 g of nitric acid acidic silica sol having a solid content of 25% by mass as a binder was further added. Then, nitric acid was further added to adjust the pH of the solution to 3, and 250 g of a photocatalyst coating solution 1 having a solid content of 10% by mass was obtained. The color of this photocatalyst coating liquid 1 was light brown.
Next, 100 g of the above-described photocatalyst coating solution 1 exhibiting a light brown color is placed in a 500 ml three-necked flask, and is one of the sulfonic acids represented by the above formula (1) while stirring. Further, in the above formula (2) Vinyl sulfonic acid (VSA-H: Trademark: manufactured by Asahi Kasei Finechem Co., Ltd., hereinafter may be simply referred to as “VSA”) 0.506 g (solid content of photocatalyst coating liquid 1) 5.1 mass%) was added and mixed to obtain a photocatalyst coating liquid 2.
The photocatalyst coating liquid 2 was stirred at room temperature for 30 minutes, then heated to 80 ° C. with stirring, and reacted at 80 ° C. for 3 hours to obtain a sample liquid A3 which was a liquid titanium oxide-containing composition. The color of the titanium oxide-containing composition was white.

  Hereinafter, the specific Example of this invention and its evaluation using a comparative example are demonstrated.

<Production of sample solution A1> (mixed at room temperature)
In a 500 ml three-necked flask, 100 g of light brown photocatalyst coating solution 1 produced in the same manner as described for sample solution A3 was added, and 0.126 g of vinyl sulfonic acid (VSA-H) (photocatalyst coating solution 1) with stirring. And 1.26% by mass with respect to the solid content of the mixture was added and mixed, and stirred at room temperature for 6 hours.
Thereafter, the mixed solution was transferred to a translucent plastic sample bottle and allowed to stand at room temperature for 2 weeks to obtain a sample solution A1 which was a titanium oxide-containing composition. The color of the sample liquid A1 was white.

<Generation of sample liquids A2, A4 to A7>
The method for obtaining the sample liquids A2, A4 to A7 is basically the same as the method for obtaining the sample liquid A1. The only difference is the amount of vinyl sulfonic acid (VSA-H) added to the photocatalyst coating solution 1 when the sample solutions A2, A4 to A7 are produced.
The amount of vinyl sulfonic acid (VSA-H) added to 100 g of the photocatalyst coating solution 1 when producing the sample solution A2 that is a titanium oxide-containing composition is 0.250 g (based on the solid content of the photocatalyst coating solution 1). 2.50 mass%), in the case of sample liquid A4, 0.760 g (7.60 mass% with respect to the solid content of photocatalyst coating liquid 1), and in the case of producing sample liquid A5, 1.01 g (photocatalyst) In the case of producing the sample liquid A6, the solid content of the coating liquid 1 is 1.260 g (12.6 mass% with respect to the solid content of the photocatalyst coating liquid 1). In the case of manufacturing, it is 2.53 g (25.3 mass% with respect to the solid content of the photocatalyst coating liquid 1).
All of the titanium oxide-containing compositions using the sample liquids A2 and A4 to A7 were white in color.

<Production of sample liquid A8>
In a 500 ml three-necked flask, 50 g of organosilica sol (IPA-ST (trademark): manufactured by Nissan Chemical Co., Ltd .: isopropyl alcohol (IPA) solvent, solid content 30.5 mass%, particle size 12 nm), IPA 26.3 g, Was added to adjust the solid content to 20.0% by mass, and 1.5 g of vinyl sulfonic acid (VSA-H) was added and uniformly dispersed while stirring.
Thereafter, the temperature was raised to 55 ° C. with further stirring, and further irradiated with ultraviolet rays with a BLB lamp (ultraviolet rays were adjusted to have an intensity of 1.0 to 1.5 mw / cm ^{2 on} the flask surface). Reacted for hours. The product was considerably thickened, resulting in a viscous reaction product (Reaction Product 1). That is, generation of a reaction product of silica sol as a binder and vinyl sulfonic acid was promoted by the above treatment. Viscous nature of the reaction products, and reaction with ~Si-OH bond of a double bond group and the silica sol vinylsulfonic _{acid, ~Si-O-CH 2 -CH} 2 -SO 3 H are generated This is thought to be due to this.
The reaction product 1 contains 1.93% by mass of VSA and 19.6% by mass of SiO ₂ .
Next, 100 g of the photocatalyst coating solution 1 was added to a 500 ml three-necked flask, and 15.54 g of the reaction product 1 was added with stirring, and mixed at room temperature for 30 minutes. While stirring, the temperature is raised to 70 ° C. for 1 hour, further raised to 80 ° C. for 1.5 hours, and finally heated to 100 ° C. and reacted for 1 hour to form a liquid titanium oxide-containing composition. Sample liquid A8 was obtained. The color of the titanium oxide-containing composition A8 was white.
The obtained sample liquid A8 is 115 g, and the amount of VSA added is 3.0 mass% of the solid content of the photocatalyst coating liquid 1. The (molar ratio) of VSA / Cu is 1.18. Thus, it was found that VSA can whiten CuO in the photocatalyst coating liquid 1 even when it is not a single substance but a silica sol and at least a part thereof are reacted in advance.

<Creation of sample sheets B1 to B8>
Next, the sample liquid A1 to the sample liquid A8 are applied to the surface of the sheet as an example of the base material in the present invention (although this is not necessarily limited to one surface of the sheet in this example) and dried, thereby allowing the sample liquid to dry. The photocatalyst layer was formed by fixing mainly the solid content of each of A1 to Sample solution A8 to the surface of the sheet.
The sheet used here contains a glass fiber base fabric, polyvinyl chloride, a plasticizer, and the like, and a tent base material (Clearliteron V-2000) for use in membrane ceilings, partitions, small tents, and the like. (Trademark): manufactured by Hiraoka Orizome Co., Ltd.
First, in this example, an adhesive layer was formed on the sheet. The adhesive layer was produced by applying an adhesive layer coating solution 1 produced as follows to the sheet.
The adhesive layer coating solution 1 was prepared by adding 30% by mass of polysiloxane (methyl) to a xylene-isopropanol (50/50) solution containing 10% by mass of an acrylic-silicon resin having a silicon content of 3% by mass. (Silicate 51 (trademark): manufactured by Colcoat Co., Ltd.) and a surfactant were added and mixed.
Application of the adhesive layer coating solution 1 to the sheet was performed using a general bar coater. Then, it dried at 100 degreeC for 15 minute (s), and the apply | coated adhesive layer coating liquid 1 was used as the contact bonding layer. The thickness of the adhesive layer is about 1.5 μm. The sheet provided with the adhesive layer was A4 in size, and eight of the same were made.
Next, the sample liquid A1 to the sample liquid A8 were applied on each of the adhesive layers of the sheet provided with the adhesive layer prepared as described above, and dried. The application of the sample liquid A1 to the sample liquid A8 was performed using a general bar coater. Then, it dries for 15 minutes at 100 ° C., and forms a photocatalyst layer derived from any of sample liquid A1 to sample liquid A8 on the adhesive layer, whereby sample sheet B1 to sample which are sheets having a photocatalyst layer Sheet B8 was obtained.
The color of the photocatalyst layer of sample sheet B1 to sample sheet B8 could be evaluated as white.

<Generation of Comparison Sheet 1>
The photocatalyst coating solution 1 described in the sample solution A3 is used as the comparison solution 1 instead of the sample solution A1 to the sample solution A8, and the same method as described in <Preparation of the sample sheets B1 to B8> is performed. Got.
The thicknesses of the adhesive layer and the photocatalyst layer included in the comparative sheet 1 were 1.5 μm and 1 μm, respectively. Moreover, the color of the photocatalyst layer of the comparative sheet 1 was light brown.

<Generation of Comparative Solution 2 and Comparative Sheet 2>
The method for obtaining the comparison liquid 2 is basically the same as the method for obtaining the sample liquid A3. The only difference is the amount of vinyl sulfonic acid (VSA-H) added to the photocatalyst coating solution 1 when the comparative solution 2 is produced.
The amount of vinyl sulfonic acid (VSA-H) added to 100 g of the photocatalyst coating liquid 1 when producing the comparative liquid 2 that is a titanium oxide-containing composition is 0.0300 g (based on the solid content of the photocatalyst coating liquid 1 0.30% by mass).
The comparative liquid 2 thus obtained was used in place of the sample liquid A1 to the sample liquid A8, and the comparative sheet 2 was obtained by the same method as described in <Preparation of Sample Sheets B1 to B8>.
The thicknesses of the adhesive layer and the photocatalyst layer included in the comparative sheet 2 were 1.5 μm and 1 μm, respectively. Moreover, the color of the photocatalyst layer of the comparative sheet 2 was light brown, which is slightly whiter than that of the comparative catalyst layer of the comparative sheet 1.

[Evaluation of colors at the time of completion of sample solutions A1 to A8, comparison solutions 1 and 2, sample sheets B1 to B8, and comparison sheets 1 and 2]
Table 1 of FIG. 1 shows the evaluation of the sample liquids A1 to A8, the comparative liquids 1 and 2, the sample sheets B1 to B8, and the comparative sheets 1 and 2. The comparative liquid 1 is the same as the photocatalyst coating liquid 1 to which VSA is not added.
In Table 1, only the item “photocatalyst layer”, which is the rightmost item, is an evaluation of the sample sheets B1 to B8 and the comparative sheets 1 and 2, and the other items are the sample solutions A1 to A8 and the comparative solution. It is evaluation about 1 and 2.
The amount of copper in each of the sample solutions A1 to A8 and the comparison solutions 1 and 2 is 3.0% by mass. Moreover, the addition amount of VSA in each liquid is gradually increased in the range of 0.0 to 25.3 mass% in the order of the comparative liquid 1, the comparative liquid 2, the sample liquid A1 to the sample liquid A7. However, in sample solution A8, the amount of VSA added is as small as 3.0.
And VSA / Cu which is the ratio in the case of the molar conversion of VSA to copper is also gradually in the range of 0.0 to 10.0 in the order of Comparative Solution 1, Comparative Solution 2, Sample Solution A1 to Sample Solution A7. Is getting bigger. VSA / Cu in sample liquid A8 is 1.2.
The colors of the comparison liquid 1, the comparison liquid 2, and the sample liquid A1 to the sample liquid A8 determined visually are the comparison liquid 1 and the comparison liquid 2 are light brown, and in the case of the sample liquid A1 to the sample liquid A8, they are white. .

  As is clear from the above results for the comparative liquid 1, the comparative liquid 2, and the sample liquid A1 to the sample liquid A8, the comparative liquid 1 in which the amount of VSA in terms of solid content in the liquid is smaller than 0.3% by mass, comparison In the case of the liquid 2, the color will be light brown. On the other hand, in the case of sample liquid A1 to sample liquid A8 in which the amount of VSA in terms of solid content in the liquid is larger than 1.3% by mass and smaller than 25.3%, the color is all white. In addition, according to this inventor, if the quantity of VSA of solid content conversion in a liquid is larger than 0.5 mass%, it has also been confirmed that the color of a sample liquid becomes white.

According to the applicant's consideration, the comparative liquid 1 and the comparative liquid 2 are light brown because of the black color of divalent copper oxide (CuO) contained therein.
Here, since CuO is a basic oxide, for example, when it reacts with 2 mol of hydrochloric acid (HCl), yellow cupric chloride (CuCl ₂ ) and water are generated according to the following chemical formula 1.
Chemical formula 1 CuO + 2HCl → CuCl ₂ + H ₂ O
Chemical formula 2 2CuO + HCl + H ₂ O → Cu ₂ (OH) ₃ Cl
Or → Cu (OH) Cl + Cu (OH) ₂
Since vinyl sulfonic acid is a strong acid, it reacts with cupric oxide in the same manner as in Chemical Formula 1 to produce a disubstituted product “Cu— (OSO ₂ —CH═CH ₂ ) ₂ ”, or reacts as in Chemical Formula 2. To produce the mono-substituted product “Cu— (OH) —OSO ₂ —CH═CH ₂ ”, whereby the black color of CuO disappears. By this mechanism, the inventors of the present application consider that the colors of the sample liquid A1 to the sample liquid A8 are white.
Table 1 shows VSA / Cu, which is a ratio in terms of mole of VSA with respect to copper. If the mole ratio is greater than 0.5 and up to 10, sample solution A1 to sample solution A8. As shown, the color of the liquid is white. More specifically, the liquid starts to be whitened at a molar ratio of 0.5 or more. However, when the molar ratio is 10, the value of YI of the photocatalytic layer starts to increase. Therefore, a sufficient effect can be exhibited when the molar ratio is 10 or less. If the molar ratio exceeds 10, side reactions are expected to occur, and the yellowing degree is expected to increase. Therefore, the molar ratio is preferably 10 or less.

In the item of “photocatalyst layer”, the color tone of the photocatalyst layers of the sample sheets B1 to B8 and the comparative sheets 1 and 2 at the time of completion was evaluated.
The color tone was evaluated by yellowness YI.
YI was determined by the following formula using an auxiliary illuminant C and an XYZ color system.
YI = 100 (1.2769 × X−1.0592 × Z) / Y
The color of the photocatalyst layer is the same as in Comparative liquid 1, Comparative liquid 2, Sample liquid A1 to Sample liquid A8, Comparative sheet 1 in which the amount of VSA in terms of solid content in the liquid is smaller than 0.3% by mass, In the case of the comparative sheet 2, the color becomes light brown. On the other hand, in the case of Sample Sheet B1 to Sample Sheet B8 in which the amount of VSA in terms of solid content in the liquid is larger than 1.3% by mass and smaller than 25.3%, the color is white. In addition, according to this inventor, if the quantity of VSA of solid content conversion in a liquid is larger than 0.5 mass%, it has also been confirmed that the color of a photocatalyst layer turns white.
As for the molar ratio (VSA / Cu), if the molar ratio is greater than 0.5 and up to 10, the color of the photocatalyst layer is white as in Sample Sheet B1 to Sample Sheet B8. Become. In particular, when the molar ratio is in the range of 1 to 10, the photocatalyst layer is completely white.

[Evaluation of fading of sample sheets B1 to B8 and comparative sheets 1 and 2]
The sample sheets B1 to B8 and the comparative sheets 1 and 2 were evaluated by performing the fading tests 1 to 4 under the following conditions 1 to 4, and the results are shown in Table 2 in FIG.
Condition 1 in the fading test 1 is a fading test under high humidity. At 30 ° C. in an atmosphere with a relative humidity of 90%, it was left for 4 weeks while irradiating 1000 lx light from a white fluorescent lamp, and then the change in the color of the surface of the photocatalyst layer was evaluated by visual observation and yellowness YI. .
Condition 2 in the fading test 2 is a fading test impregnated in water. The photocatalyst carrying sheet was immersed in a container filled with tap water at room temperature, and after maintaining for 1 week, water on the surface of the photocatalyst layer was gently wiped off and evaluated in the same manner as in Condition 1.
Condition 3 in the fading test 3 is a fading test in which oleic acid is impregnated. The photocatalyst carrying sheet was immersed in a container filled with oleic acid at room temperature, and after holding for 1 week, the oleic acid on the surface of the photocatalyst layer was gently wiped off and evaluated in the same manner as in Condition 1.
Condition 4 in the fading test 4 is a fading test in which a human hand is brought into contact. A palm or a finger was pressed against the surface of the photocatalyst layer and allowed to stand at room temperature for 1 week, and then the surface of the photocatalyst layer was evaluated in the same manner as in Condition 1.

As shown in Table 2, the sample sheets B1 to B8 were evaluated with no change in all of the fading tests 1 to 4. However, in the sample sheet B2, the color of the photocatalyst layer approaches white in the fading test 2 and the fading test 3. However, the change does not correspond to a slight change in color tone of YI of 2 or 3, and from the viewpoint of design, no major problem that would cause a reduction in commercial value has occurred.
On the other hand, in comparison sheets 1 and 2, in all of fading test 1 to fading test 3, whitening due to fading occurs relatively larger than in the case of sample sheets B1 to B8. The color of the layer mottled. From a design standpoint, this can be said to be a change that causes a reduction in the commercial value, depending on the application.

[Evaluation of performance of sample sheets B1 to B4 and sample sheet B8]
There are three performance tests: an antibacterial test, an antiviral test, and a humidity resistance test.
The antibacterial test and the antiviral test were evaluated according to JIS R 1752 and JIS R 1756, respectively, with respect to Staphylococcus aureus, Escherichia coli and Qβ bacteriophage. A white fluorescent lamp was used as the light source, and visible light with λ ≧ 380 nm using a UV cut filter (N-169) was irradiated for 1 hour so that the illuminance on the surface of the photocatalyst layer of the sample sheet was 1000 lx.
On the other hand, in the humidity resistance test, a white fluorescent lamp (all light) is used in a constant temperature and humidity chamber at 30 ° C. and a humidity of 90 RH, and the illumination of the sample surface is set to 1000 lx and light irradiation is continued for 4 weeks. Samples were later taken out and evaluated for antibacterial and antiviral properties.
The above evaluation results are shown in Table 3 in FIG.
The antibacterial and antiviral properties of each photocatalyst-supported sheet are very high when completed, and no deterioration in antibacterial and antiviral properties is observed even after 4 weeks in a harsh environment in a humidity resistance test. It was.
According to the results shown in Tables 1 to 3, the sample sheets B1 to B4 and the sample sheet B8 are white when applied to the sheets, regardless of how VSA is added, and various fadings are observed. In the test, there was almost no change in the color, and the extremely high antibacterial and antiviral properties did not change even in harsh environments, and the above results did not change even under high humidity. It was.

<Generation of sample solutions A9 to A11>
Sample liquids A9, A10, and A11 are manufactured by using methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) that is one of the sulfonic acids represented by the above formula (1) instead of adding VSA to the photocatalyst coating liquid 1 described above. The sample was prepared in the same manner as in the case of the sample solution A1, except that a reagent, hereinafter sometimes referred to as “MSA”) was added.
Specifically, in the production of the sample liquids A9, A10, and A11, MSA was added to the photocatalyst coating liquid 1 and stirred at room temperature to be uniformly dissolved. The amount of MSA added to 100 g of photocatalyst coating liquid 1 is 0.060 g (0.60% by mass with respect to the solid content of photocatalyst coating liquid 1) in the case of sample liquid A9, and in the case of sample liquid A10. Is 0.100 g (1.00 mass% with respect to the solid content of the photocatalyst coating liquid 1), and 0.200 g (2.00 mass% with respect to the solid content of the photocatalyst coating liquid 1) in the case of the sample liquid A11 did.

<Creation of sample sheets B9 to B11>
Next, the sample liquid A9, the sample liquid A10, or the sample liquid A11 was applied to one side of the sheet and dried to fix mainly the solid content of each sample liquid to the surface of the sheet to form a photocatalyst layer. . The method is the same as in the case of <preparation of sample sheets B1 to B8> regardless of the difference in the sample solution.
The sheet used here is the same as that in <Preparation of Sample Sheets B1 to B8>. An adhesive layer was formed on the surface of this sheet by the same method as described in <Preparation of Sample Sheets B1 to B8>.
Next, the sample liquids A9 to A11 were applied on the respective adhesive layers of the sheet provided with the adhesive layer prepared as described above, and dried. Application | coating of sample liquid A9-A11 was performed using the common bar coater. Then, it dries for 15 minutes at 100 degreeC, sample sheet B9-B11 which is a sheet | seat which has a photocatalyst layer is obtained by forming the photocatalyst layer derived from either of sample liquid A9-A11 on an adhesion layer. It was.
The colors of the photocatalyst layers of the sample sheets B9 to B11 were all white.

<Generation of sample liquids A12 and A13 and sample sheets B12 and B13>
The method for obtaining the sample liquids A12 and A13 is basically the same as the method for obtaining the sample liquid A1, and only the amount of VSA added to the photocatalyst coating liquid 1 during production is different. The amount of vinyl sulfonic acid added to 100 g of the photocatalyst coating liquid 1 is 0.060 g (0.60% by mass with respect to the solid content of the photocatalyst coating liquid 1) in the case of the sample liquid A12, and in the case of the sample liquid A13. Was 0.100 g (1.00 mass% with respect to the solid content of the photocatalyst coating liquid 1).
Using the sample liquids A12 and A13 instead of the sample liquid A1, sample sheets B12 and B13 were obtained in the same manner as described in <Preparation of Sample Sheets B1 to B8>.
The color of the photocatalyst layer of sample sheets B12 and B13 was white.

<Generation of Comparative Solution 3 and Comparative Sheet 3>
The method for obtaining the comparison liquid 3 is basically the same as the method for obtaining the sample liquids A9 to A11. When the comparison liquid 3 is produced, the amount of MSA added to 100 g of the photocatalyst coating liquid 1 is determined. , 0.010 g (0.10% by mass with respect to the solid content of the photocatalyst coating solution 1).
The comparative liquid 3 was used in place of the sample liquids A9 to A11, and the comparative sheet 3 was obtained by the same method as described in <Preparation of the sample sheets B9 to B11>.
The color of the photocatalyst layer of the comparative sheet 3 was light brown.

<Preparation of sample sheets B14 and B15>
In the preparation of the sample sheets B14 and B15, a polyethylene terephthalate resin (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 # 188, thickness 188 μm) was used as a base material. Except for the difference in the base material, an adhesive layer was formed on one side thereof by the same method as described in <Creation of Sample Sheets B9 to B11>.
Next, the sample liquid A10 and the sample liquid A13 are respectively applied to the above-described adhesive layers of the sheet including the adhesive layer prepared as described above in the same manner as described in <Creation of Sample Sheets B9 to B11>. It was applied and then dried by the same method as described in <Creation of Sample Sheets B9 to B11> to obtain Sample Sheet B14 and Sample Sheet B15, which are sheets having a photocatalyst layer.
The color of the photocatalyst layer of sample sheet B14 and sample sheet B15 was white.

[Evaluation of Color at Completion of Sample Liquids A9 to A11, Comparative Liquids 1 and 3, Sample Sheets B9 to B11, and Comparative Sheets 1 and 3]
Table 4 in FIG. 4 shows the evaluation of the sample solutions A9 to A11, the comparison solutions 1 and 3, the sample sheets B9 to B11, and the comparison sheets 1 and 3, that is, the comparison of colors according to the amount of MSA added.
In Table 4, only the item “photocatalyst layer”, which is the rightmost item, is an evaluation of the sample sheets B9 to B11 and the comparison sheets 1 and 3, and the other items are the sample solutions A9 to A11 and the comparison solution. 1 and 3 are evaluations. The amount of MSA added to each sample solution increases in the range of 0.0 to 2.00% by mass in the order of Comparative Solution 1, Comparative Solution 3, Sample Solution A9 to Sample Solution A11.
The colors of the liquids visually determined were that the comparative liquid 1 was light brown and the comparative liquid 3 was light gray, but the sample liquids A9 to A11 were white. Moreover, as for the color of the photocatalyst layer at the time of application | coating with respect to each sheet | seat, although the comparison liquid 1 and the comparison liquid 3 were light brown, the sample liquid A9-sample liquid A11 was white.
That is, even when MSA of 0.5% by mass or more based on the solid content was used by mixing at room temperature, the sample solution and the photocatalyst layer at the time of application became white as in the case of using the same amount of VSA. .

[Evaluation of UV Light Discoloration of Sample Sheets B10, B11, B13 and Comparative Sheets 1 and 3]
Comparison between sample sheets B10, B11, and B13 and comparative sheets 1 and 3 under UV light irradiation with MSA addition amount and VSA (1.00 mass% in solid content) under the following condition 5 A certain discoloration test 5-1 was performed, and the results are shown in Tables 5 to 6 in FIGS.
Condition 5 is to evaluate the color after UV light irradiation for a certain time. Each sheet is irradiated with 1.0 mW / cm ² UV light from a black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) at room temperature. Each time shown in Table 5 and Table 6 from the start of irradiation. L * measured by using a color difference meter (0 to black) Numerical value: 0 (black) Numerical value: 100 (white) How the color change of the surface of the photocatalytic layer occurs after (0 to 28 hours) ) And YI (yellowing index, the larger the value, the darker the yellow). The test results are shown separately in Table 5 and Graph 5 (L *), and in Table 6 and Graph 6 (YI).

  According to the results shown in Tables 5 and 5 and Tables 6 and 6, in the sheet which is the photocatalyst structure of the present invention, VSA or MSA of 0.5% by mass or more based on the solid content by mixing at room temperature. The sample sheets B10, B11, and B13 that use the sample are almost the same in color in the discoloration test for UV light irradiation as compared with the comparative sheets 1 and 3 in which MSA and VSA with respect to the solid content are less than 0.5% by mass. There was no change, and in particular, the darkening prevention effect evaluated by L * was remarkable. Further, in the sample sheets B10, B11, and B13 using VSA or MSA of 0.5% by mass or more based on the solid content, the LSA is not limited regardless of the difference between the VSA and the MSA and the amount of MSA used. There was almost no difference in the effect of preventing darkening evaluated by *.

[Evaluation of UV light discoloration of sample sheets B12 and B13 and comparative sheets 1 and 2]
The sample sheets B12 and B13 and the comparative sheets 1 and 2 were subjected to a discoloration test 5-2, which is a comparison under UV light irradiation according to the amount of VSA added, and the results are shown in Tables 7 to 8 in FIGS. The data of each table are shown in graphs 7 to 8 which are graphed. The conditions were the same as those described above, except that UV irradiation was performed for a longer time (0 to 188 hours) than the discoloration test 5-1. The test results are shown separately in Table 7 and Graph 7 (L *), and Table 8 and Graph 8 (YI).

  According to the results shown in Table 7 and Graph 7, and Table 8 and Graph 8, in the sheet which is the photocatalyst structure of the present invention, VSA of 0.5% by mass or more based on solid content is used by mixing at room temperature. Both the sample sheets B12 and B13 were evaluated by L * and YI in the discoloration test for UV light irradiation as compared with the comparative sheets 1 and 2 having a VSA of less than 0.5% by mass relative to the solid content. Was also excellent.

[Evaluation of Fading of Sample Sheets B10, B11, B13 and Comparative Sheets 1 and 3]
The sample sheet B10, B11, B13 and the comparison sheets 1 and 3 were evaluated by performing a fading test 6 under the following conditions 6, and the results were graphed in Table 9 and its data in FIG. This is shown in graph 9.
Condition 6 in the fading test 6 evaluates fading under water immersion. Each sheet is immersed in ion-exchanged water at room temperature, then irradiated with light at 300 lx with a white fluorescent lamp for 12 hours, and not irradiated with light for 12 hours (that is, illumination with a fluorescent lamp is performed in the daytime). Yes, there was no lighting at night, and the sheet was immersed in ion-exchanged water in a normal room for 7 days. After holding in that state for 1 week, the water on the surface of the photocatalyst layer was gently wiped, and the change in the color of the surface of the photocatalyst layer was evaluated by the color difference L * measured using a color difference meter and visually. For comparison, L * of a sheet not subjected to the above-described treatment immediately after film formation was measured in the same manner and indicated as evaluation time 0.

  According to the results shown in Table 9 and Graph 9, all of the sample sheets B10, B11, and B13 using MSA or VSA of 0.5% by mass or more have MSA and VSA of 0.5% by mass with respect to the solid content. Compared to the case of less than 1% of the comparative sheets 1 and 3, the initial coating color can be whitened, so that discoloration before and after water immersion can be suppressed. In addition, in sample sheets B10, B11 and B13 using VSA or MSA of 0.5% by mass or more based on the solid content, blackening prevention is possible regardless of the difference between VSA and MSA and the amount of MSA used. There was almost no difference in effect.

[Antiviral evaluation of sample sheets B14 and B15]
As a performance test, an antiviral test was performed. The test method is the same as the antiviral test method described in [Evaluation of performance of sample sheets B1 to B4 and sample sheet B8], except that the evaluation time is 1 hour and 2 hours. In this test, MSA and VSA are compared at the same addition amount (1.00% by mass in the solid content).
The evaluation results are shown in Table 10 in FIG.

  According to the results shown in Table 10, the antiviral effect was almost the same when compared between the sample sheet B14 and the sample sheet B15 using VSA and MSA, respectively.

[Evaluation of antibacterial properties of sample sheets B14 and B15]
An antibacterial test was conducted as a performance test. The test method is the same as the method of the antibacterial test described in [Evaluation of performance of sample sheets B1 to B4 and sample sheet B8], except that the evaluation time is 1 hour and 2 hours using only Escherichia coli. Different. In this test, MSA and VSA are compared at the same addition amount (1.00% by mass in the solid content).
The evaluation results are shown in Table 11 in FIG.

  According to the results shown in Table 11, the antibacterial effect was almost equivalent when compared with the sample sheet B14 and the sample sheet B15 using VSA and MSA, respectively. Antibacterial properties were slightly better than MSA.

Claims (28)

As a solid content, a titanium oxide-containing composition containing a titanium oxide compound, divalent copper oxide, and a binder and a solvent for suspending them,
Formula (1) in an amount corresponding to 0.5 to 25% by mass with respect to the solid content.
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, a C3-10 cycloalkyl group which may have a substituent, C3-10 cycloalkenyl group which may have a substituent, or C6-10 aryl group which may have a substituent.
Comprising a sulfonic acid represented by
Titanium oxide-containing composition. The titanium oxide compound has a molar ratio of rutile titanium oxide in titanium oxide of 50% or more.
The titanium oxide-containing composition according to claim 1. At least a part of the copper oxide is a reaction product with the sulfonic acid represented by the formula (1).
The titanium oxide containing composition of Claim 1 or 2. The binder is an oxide gel or hydroxide gel of a metal such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin,
The titanium oxide containing composition in any one of Claims 1-3. The binder is an oxide gel or hydroxide gel of a metal such as silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, tin, and the formula (2)
R ₂ —SO ₂ OH (2)
Wherein R ₂ represents a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkenyl group which may have a substituent. including,
The titanium oxide containing composition in any one of Claims 1-3. The solvent is one of water, alcohols, ketones or a mixture of two or more thereof.
The titanium oxide containing composition in any one of Claims 1-5. The sulfonic acid represented by the formula (1) is vinyl sulfonic acid or methane sulfonic acid,
The titanium oxide containing composition in any one of Claims 1-4. The sulfonic acid represented by the formula (2) is vinyl sulfonic acid,
The titanium oxide-containing composition according to claim 5. It is a titanium oxide containing composition in any one of Claims 1-8,
Its use is a photocatalyst,
Titanium oxide-containing composition. It is a titanium oxide containing composition in any one of Claims 1-8,
Its use is antibacterial or antiviral agent,
Titanium oxide-containing composition. As a solid content, a titanium oxide compound, a divalent copper oxide, and a binder and a solvent for suspending them, and an amount corresponding to 0.5 to 25% by mass with respect to the solid content (1)
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, a C3-10 cycloalkyl group which may have a substituent, C3-10 cycloalkenyl group which may have a substituent, or C6-10 aryl group which may have a substituent.
A suspension comprising a sulfonic acid represented by
A titanium oxide-containing composition is obtained by stirring and mixing.
A method for producing a titanium oxide-containing composition. The stirring and mixing is performed at room temperature.
The manufacturing method of the titanium oxide containing composition of Claim 11. A titanium oxide-containing composition is obtained by performing the stirring and mixing at a temperature of 50 ° C. or higher and 200 ° C. or lower.
The manufacturing method of the titanium oxide containing composition of Claim 11. A titanium oxide-containing composition is obtained by performing the stirring and mixing at a temperature of 50 ° C. or more and 150 ° C. or less under irradiation of ultraviolet rays having a wavelength of 280 to 400 nm and an intensity of 0.5 to 5 mw / cm ² .
The manufacturing method of the titanium oxide containing composition of Claim 11. Formula (2) in the binder
R ₂ —SO ₂ OH (2)
(In the formula, R ₂ represents a C2-10 alkenyl group which may have a substituent, or a C3-10 cycloalkenyl group which may have a substituent.)
The reaction product obtained by adding and reacting the sulfonic acid represented by is added to a suspension containing a titanium oxide compound and divalent copper oxide and a solvent for suspending them,
By stirring and mixing the suspension to which the reactant is added, an amount corresponding to 0.5 to 25% by mass with respect to the titanium oxide compound as a solid content, divalent copper oxide, and a binder. A titanium oxide-containing composition comprising a sulfonic acid represented by formula (1) is obtained.
A method for producing a titanium oxide-containing composition. In order to obtain the reaction product, the sulfonic acid represented by the formula (2) is added to the binder and reacted at a temperature of 50 ° C. or more and 200 ° C. or less.
The manufacturing method of the titanium oxide containing composition of Claim 15. In order to obtain the reaction product, the sulfonic acid represented by the formula (2) is added to the binder, and the irradiation with ultraviolet rays having an intensity of 1 to 10 mw / cm ² at a wavelength of 280 to 400 nm is performed at 50 ° C. or higher and 200 ° C. React at a temperature below ℃,
The manufacturing method of the titanium oxide containing composition of Claim 15. The suspension to which the reactant is added is heated at a temperature of 50 ° C. or higher and 200 ° C. or lower.
The manufacturing method of the titanium oxide containing composition in any one of Claims 15-17. The sulfonic acid represented by the formula (1) is vinyl sulfonic acid or methane sulfonic acid,
The manufacturing method of the titanium oxide containing composition in any one of Claims 11-14. The sulfonic acid represented by the formula (2) is vinyl sulfonic acid,
The manufacturing method of the titanium oxide containing composition in any one of Claims 15-18. A base material, a titanium oxide compound, a divalent copper oxide, a binder, and a formula (1) provided on the surface of the base material
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, a C3-10 cycloalkyl group which may have a substituent, C3-10 cycloalkenyl group which may have a substituent, or C6-10 aryl group which may have a substituent.
And a photocatalyst layer containing a sulfonic acid represented by
The amount of the sulfonic acid represented by the formula (1) corresponds to 0.5 to 25% by mass with respect to the total mass of the titanium oxide compound, the divalent copper oxide, and the binder. Has become,
Photocatalyst structure. The sulfonic acid represented by the formula (1) is vinyl sulfonic acid or methane sulfonic acid,
The photocatalyst structure according to claim 21. On the substrate,
A titanium oxide-containing composition containing a titanium oxide compound, divalent copper oxide, and a binder as a solid content, and a solvent for suspending the titanium oxide compound, 0.5 to 25 mass based on the solid content Of the amount corresponding to% (1)
R ₁ —SO ₂ OH (1)
Wherein R ₁ is a C1-10 alkyl group which may have a substituent, a C2-10 alkenyl group which may have a substituent, a C3-10 cycloalkyl group which may have a substituent, C3-10 cycloalkenyl group which may have a substituent, or C6-10 aryl group which may have a substituent.
A titanium oxide-containing composition comprising a sulfonic acid represented by:
Apply
By drying and evaporating the solvent,
Producing a photocatalyst structure having a photocatalyst layer that is obtained by fixing the solid content in the titanium oxide-containing composition on the surface of the substrate;
A method for producing a photocatalyst structure. The applied titanium oxide-containing composition is dried at a temperature of 150 ° C. or lower.
The manufacturing method of the photocatalyst structure of Claim 23. The applied titanium oxide-containing composition is dried at a temperature of 150 ° C. or lower and under ultraviolet irradiation.
The manufacturing method of the photocatalyst structure of Claim 23. The sulfonic acid represented by the formula (1) is vinyl sulfonic acid or methane sulfonic acid,
The manufacturing method of the photocatalyst structure in any one of Claims 23-25. The substrate is a sheet;
The photocatalyst structure according to claim 21 or 22. The sheet is a sheet formed by coating a polymer resin with a polymer resin molding, a fabric made of fibers, and a fiber fabric as a core material.
The photocatalyst structure according to claim 27.