JP2022085649A - Antibacterial/antiviral coating composition - Google Patents

Abstract

To provide an antibacterial/antiviral coating composition with which it is possible to form an antibacterial/antiviral coating layer having water rubbing resistance, and which has good storage stability and workability during coating.SOLUTION: The present disclosure relates to an antibacterial/antiviral coating composition including an inorganic binder (A), photocatalytic titanium oxide (B), and alcohol (C), wherein: the inorganic binder (A) is of an acidic type; and the mass ratio [(B)/(A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) is in the range of 0.5 to 5.0.SELECTED DRAWING: None

Description

The present invention relates to an antibacterial / antiviral coating composition.

In recent years, infectious diseases caused by viruses such as new influenza and bacteria such as O157 have become a life-threatening situation, and there is an increasing need for products having antiviral and / or antibacterial functions.

For example, Patent Document 1 is characterized in that antibacterial inorganic fine particles containing silver, copper, zinc or a complex thereof are attached to the surface of powder coating material particles containing at least a resin and a curing agent. It describes the antibacterial powder coating material. Further, Patent Document 2 describes an antibacterial powder coating material in which an antibacterial agent containing an antibacterial metal component and a metal oxide other than the antibacterial metal component is adhered to the surface of the powder coating particles. Further, Patent Document 3 describes an antibacterial agent composed of an antibacterial inorganic oxide colloidal solution in which an antibacterial metal component is attached to negatively charged inorganic oxide colloidal particles. Further, Patent Document 4 describes that a composition containing an amine compound having a predetermined structure has excellent antiviral activity. Further, Patent Document 5 describes a titanium oxide solution obtained by heat-treating a solution containing titanium hydroxide obtained by a reaction between a titanium compound and an aqueous ammonia solution on the surface of a material to be coated at a temperature equal to or lower than the boiling point of the solution. The photocatalyst coating material used is described, and it is described that the photocatalyst coating obtained by applying and drying the photocatalyst coating material has antibacterial properties.

Attempts have also been made to combat viruses and microorganisms by using chemicals such as hypochlorous acid and hydrogen peroxide.

Japanese Unexamined Patent Publication No. 09-263715 Japanese Unexamined Patent Publication No. 10-168346 Japanese Unexamined Patent Publication No. 6-80527 Japanese Unexamined Patent Publication No. 2020-12259 Japanese Unexamined Patent Publication No. 2005-219967

However, it was found that all of the compositions described in Patent Documents 1 to 4 have a problem in the persistence of antibacterial or antiviral properties. Further, it was found that the composition described in Patent Document 5 is inferior in durability (water rubbing resistance) because it does not sufficiently adhere to the object to be coated, although the antibacterial property is maintained.

On the other hand, chemicals such as hypochlorous acid and hydrogen peroxide solution have a large effect on the human body or the environment, and have a problem in sustainability of antibacterial or antiviral properties.

The present invention focuses on the above-mentioned problems, is an antibacterial / antiviral coating composition capable of forming an antibacterial / antiviral coating layer having water rubbing resistance, and further provides storage stability and work during coating. It is an object of the present invention to provide an antibacterial / antiviral coating composition having good properties.

The present disclosure provides the following [1] to [16].
[1]
It contains an inorganic binder (A), a photocatalytic titanium oxide (B) and an alcohol (C).
The inorganic binder (A) is an acidic type and is of an acidic type.
The mass ratio [(B) / (A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) is in the range of 0.5 to 5.0.
Antibacterial / antiviral coating composition.
[2]
The antibacterial / antiviral coating composition according to [1], wherein the inorganic binder (A) contains a silicon compound-based binder.
[3]
The antibacterial / antiviral coating composition according to [1] or [2], wherein the inorganic binder (A) contains at least one selected from the group consisting of colloidal silica and alkyl silicates.
[4]
The antibacterial / antiviral coating composition according to any one of [1] to [3], wherein the photocatalytic titanium oxide (B) contains silver and copper and tetraammonium hydroxide.
[5]
The antibacterial / antiviral coating composition according to any one of [1] to [4], wherein the alcohol (C) contains an alcohol having 1 to 7 carbon atoms.
[6]
The antibacterial / antiviral coating composition according to any one of [1] to [5], wherein the alcohol (C) is at least one selected from the group consisting of ethanol, isopropanol, normal propanol and propylene glycol. ..
[7]
The antibacterial / antiviral coating composition according to any one of [1] to [6], further comprising water.
[8]
The antibacterial / antiviral coating composition according to any one of [1] to [7], further comprising a surfactant.
[9]
The antibacterial / antiviral coating composition according to [8], wherein the surfactant is a nonionic surfactant.
[10]
The antibacterial / antiviral coating composition according to any one of [1] to [9], further comprising a decolorizing dye.
[11]
An antibacterial / antiviral coating layer formed by the antibacterial / antiviral coating composition according to any one of [1] to [10].
[12]
An article comprising a base material and the antibacterial / antiviral coating layer according to [11] on the surface of the base material.
[13]
The antibacterial / antiviral coating composition according to any one of [1] to [10] is applied to the object to be coated, and the weight of the antibacterial / antiviral coating composition after drying is 0.02 to 0.20 g. A method for forming an antibacterial / antiviral coating layer, which comprises a step of forming an antibacterial / antiviral coating layer by painting at / m ² .
[14]
To form the antibacterial / antiviral coating layer, the antibacterial / antiviral coating composition is subjected to dip coating, brush coating, cloth coating, roller coating, roll coater coating, spray coating, curtain flow coater coating, roller coating. The method for forming an antibacterial / anti-virus coating layer according to [13], which is performed by coating by at least one method selected from the group consisting of curtain coater coating and die coating.
[15]
The method for forming an antibacterial / antiviral coating layer according to [14], wherein the spray coating is an aerosol spray coating or a non-aerosol spray coating.
[16]
The method for forming an antibacterial / antiviral coating layer according to [14], wherein the coating using the cloth is performed by impregnating the cloth with the antibacterial / antiviral coating composition and wiping the surface of the object to be coated. ..

According to the present invention, it is an antibacterial / antiviral coating composition capable of forming an antibacterial / antiviral coating layer having water rubbing resistance, and further, storage stability and workability at the time of coating, particularly wettability to an object to be coated. Can provide a good antibacterial / antiviral coating composition.

[Antibacterial / antiviral coating composition]
The antibacterial / antiviral coating composition of the present invention (hereinafter, also referred to as “coating composition”) contains an inorganic binder (A), a photocatalytic titanium oxide (B) and an alcohol (C).
The inorganic binder (A) is an acidic type and is of an acidic type.
The mass ratio [(B) / (A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) is in the range of 0.5 to 5.0.

In the present disclosure, the antibacterial property refers to the property of inactivating bacteria, and can be evaluated by, for example, the antibacterial activity value of JISR 1752 (2020). The antiviral property refers to the property of inactivating the virus, and can be evaluated by, for example, the antiviral activity value of JIS R 1756 (2020).

<Inorganic binder (A)>
Since the coating composition of the present invention contains the inorganic binder (A), the antibacterial / antiviral coating layer (hereinafter, also referred to as “coating layer”) formed from the composition has good durability. Specifically, it has water rubbing durability and can maintain good antibacterial and antiviral properties. For example, the coating layer also improves durability against routine wiping. Further, the inorganic binder (A) is less likely to be decomposed even when used with the photocatalytic titanium oxide (B). Therefore, when the inorganic binder (A) is used, deterioration of the coating composition is unlikely to occur even in long-term use.
In the present disclosure, water rubbing resistance means that the photocatalyst is retained in the coating layer when the surface of the coating layer is wiped with a cloth soaked in water for daily care, in other words. , It means that antibacterial and antiviral properties can be maintained. For example, the coating layer formed from the antiviral coating composition of the present invention is less likely to come off when the surface of the coating layer is wiped with a cloth soaked in water.

As the inorganic binder (A), an acidic type binder is used. By using an acidic type, the coating composition can be stably present. Here, the term "stable" means that, for example, when the coating composition is allowed to stand, the inorganic binder (A), the photocatalytic titanium oxide (B), and the like are less likely to settle. In other words, the storage stability of the coating composition is good.
The acidic type refers to a binder (A) that can stably exist when it is in the acidic region. For example, in the case of a suspension of silica fine particles described later, the acidic type means that gelation is difficult in an acidic region (for example, pH 2.0 to 5.0).

The content of the inorganic binder (A) is preferably, for example, 0.05 to 5.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass with respect to the coating composition. If the content of the inorganic binder (A) is less than 0.05 parts by mass, the formed coating layer may not have sufficient rubbing durability, and if it exceeds 5.0 parts by mass, the coating is applied. There is a risk that the appearance of the layer will deteriorate, for example, the degree of hue change (for example, whitening due to thickening) will increase. Further, by being in the above range, the coating composition can be stably present. In the present disclosure, the content of the inorganic binder (A) means the solid content mass or the active ingredient mass of the inorganic binder (A) with respect to the total mass of the coating composition, and specifically, the inorganic binder. When (A) is a silicon compound, it means the mass of the active ingredient, and in other cases, it means the mass of the solid content. Here, the active ingredient of the inorganic mechanical binder means the residue after hydrolysis with dilute ammonia water, evaporating the water content, and further firing at 900 ° C., and the solid content is 1 at 100 ° C. It means the residual heating after time drying.

Examples of the inorganic binder (A) include a binder containing a zirconium compound, a silicon compound, an aluminum compound and the like. In one embodiment, the inorganic binder (A) is at least one selected from the group consisting of a zirconium compound, a silicon compound and an aluminum compound.

Specifically, the zirconium compound includes zirconium salts such as zirconium tetrachloride, zirconium oxychloride, zirconium nitrate, zirconium sulfate, zirconium acetate, and zirconium carbonate; tetraethoxyzirconium, tetra-i-propoxyzirconium, and tetra-n-butoxy. Examples thereof include zirconium, zirconium alkoxides such as tetra-t-butoxyzirconium, and the like.
Examples of the silicon compound include alkaline silicates such as sodium silicate, potassium silicate, lithium silicate, cesium silicate and rubidium silicate; alkyl silicates such as tetramethoxysilane and tetraethoxysilane, and hydrolysis products of alkyl silicates; methyltrimethoxysilane, Methyltriethoxysilane, Methyltricrolsilane, Methyltribromsilane, Methyltriisopropoxysilane, Methyltrit-butoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Ethyltricrolsilane, Ethyltribromsilane, Ethyltriisopropoxysilane Examples thereof include alkoxysilanes such as, silanol, which is a hydrolysis product of alkoxysilanes, and the like.
Examples of the aluminum compound include aluminum salts such as aluminum lactate, aluminum phosphate, and aluminum chloride; aluminum alkoxides such as triethoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, and trit-butoxyaluminum aluminum alkoxide. And so on.

The inorganic binder (A) preferably contains a silicon compound-based binder from the viewpoint of water rubbing resistance, antibacterial property and antiviral property. By including the silicon compound-based binder in the coating composition, the fixability to the object to be coated can be particularly good. Examples of the silicon compound-based binder include a particle type such as silica and a dissolved molecule type such as a silanol oligomer.

The silicon compound-based binder is more preferably a silicon compound. Examples of the silicon compound include alkali-based acid salts, specifically, silica fine particles, alkyl silicates, and the like. It is considered that such compounds are more likely to exhibit antibacterial and antiviral properties because they attract water to the coating layer due to their own hydrophilicity and efficiently generate hydroxyl radicals by a photocatalyst.

The shape of the silicon compound is not particularly limited, and examples thereof include a spherical shape and a chain shape.

(Silica fine particles)
The average primary particle size of the silica fine particles is, for example, 3 to 50 nm, preferably 10 to 25 nm, and more preferably 10 to 15 nm. When the average primary particle size is in the above range, the coating composition can be stably present and can be stably present. In addition, the coating composition can contribute to the formation of a coating layer having a good appearance.
The average primary particle size of the silica fine particles can be measured by a known measuring method such as electron microscope observation and BET method (specific surface area method). In one embodiment, the average primary particle size of the silica fine particles is a value obtained by converting from the specific surface area by the BET method.

The silica fine particles can be used as a suspension containing the silica fine particles (that is, colloidal silica).
Examples of the dispersion medium of the suspension include water; an organic solvent such as methanol, ethanol, isobutanol, and propylene glycol monomethyl ether.
As the suspension, those containing silica fine particles in an amount of, for example, 5 to 50% by mass with respect to the suspension can be used.

As the suspension containing silica fine particles, for example, a suspension containing silica fine particles from which an electrolyte such as sodium generally contained is removed, or an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid is used for stabilization. However, it is preferable to use the one from which the electrolyte has been removed. Only one of these components or a combination of two or more can be used.

The pH of the suspension of the silica fine particles is preferably 2.0 to 5.0, more preferably 2.5 to 4.5. When the pH is within this range, it can stably exist in the suspension of silica fine particles without gelation or precipitation of solid content. Further, even when added to the coating composition, the coating composition is less likely to cause gelation or sedimentation of solid content, and can exist stably.

Commercially available products may be used as such silica fine particles (including those in the form of a suspension of silica fine particles).
Examples of commercially available products include Snowtex (registered trademark) O, O-40, OL, OXS, OS, OUP, PS-SO, PS-MO (manufactured by Nissan Chemical Industries, Ltd.) and the like. These may be used alone or in combination of two or more.

(Alkyl silicate)
Alkyl silicate means an alkyl silicate compound and / or a partially hydrolyzed condensate thereof. The alkyl silicate compound is a compound having silicon to which a hydrolyzable group is bonded, and is represented by, for example, the following general formula (1).
Si (OR) ₄ ... (1)
In the above formula (1), R represents an alkyl group having 1 to 4 carbon atoms, and may be the same or different.

Examples of the alkyl silicate compound represented by the above formula (1) include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate and tetra. -T-Butyl silicate, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like can be mentioned. These may be used alone or in combination of two or more.

Examples of the partially hydrolyzed condensate of the alkyl silicate compound include those obtained by partially hydrolyzing and condensing the above alkyl silicate compound. The degree of condensation is preferably 1 to 20, more preferably 3 to 15.

The alkyl silicate can be used, for example, in a state of being dissolved in water. At this time, the pH of the aqueous solution is, for example, 2 to 3.

As the alkyl silicate, a commercially available product can be used.
Examples of commercially available products include ethyl silicate 48 (tetraethoxysilane partial hydrolysis condensate, manufactured by Corcote), MKC silicate MS51 (tetramethoxysilane partial hydrolysis condensate, manufactured by Mitsubishi Chemical Corporation), and EMS485 (ethyl methyl silicate moiety). Hydrolyzed condensate, manufactured by Corcote Co., Ltd.) and the like.

<Photocatalytic titanium oxide (B)>
By including the photocatalytic titanium oxide (B) in the coating composition, antibacterial and antiviral properties can be imparted to the coating layer. The photocatalytic type titanium oxide (B) exhibits a photocatalytic effect by being applied with light energy. Light energy is imparted by, for example, ultraviolet light or visible light.

The photocatalytic titanium oxide (B) is not particularly limited in its use as long as it exhibits photocatalytic properties, but it can be used in the form of powder, sol, solution or the like. From the viewpoint that it can be stably present in the coating composition, the photocatalytic titanium oxide (B) is preferably used as a titanium oxide sol in which titanium oxide is present as fine particles.

The photocatalytic titanium oxide (B) consists of anatase-type or rutile-type crystals having a photocatalytic effect and a mixture thereof. It means that the result of powder X-ray diffraction of the powder obtained by at least drying is clearly identified as anatase type or rutile type. Titanium oxide showing anatase type or rutile type shows high photocatalytic performance.
The photocatalytic titanium oxide (B) is preferably anatase type. This is because sufficient light energy can be obtained even with weak light energy indoors.

The average particle size of the photocatalytic titanium oxide (B) is preferably more than 5 nm and 20 nm or less, and more preferably 10 nm or more and 20 nm or less. In the present disclosure, the average particle size of the photocatalytic titanium oxide means a value calculated as a number average value obtained by measuring the length of any 100 particles in the field of view 200,000 times by scanning electron microscope observation. .. As the shape of the particles, a true sphere is the best, but a substantially circular shape or an elliptical shape may be used, and the particle diameter in that case is approximately calculated as ((major diameter + minor diameter) / 2).

When the photocatalytic titanium oxide (B) exists as a photocatalytic titanium oxide sol, the concentration of titanium oxide (TiO ₂ ) contained in the photocatalytic titanium oxide sol can be adjusted by an operation such as ordinary concentration. For example, it is preferable that the amount of TiO ₂ is in the range of 3 to 15% by mass with respect to the photocatalytic titanium oxide sol. Within the above range, the titanium oxide sol does not settle, thicken, etc., has an advantage that storage stability can be improved, and the productivity of the coating liquid is also improved.

The photocatalytic titanium oxide (B) contains silver and copper and tetraammonium hydroxide, as well as titanium oxide (TiO ₂ ).

The silver is preferably contained in the photocatalytic titanium oxide (B) in a non-ionized form such as an oxide or a hydroxide. _The silver content is preferably in the range of _0.1 to 5.0% by mass, _more preferably ₀ . It is in the range of 8 to 3.0% by mass. When the silver content is within the above range, there is an advantage that titanium oxide can be well dispersed in the sol and the antibacterial and antiviral effects are sufficiently exhibited.

The tetraammonium hydroxide is added to stabilize the photocatalytic titanium oxide (B) as a photocatalytic titanium oxide sol.
Since tetraammonium hydroxide hardly dissolves the antibacterial metal, discoloration of the antibacterial metal can be suppressed while stabilizing the titanium oxide sol.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. From the viewpoint of availability, tetraethylammonium hydroxide is preferable.

The tetraammonium hydroxide is preferably contained in the range of 0.01 to 0.1 mol with respect to ₂₁ mol of TiO. By being in the above range, the titanium oxide sol may exist more stably.

When added together with tetraammonium hydroxide, the copper can contribute to the suppression of silver discoloration in the photocatalytic titanium oxide sol. Copper is preferably added as an oxide, a hydroxide, or the like from the viewpoint of not containing nitrate ions or chlorine ions that destabilize the sol.
The copper content is preferably in the range of 1 to 30, more preferably in the range of 1 to 10, when converted as the ratio of copper oxide to silver oxide, in other words, CuO / Ag _2O (mass ratio).

As described above, when the photocatalytic titanium oxide (B) is a titanium oxide sol containing silver, copper and tetraammonium hydroxide, discoloration of silver can be significantly suppressed. For example, when the color quality index ΔL value of the photocatalytic titanium oxide (B) is measured, the ΔL value due to light irradiation having a wavelength threshold of 300 to 400 nm can be 10 or less.

The mass ratio [(B) / (A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) is in the range of 0.5 to 5.0, preferably 0.5 to 2.5. More preferably, it is 0.5 to 2.0.
In the present disclosure, the amount of the inorganic binder means the solid content mass or the active ingredient mass of the inorganic binder, and the amount of the photocatalytic titanium oxide means the solid content mass of the photocatalytic titanium oxide.
When only photocatalytic titanium oxide (B) is used, water rubbing resistance is poor, and it is possible to maintain antibacterial and antiviral properties in the coating layer even when, for example, daily wiping with water is performed. Can not. On the other hand, by using the inorganic binder (A) and the photocatalytic titanium oxide (B) in the above ratio, the coating layer can exhibit antibacterial and antiviral properties and good water rubbing resistance. can. Further, when used in the above ratio, the coating layer exhibits good durability and can maintain antibacterial and antiviral properties.

For example, when the inorganic binder (A) is a silicon compound, the mass ratio [(B) / (A)] is the photocatalytic titanium oxide (B) with respect to SiO ₂ contained in the inorganic binder (A). The mass ratio of TiO ₂ contained, in other words, TiO ₂ / SiO ₂ is preferable. The mass of SiO ₂ contained in the inorganic binder (A) is a value obtained by converting the silicon content contained in the inorganic binder (A) into SiO ₂ .

For the formation of the photocatalytic titanium oxide (B) sol, a titanium acid gel obtained by neutralizing and decomposing a titanium salt with aqueous ammonia can be used as a starting material. As for the method for producing the photocatalytic titanium oxide sol, the following methods can be specifically exemplified.
(1) A method of adding a silver and copper oxide or a hydroxide to a titanium acid gel, hydrothermally treating the gel, and then adding tetraammonium hydroxide.
(2) A method in which only tetraammonium hydroxide is added to a titanium acid gel, and then a hydrothermal treatment is performed, and then an oxide or hydroxide of silver and copper is added.
(3) A method in which silver and copper oxides or hydroxides and tetraammonium hydroxide are simultaneously added to a titanium acid gel and then hydrothermally treated.
(4) A method of adding an oxide or hydroxide of silver and copper and a tetraammonium hydroxide after hydrothermally treating a gel of titanium acid.
Discoloration of silver can be suppressed by hydrothermal treatment in the coexistence of silver and copper oxides or hydroxides as in (1) and (3) above. In general, as the amount of these additives increases, the crystallization of titanium oxide into an anatase type may be inhibited. Therefore, the type, amount and the like of these additives can be appropriately selected and produced within the scope of the present invention. preferable. Further, when silver and copper oxides or hydroxides and tetraammonium hydroxide are added after the hydrothermal treatment as described in (4) above, further stabilization can be achieved by further heating as necessary. .. The heating time may be 1 to 3 hours at a temperature of 60 to 100 ° C.

<Alcohol (C)>
When the coating composition contains alcohol (C), the wettability to the object to be coated (for example, the surface of the substrate, the coating film preformed on the surface of the substrate, etc.) is improved, and the workability at the time of coating is improved. Become good. Further, by using the alcohol (C), the storage stability of the coating composition can be improved. In the present application, the alcohol (C) means a compound having at least one hydroxyl group.

As the alcohol (C), an alcohol having 1 to 7 carbon atoms can be preferably used. Examples of alcohols having 1 to 7 carbon atoms include monoalcohols such as methanol, ethanol, normal propanol, isopropanol and butanol; alkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Examples thereof include alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and propylene glycol monobutyl ether. The above alcohol may be used alone or in combination of two or more.

The alcohol (C) is, in one embodiment, at least one selected from the group consisting of ethanol, isopropanol, normal propanol and propylene glycol. It is particularly preferable to use these alcohols (C) from the viewpoint of improving coating workability.

The alcohol (C) is more preferably an alcohol having 1 to 4 carbon atoms.

As the alcohol (C), monoalcohol is preferable, and ethanol, normal propanol, and isopropanol are more preferable from the viewpoint of volatile drying property.

As the alcohol (C), it is preferable to use at least one selected from the group consisting of ethanol, normal propanol and isopropanol. When the above alcohol is used, the time until the coating layer exhibits antibacterial and antiviral properties can be shortened, and the antibacterial and antiviral properties can be exhibited immediately after the coating composition is applied.

In one embodiment, the alcohol (C) is preferably contained in an amount of 15 to 90% by mass, more preferably 50 to 80% by mass, still more preferably 50 to 59% by mass, based on the coating composition. With the above content, the time until the antibacterial and antiviral properties are exhibited in the coating layer becomes shorter. Further, the above-mentioned content is advantageous from the viewpoint of transportation, storage and the like.

In one embodiment, the alcohol (C) is preferably contained in an amount of 10 to 50% by mass, more preferably 10 to 30% by mass, based on the coating composition.

The coating composition of the present invention may contain a solvent other than alcohol. Examples of the solvent other than alcohol include water and organic solvents (excluding alcohol).

The coating composition of the present invention preferably contains water. By including water, workability is improved.
From the viewpoint of storage stability of the coating composition, the water is preferably ion-exchanged water, distilled water, filtered water or pure water.
The content of water is not particularly limited and may be adjusted so that the total amount of the coating composition with other components is 100% by mass. For example, 5 to 85% by mass, specifically 35. It may contain up to 70% by mass.

The coating composition of the present invention may contain a surfactant. By including the surfactant, the coating workability of the composition, particularly the wettability to the object to be coated, can be improved.

As the surfactant, it is preferable to use a nonionic surfactant. Nonionic surfactants can contribute to improving the stability of the coating composition. In addition, the nonionic surfactant can contribute to the improvement of the wettability of the coating composition to the object to be coated. Further, by containing a nonionic surfactant, it is possible to reduce the bias of the composition in the coating layer. This is because even when the alcohol (C) volatilizes first from the coating composition, the presence of the nonionic surfactant causes the inorganic binder (A) and the photocatalytic titanium oxide (B) in the composition. ) Can be prevented from being biased.

The content of the nonionic surfactant is preferably 0.02 to 5% by mass, more preferably 0.02 to 1% by mass, based on the coating composition. By including the nonionic surfactant in the above range, antibacterial and antiviral properties can be exhibited in the coating layer obtained from the coating composition. Further, by including the above range, it is possible to secure the wettability to the object to be coated while suppressing foaming during the production of the coating composition.
When two or more kinds of nonionic surfactants are used in combination, the total amount of the nonionic surfactants is adjusted so as to be within the above range with respect to the coating composition.

The HLB of the nonionic surfactant is preferably 12 or less, more preferably 4 to 12. Here, HLB has a balance between hydrophilicity and lipophilicity, which is defined by the Griffin method and is expressed by (molecular weight of the hydrophilic portion of the nonionic surfactant) ÷ (total molecular weight of the nonionic surfactant) × 20. It is an index to represent.
When the HLB of the nonionic surfactant is in such a range, it is possible to secure the wettability to the object to be coated while suppressing foaming during the production of the coating composition. When two or more nonionic surfactants are used in combination, the average HLB of each surfactant is appropriately adjusted to be within the above range.

Examples of the nonionic surfactant include a surfactant having an alkylene oxide unit, an acetylenediol-based surfactant, a vinyl-based polymer surfactant, a silicone-based surfactant, and a fluorine-based surfactant. These surfactants may be used alone or in combination of two or more.

Examples of the surfactant having the alkylene oxide unit include polyoxyalkylene alkyl ether-based surfactants such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether; and polyoxyalkylene fatty acid ester-based surfactants. can.
As such a surfactant, a commercially available product may be used. Examples of the polyoxyalkylene alkyl ether-based surfactant include Newcol (registered trademark) 2302, 2303, 2305, 3508, 1204, 1305, 2502-A, 2303-Y, 2304-YM, 2304-Y, (Japan). Emulmin (registered trademark) 40, 50, 70, NL-70, NL-80, Cedran (registered trademark) FF-180, SF-506, New Pole (registered trademark) PE-62, 64, 74, 75, (manufactured by Sanyo Kasei Co., Ltd.) and the like can be mentioned. Examples of the polyoxyalkylene fatty acid ester-based surfactant include Ionet (registered trademark) MS-400, MS-1000, MO-600, DS-4000, and DO-1000 (manufactured by Sanyo Chemical Industries, Ltd.).

The acetylene diol-based surfactant is, for example, a surfactant having an acetylene diol unit (that is, having an acetylene bond and two hydroxyl groups at the same time in the same molecule), and an alkylene oxide unit in which an alkylene oxide is introduced into the hydroxyl group. It can be a surfactant having an acetylene diol unit and an acetylene diol unit.
As such a surfactant, a commercially available product may be used. For example, Surfinol® 104E, 420, 440, 2502, Dynol® 604, 607, Orfin® PD-001, 002W, 004, EXP. 4001, 4200, 4300 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like can be mentioned.

Examples of the vinyl-based polymer surfactant include polyvinylpyrrolidone (PVP); a surfactant obtained by graft-polymerizing polyvinylpyrrolidone to polyvinyl alcohol (PVA).
As such a surfactant, a commercially available product may be used. For example, Pittscol (registered trademark) K-30, K-30L, K-90, K-90L, V-7154 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) can be mentioned.

Examples of the silicone-based surfactant include Granol (registered trademark) 100, 400, 440, Polyflow (registered trademark) KL-245, KL-270, KL-280, KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BYK. -307, 333, 345, 346, 348, 375, 378 (manufactured by Big Chemie Japan), SN Wet (registered trademark) 125, 126 (manufactured by San Nopco Ltd.) can be mentioned.

Examples of the fluorine-based surfactant include Futergent (registered trademark) 250, 251, 222F, 208G (manufactured by Neos), Megafuck (registered trademark) F-443, F-444, F-445, F-. 470, F-471, F-475, F-477, F-479 (manufactured by DIC), NOVEC FC-4430, 4432 (manufactured by 3M), Unidyne (registered trademark) DS-401, 403 (Nippon Evolution Seisha) EF-121, EF-122A, EF-128B, EF-122C (manufactured by Gemco).

In one embodiment, the acetylene diol-based surfactant is represented by a preferable chemical formula as follows.

Surfactant with acetylene diol unit:

In the above formula, R ¹ , R ² , R ³ , and R ⁴ are the same or different, and are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, preferably linear chains having 1 to 8 carbon atoms. Or represents a branched alkyl group.

Surfactant with alkylene oxide unit and acetylene diol unit:

In the above formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different, and are linear or branched hydrocarbon groups having 1 to 10 carbon atoms, preferably linear chains having 1 to 8 carbon atoms. Or represents a branched alkyl group. n1 and n2 are the same or different and represent integers of 0 to 20, and do not represent 0 at the same time, but preferably represent integers of 1 to 20.

In one embodiment, the coating composition contains 5 to 20% by mass of water and 0.0 to 0.05 parts by mass of a nonionic surfactant.

In one embodiment, water is contained in an amount of 50 to 85% by mass and 0.02 to 1.0 part by mass of a nonionic surfactant is contained in the coating composition.

In one embodiment, the coating composition contains 50 to 90% by mass of alcohol (C), 5 to 45% by mass of water, and 0.0 to 0.05 parts by mass of a nonionic surfactant.

In one embodiment, the coating composition contains 10 to 30% by mass of alcohol (C), 65 to 85% by mass of water, and 0.02 to 1.0 part by mass of a nonionic surfactant.

The coating composition of the present invention has, for example, a surface tension of 20 to 40 mN / m, preferably 24 to 35 mN / m.
When the surface tension of the coating composition is within the above range, the coating composition can be uniformly coated on the surface of the object to be coated.
The surface tension of the coating liquid of the present invention is, for example, "Latest instrument analysis method for coloring materials and polymer materials-Analysis and evaluation of physical properties-" (Yunori Hoshino, Editor-in-Chief, edited by Japan Society of Color Material). p.289 Surface tension measurement method, "Du Nouy ring method") is measured according to the method described.

The coating composition of the present invention may contain other additives other than the above, if necessary.

Other additives include, for example, pigments, aggregates (sand, etc.), film-forming aids, drying delay aids, viscosity regulators, preservatives, fungicides, preservatives, antifoaming agents, light stabilizers, etc. Examples thereof include antioxidants, ultraviolet absorbers, pH adjusters and the like.

The coating composition of the present invention may be an enamel coating composition containing a pigment or a clear coating composition containing no pigment.

When the coating composition of the present invention is used as a clear coating composition, since the clear coating composition is colorless and transparent or lightly colored and transparent, it is difficult to distinguish the boundary between the coated layer and the uncoated layer, and the coating layers overlap. A painted part or a forgotten part of the coating composition may occur. In the overlapping coated portion, for example, the coating composition is wasted because the coating composition is used more than necessary, the film thickness of the coating layer becomes thicker than necessary, and the excess coating layer sags. May occur. Further, since the coating layer does not exist in the portion where the coating is forgotten, the antiviral property cannot be obtained.
In contrast, the antiviral coating composition of the present invention may contain a decolorizing dye. In one embodiment, the decolorizing dye is a component that is colored in the state of the coating composition and can be decolorized by, for example, light, pH change, etc. after the formation of the coating layer (a component that can be decolorized by light). Also called "photochromatic pigment").

In the coating composition of the present invention, for example, the photochromic dye may include one or more selected from the group consisting of Monascus-based dyes, betalain-based dyes and Spirulina-based dyes.

Although not bound by theory, it is believed that the molecules of these photochromic dyes are decolorized by destroying their structure by light of a certain intensity or higher. Therefore, when the coating composition of the present invention having such a photochromic dye is used, the coating layer can be decolorized by a simple means of light.

-Monascus pigments Examples of Monascus pigments include ancaflavin (CAS number 50980-32-0), monascorbrin (CAS number 13283-90-4), monascorbramin (CAS number 3627-51-8), and the like. Examples thereof include xanthomonasin A1 (Xanthomonascin A1), xanthomonasin A2 (Xanthomonasin A2), xanthomonasin A (Xanthomonasin A) and xanthomonasin B (Xanthomonasin B). As the Monascus pigment, one kind may be used alone, or two or more kinds may be used in combination. The structures of xanthomonasin A1 (Xanthomonasin A1), xanthomonasin A2 (Xanthomonasin A2), xanthomonasin A (Xanthomonasin A) and xanthomonasin B (Xanthomonasin B) are as follows.

-Betalain dyes Examples of betalain dyes include betanin (CAS number 7569-95-2), betanidin (CAS number 2181-76-2), isobetanin (CAS number 15121-53-6), and isobetanin (CAS number 15121-53-6). No. 4934-32-1), betaxanthine, betacyanin and the like can be mentioned. As the betalain dye, one type may be used alone, or two or more types may be used in combination. The structures of betaxanthine and betacyanin are as follows.

-Spirulina dyes Examples of Spirulina dyes include phycocyanobilin (CAS No. 20298-86-6) and the like. One type of Spirulina dye may be used alone, or two or more types may be used in combination.

In one embodiment of the coating composition according to the present invention, the Monascus pigment comprises ancaflavin, monascorbrin, monascolbramin, xanthomonasin A1, xanthomonasin A2, xanthomonasin A and xanthomonasin B. Includes one or more species selected from the group.
In another embodiment of the coating composition according to the present invention, the Monascus pigment comprises one or more selected from the group consisting of ancaflavin, monascorbrin, monascorbramine, xanthmonacin A2 and xantomonasin A. ..

In one embodiment of the coating composition according to the present invention, the betalain-based dye comprises one or more selected from the group consisting of betanin, betanidin, isobetanin, isobetanidin, betaxanthine, and betacyanin.

In one embodiment of the coating composition according to the invention, the spirulina dye comprises phycocyanobilin.

Further, as one aspect of the decolorizing dye, a dye that develops or decolorizes depending on the pH of the coating composition may be used. Specifically, pH indicators having a colorless acidic to neutral color and a basic color, such as phenolphthalein, thymolphthalein, bromcarboxythymolphthalein, o-cresolphthalein, cyanine, and α-naphthol. Examples thereof include phthalein and p-nitrophenyl.

The amount of the decolorizing dye in the coating composition can be appropriately adjusted according to the color intensity of the decolorizing dye, the concentration or viscosity of the coating composition, the thickness of the coating layer, the time until decolorization, and the like. The amount of the decolorizing dye in the coating composition is, for example, 0.001 to 5.00 parts by mass with respect to 100 parts by mass of the coating composition.

(Manufacturing method of coating composition)
The method for preparing the coating composition is not particularly limited. For example, it can be prepared by selecting and using a mixer such as a sand grind mill, a ball mill, a blender, a paint shaker or a disper, a disperser, a kneader and the like, and mixing each component.

(How to use the coating composition)
The method of using the coating composition of the present invention is not particularly limited, and for example, the coating composition can be coated or pre-painted on a portion to which bacteria or viruses adhere or may adhere.

In one embodiment, the coating composition of the present invention may be, for example, dip coating, brush coating, roller coating, coating with a cloth, roll coater coating, spray coating, curtain flow coater coating, roller curtain coater coating, Daiko. It can be painted using a tar paint or the like. The coating method is appropriately selected according to the type and application of the object to be coated.

Examples of the spray coating include air spray coating and airless spray coating in one embodiment.

Examples of the spray coating include aerosol spray coating and non-aerosol spray coating in one embodiment.
In this case, the coating composition can be used, for example, by filling it in a discharge container.
Examples of the discharge container include a spray container and a squeeze container. It is preferable to use a spray container as the discharge container from the viewpoint of excellent paintability on the object.
The spray container, that is, the aerosol spray container and the non-aerosol spray container may be a manual type or an electric type.

As the aerosol spray container, a pressure resistant container is used. In this case, the coating composition of the present invention is used together with a gas such as a liquid gas and a compressed gas. Examples of the liquid gas and the compressed gas include liquefied petroleum gas, dimethyl ether, carbon dioxide gas, nitrogen gas, isopentan and the like.

The non-aerosol spray container is provided with a mechanism for ejecting the liquid filled in the container to the outside of the container in the form of mist or foam. In this case, gas such as liquid gas and compressed gas is substantially not used. Examples of the non-aerosol spray container include a pressure-accumulation type or a direct pressure type spray container such as a pump type and a trigger type.

In one embodiment, the coating composition can also form a coating layer by spraying on the coated area, covering the coated area with paper and sprinkling the composition directly.

In one embodiment, the coating composition may form a coating layer by painting with a cloth. Specifically, the coating layer can also be formed by impregnating the cloth with the coating composition and wiping the coated portion (the surface of the object to be coated). The fibers constituting the cloth are not particularly limited, and examples thereof include natural fibers, synthetic fibers, semi-synthetic fibers, and regenerated fibers. The type of cloth is not particularly limited, and examples thereof include woven cloth, non-woven fabric, and knitted fabric.

[Coating layer]
The coating layer is formed by the coating composition of the present invention.

The formation of the coating layer
A step of coating an object to be coated with a coating composition so that the mass of the coating composition after drying is 0.20 g / m ² or less to form a coating layer.
It is preferable to carry out by a method including.
The mass after drying may be, for example, 0.02 to 0.20 g / m ² . Within the above range, a coating layer having good physical properties such as antibacterial and antiviral properties can be formed.
The coating composition may be applied a plurality of times as needed, and the number of times of application is appropriately adjusted depending on the solid content concentration of the coating composition and the amount of one application. ..
The film thickness of the coating layer (film thickness after drying) is preferably 50 nm to 5 μm, and more preferably 50 nm to 1 μm.

The coating layer may be provided on the entire surface of the object to be coated, or may be provided only on a part of the surface of the object to be coated.

The coating layer is obtained by applying the coating composition to an object to be coated and then drying it at room temperature (for example, 5 ° C to 35 ° C).
In another embodiment, the coating layer is obtained by drying the coating composition at room temperature to 80 ° C. In another embodiment, the coating layer is obtained by drying the coating composition at 80 ° C to 130 ° C.
The drying time is not particularly limited, but is preferably 30 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.

The object to be coated is not particularly limited, and examples thereof include a metal base material, a plastic base material, and an inorganic material base material. Further, a coating film previously formed on these substrates may be used as an object to be coated. By coating the surface of the object to be coated with the coating composition of the present invention, the coating has good water-rubbing resistance, good antibacterial and antiviral properties, and can maintain antibacterial and antiviral properties. You can get a layer.

The metal base material is not particularly limited, and examples thereof include an aluminum plate, an iron plate, a galvanized steel plate, an aluminum galvanized steel plate, a stainless steel plate, and a tin plate.
Examples of the plastic base material include an acrylic plate, a polyvinyl chloride plate, a polycarbonate plate, an ABS plate, a polyethylene terephthalate plate, a polyolefin plate and the like.
Examples of the inorganic material base material include ceramic base materials and glass base materials described in JIS A 5422, JIS A 5430, and the like.

In one embodiment, the material of the object to be coated includes, for example, acrylic resin, methacrylic resin, alkyd resin, phenol resin, epoxy resin, isocyanate resin, melamine resin, silicone resin, polyester resin, polyurethane resin, fluororesin, rubber and the like. Organic or plastic materials; glass; tin, iron, steel, copper, gold, silver, aluminum and other metals; asphalt; ceramics; concrete, mortar, brick, slate, marble and other stones; wood, plywood, etc. Can be done.

Examples of the coating film include an organic coating film, an inorganic coating film, an organic-inorganic hybrid coating film, and a fluororesin coating film. The antiviral coating composition of the present invention can adhere well to these coating films. By coating the coating composition of the present invention on these coating films and forming a layer, not only antibacterial properties and antiviral properties can be imparted, but also a good appearance can be obtained and hue changes and the like can be suppressed. .. In addition, peeling of the formed coating layer can be suppressed.
Further, by using the coating layer, chalking, fading, etc. of the enamel-based coating film can be suppressed.

[Article]
The present invention also relates to an article comprising a substrate and a coating layer of the invention on the surface of the substrate.

The article is not particularly limited and may be appropriately selected. For example, the interior and exterior of vehicles such as automobiles, trains, buses, and taxis; the interior and exterior of aircraft such as ships; airplanes and helicopters; the exterior of transportation means such as escalator and elevator; , Public facilities, commercial facilities, education / research facilities, etc. Building interiors and exteriors (walls, floors, ceilings, roofs, pillars, signs, electronic signs (digital signage), toilets, gates, handrails, door knobs, window frames, switches (Including curtains, etc.), desks, tables, chairs, shelves, partitions, mirrors, beds and other furniture; TVs, refrigerators and other home appliances; copy machines, lockers, delivery boxes and other equipment; touch panels for various products ; Vending machines; Clothing; Footwear such as shoes; Rain gear such as umbrellas; Packaging materials, etc.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are based on mass unless otherwise specified.

[Preparation method for photocatalytic titanium oxide (B1)]
Ammonia water (containing 3.0% by mass of NH ₃ ) was added to an aqueous solution of titanium tetrachloride (containing 0.5% by mass of TiO ₂ ) under stirring to generate a titanium gel. This titanium gel was filtered and washed with water until the chlorine ion content was 100 ppm or less with respect to the titanium gel to obtain a slurry composed of the titanium gel (containing 6.2% by mass of TiO ₂ with respect to the slurry). Silver oxide (Mass ratio) is 5 in _{200 g of this slurry so that the total of Ag 2 O and Cu O is 5% by mass and the ratio of copper to silver [CuO / Ag 2 O (} mass ratio)] is 5. Ag ₂ O (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g and copper hydroxide (Cu (OH) ₂ , manufactured by Kanto Chemical Co., Ltd.) 0.6 g were added. Further, 1.7 g of a 25% aqueous solution of tetraethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) was added to 1 mol of titanium oxide (TiO ₂ ) so as to be 0.03 mol, and the mixture was well stirred. Then, this was put into an autoclave and subjected to a hydrothermal treatment at 130 ° C. for 10 hours to prepare a photocatalytic titanium oxide (B1). The content of each component was TiO ₂ : 6.10% by mass, Ag _2O : 0.05% by mass, CuO: 0.24% by mass, and tetraethylammonium hydroxide: 0.21% by mass. When the powder obtained by drying this at 100 ° C. was measured by powder X-ray diffraction method, an anatase-type titanium oxide peak was observed.

[Preparation method for photocatalytic titanium oxide (B2)]
Except for changing the amount of Ag ₂ O and Cu O to 7% by mass of the total of Ag ₂ O and Cu O with respect to TiO ₂ and changing the ratio of copper to silver [CuO / Ag ₂ O (mass ratio)] to 5. Prepared photocatalytic titanium oxide (B2) in the same manner as above. The content of each component was TiO ₂ : 6.10% by mass, Ag _2O : 0.07% by mass, CuO: 0.36% by mass, and tetraethylammonium hydroxide: 0.21% by mass.

The inorganic binders, alcohols, surfactants, and decolorizing dyes used in Examples and Comparative Examples are as follows.

(A1) ST-O, colloidal silica, acidic type, spherical (manufactured by Nissan Chemical Industries, Ltd.); average particle diameter 12 nm, active ingredient concentration: 20% by mass
(A2) ST-OUP, colloidal silica, acidic type, chain (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 12 nm, active ingredient concentration: 15% by mass
(A3) ST-PS-SO, colloidal silica, acidic type, pearl necklace (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 15 nm, active ingredient concentration: 15% by mass
(A4) ST-OXS, colloidal silica, acidic type, spherical (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 5 nm, active ingredient concentration: 10% by mass
(A5) ST-OL, colloidal silica, acidic type, spherical (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 45 nm, active ingredient concentration: 20% by mass
(A6) MKC silicate MS51, tetramethoxysilane partial hydrolysis condensate (manufactured by Mitsubishi Chemical Corporation), active ingredient concentration: 52% by mass
(A7) 50L, aluminum phosphate, acidic (manufactured by Taki Chemical Co., Ltd.), solid content concentration: 38% by mass
(A1) ST-N, colloidal silica, alkaline type, spherical (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 12 nm, active ingredient concentration: 20% by mass
(A2) ST-C, colloidal silica, neutral type, alumina treatment, spherical (manufactured by Nissan Chemical Industries, Ltd.); average primary particle size: 12 nm, active ingredient concentration: 20% by mass

(alcohol)
(C1) Ethanol, manufactured by Konishi Co., Ltd. (C2) Isopropanol, manufactured by Hayashi Junyaku Kogyo Co., Ltd. (C3) Normal propanol, manufactured by Hayashi Junyaku Kogyo Co., Ltd. (C4) Propylene glycol, manufactured by Hayashi Junyaku Kogyo Co., Ltd.

(Nonion-based surfactant)
(D1) Surfinol 420: Acetylenediol-based surfactant (manufactured by Nissin Chemical Industry Co., Ltd.), HLB: 4, active ingredient concentration: 100% by mass
(D2) Emulmin NL-70: Polyoxyalkylene alkyl ether-based surfactant (manufactured by Sanyo Chemical Industries, Ltd.), HLB: 10.6, active ingredient concentration: 100% by mass

(Decolorizing pigment)
Monascus AL900R: Monascus pigment (Kiriya Chemical), active ingredient concentration: 45% by mass (ethanol solution)

(others)
・ Toluene: Mitsubishi Chemical Corporation ・ Ion-exchanged water

(Example 1)
0.75 parts by mass of silica fine particles (A1), 4.33 parts by mass of photocatalytic titanium oxide (B1), 59.00 parts by mass of alcohol (C1) and 35.92 parts by mass of ion-exchanged water are sequentially added while stirring. And mixed to prepare the coating composition 1.

(Examples 2 to 20 and Comparative Examples 1 to 7)
Examples 2 to 20 and Comparative Examples 1 to 7 were operated in the same manner as in Example 1 except that the content and type of each component were changed to the conditions shown in Tables 1A to 1D to prepare coating compositions, respectively. ..
In (A6), 8.5 parts by mass of MKC silicate MS51, 0.1 part by mass of aluminum chelate D (manufactured by Kawaken Fine Chemical Co., Ltd., active ingredient concentration: 76% by mass), 40.0 parts by mass of ethanol and ion exchange. A product prepared by adding 51.4 parts by mass of water and stirring at 60 ° C. for 3 hours (pH: 3.5, active ingredient concentration: 5% by mass) was used.

(Preparation of test plate)
The coating compositions obtained in Examples and Comparative Examples were spray-coated on a glass plate so that the amount of the coating composition liquid applied was 10 g / m ² , and then a jet dryer (wind speed: 10 m / s) was used. A test plate was obtained by drying at 100 ° C. for 10 minutes.

The obtained coating composition and test plate were evaluated as follows.

1) Storage stability of the coating composition The coating compositions obtained in Examples and Comparative Examples were allowed to stand at 40 ° C. for 14 days. The state of the coating composition after standing was visually observed, and the stability of the coating composition was evaluated. The evaluation criteria are as follows.
◯: Separation and / or sedimentation did not occur.
X: Separation and / or sedimentation occurred.

2) Wetting property to the substrate The coating composition obtained in Examples and Comparative Examples was applied to a soda glass plate (50 mm × 50 mm × 2 mm) so that the coating amount of the coating composition was 10 g / m ² as a WET mass. Was spray painted. The state after painting was visually observed to evaluate the wettability to the substrate. The evaluation criteria are as follows.
◯: The entire surface is uniformly wet (the coating composition does not become a ball).
Δ: The entire surface is wetted almost uniformly, but the end face is leaked (the coating composition is slightly due to the central portion).
X: The entire surface is repelled (the coating composition is beaded and the entire surface is not uniformly wet).

3) Antibacterial property evaluation The test plates obtained in Examples and Comparative Examples were subjected to an antibacterial property test using Staphylococcus aureus according to the method specified in JIS R 1752 (2020).
That is, a 20 W white fluorescent lamp Neoline FL20S / W (manufactured by Toshiba Lighting & Technology Corporation) was used as a light source, and visible light of 380 nm or more was irradiated with an illuminance of 500 lux through an ultraviolet cut filter N-169 (manufactured by Nitto Jushi Kogyo Co., Ltd.). .. The illuminance was measured using an illuminance meter IM-5 (manufactured by Topcon). The antibacterial activity value (R) in the bright place was calculated by the following formula, assuming that the irradiation time of visible light was 8 hours. The reference plate used was a soda glass plate that had not been antibacterial processed.
Antibacterial activity value in the bright place: R = Log10 (UB / TB)
TB: Viable cell count per test plate after light irradiation (cfu)
UB: Viable cell count per reference plate after light irradiation (cfu)
The measured antibacterial activity value (R) in the bright place was evaluated according to the following evaluation criteria. A score of 1 was the best, a score of 5 was the worst, and a score of 3 or higher was passed.
1: R is 4 or more and 2: R is 3 or more and less than 4. 3: R is 2 or more and less than 3. 4: R is 1 or more and less than 2. 5: R is less than 1.

4) Antiviral properties The test plates obtained in the Examples and Comparative Examples were subjected to an antiviral test using bacteriophage Qβ according to the method specified in JIS R 1756 (2020).
That is, a 20 W white fluorescent lamp Neoline FL20S / W (manufactured by Toshiba Lighting & Technology Corporation) was used as a light source, and visible light of 380 nm or more was irradiated with an illuminance of 500 lux through an ultraviolet cut filter N-169 (manufactured by Nitto Jushi Kogyo Co., Ltd.). .. The illuminance was measured using an illuminance meter IM-5 (manufactured by Topcon). The antiviral activity value (V) in the bright place was calculated by the following formula, assuming that the irradiation time of visible light was 4 hours. As the reference plate, a soda glass plate without antiviral processing was used.
Antiviral activity value in the bright place: V = Log ₁₀ (UV / TV)
TV: Bacteriophage infectious titer per test plate after light irradiation (pfu)
UV: Bacteriophage infectious titer per reference plate after light irradiation (pfu)
Before evaluating the antiviral property, the front surface and the back surface of the coated body were sterilized by irradiating them with a germicidal lamp in a clean bench. As for the germicidal lamp, a 15 W germicidal lamp (wavelength 254 nm) was installed on the side surface of the clean bench, for a total of two germicidal lamps, and the distance from the painted body to the light source was set to 30 cm to 60 cm. The irradiation time of the germicidal lamp was 15 minutes.
The measured antiviral activity value (V) in the bright place was evaluated according to the following evaluation criteria. A score of 1 was the best, a score of 5 was the worst, and a score of 3 or higher was passed.
1: V is 4 or more and 2: V is 3 or more and less than 4 3: V is 2 or more and less than 3 4: V is 1 or more and less than 2 5: V is less than 1 1

5) Durability (water rubbing test)
The test plates obtained in Examples and Comparative Examples were attached to the evaluation table of the friction friction analyzer TS501 (manufactured by Kyowa Interface Science Co., Ltd.) with adhesive tape, and a rubbing test was carried out. The measurement conditions were a waste cotton wool soaked with ion-exchanged water as a friction material, a load of 20 g / cm ² , a reciprocating speed of 60 times / minute, a reciprocating distance of 60 mm, and a reciprocating number of 10 times.
After the test was completed, 1 g / 10 cm ² of a 1 mass% silver nitrate aqueous solution was applied to each of the parts where the rubbing test was performed and the parts where the rubbing test was not performed, and ultraviolet light was irradiated (illuminance: 80 mW / m ² , irradiation time: 5 seconds). .. The color difference (ΔE) was measured using a color difference meter CR-400 (manufactured by Konica Minolta Co., Ltd.) for the parts tested and the parts not tested, based on the parts not coated with the silver nitrate aqueous solution. The residual photocatalytic rate was calculated according to the formula. The evaluation criteria are as follows. When measuring the color difference, a white coated paper (manufactured by TP Giken Co., Ltd.) was laid under the test plate.
Residual photocatalytic rate (%) = Color difference (ΔE) of the part where the friction test was performed / Color difference (ΔE) of the part where the friction test was not performed × 100
⊚: Residual photocatalytic rate is 95% or more ○: Residual photocatalytic rate is 80% or more and less than 95% Δ: Residual photocatalytic rate is 40% or more and less than 80% ×: Residual photocatalytic rate is less than 40%

6) Visibility evaluation With respect to the test plate obtained in Example 20, the color of the coating layer immediately after the test plate was produced (the coating layer was formed) was visually observed and evaluated according to the following criteria. ○ The above was accepted.
⊚: The color of the colored coating layer can be clearly confirmed.
◯: The color of the colored coating layer can be confirmed.
Δ: The color of the colored coating layer can be barely confirmed.

6) Evaluation of photochromicity The test plate obtained in Example 20 was irradiated with visible light to carry out a photochromic test.
Based on the color of the coating layer immediately after the test plate was prepared (the coating layer was formed), it was coated every hour from the start of visible light irradiation using a color difference meter CR-400 (manufactured by Konica Minolta). The color difference (ΔE) of the layers was measured. The time until ΔE became 1 or less was measured and evaluated according to the following criteria. Evaluation △ or higher was regarded as acceptable.
Visible light source: White fluorescent lamp, Neoline FL20SW (manufactured by Toshiba Litec), Wavelength: 400-800 nm, Illuminance: 500 lux (wavelength less than 400 nm was removed with a cut filter)
⊚: ΔE becomes 1 or less within 3 hours from the start of irradiation.
◯: ΔE becomes 1 or less within 3 hours or more and less than 12 hours from the start of irradiation.
Δ: ΔE becomes 1 or less within 12 hours or more and 24 hours or less from the start of irradiation.
X: ΔE does not become 1 or less within 24 hours from the start of irradiation.

The conditions and evaluation results of Examples and Comparative Examples are shown in the table below.
In Example 13, the numerical value described in the column of "the content of the active ingredient of (A) in 100 parts by mass of the coating composition" in the table corresponds to the "solid content".
Further, in the fifteenth embodiment, the numerical value described in the column of "content of SiO ₂ " in the table is the "content of AlPO ₄ " and the mass ratio of "TiO ₂ to SiO ₂ (TiO ₂ / SiO). The numerical values described in the “ ₂ )” column correspond to the “mass ratio of TiO ₂ and AlPO ₄ (TIO ₂ / AlPO ₄ )”, respectively.
Further, in Comparative Examples 3 and 4, the numerical values described in the column of "Mass ratio of (B) and (A)" in the table are "Mass ratio of (B) and (a1)" and "", respectively. Corresponds to the "mass ratio of (B) and (a2)". Further, in Comparative Example 7, the numerical value described in the column of "Contents of (C) in 100 parts by mass of the coating composition" in the table corresponds to "Contents of toluene in 100 parts by mass of the coating composition". do.

According to Examples 1 to 20, a coating composition having good storage stability and wettability to a substrate could be obtained. By using the coating compositions obtained in Examples 1 to 20, a coating layer having good antiviral property, antibacterial property and durability (water rubbing test) could be obtained. In Examples 17 and 18, the surfactant (D) was added to the coating composition, and in these examples as well, the storage stability of the coating composition and the wettability to the substrate were good, and the results were obtained. The antiviral property, antibacterial property, and durability (water rubbing test) of the coating layer were also good. In Example 20, it was confirmed that good results were obtained in terms of visibility and decolorization.
The composition of Comparative Example 1 contains almost no inorganic binder. It was found that the obtained coating layer could not maintain antiviral properties due to its poor durability (water rubbing resistance).
In the composition of Comparative Example 2, the mass ratio [(B) / (A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) was low, and the antiviral property was poor.
The composition of Comparative Example 3 contained an alkaline sol as an inorganic binder, and the composition of Comparative Example 4 contained an alumina-treated sol as an inorganic binder. The resulting coating composition had poor storage stability.
The composition of Comparative Example 5 did not contain alcohol and had poor wettability to the substrate, so that the antibacterial and antiviral properties of the coating layer were not good.
The composition of Comparative Example 6 is obtained by adding a nonionic surfactant to the conditions of Comparative Example 5. The wettability to the substrate was slightly improved as compared with Comparative Example 5, but was not sufficient, and the antibacterial and antiviral properties were as poor as those of Comparative Example 5.
The composition of Comparative Example 7 used toluene instead of alcohol, but the stability of the composition was poor and other evaluations could not be performed.

The coating composition of the present invention is a coating layer having good storage stability, a short time to exhibit antibacterial and antiviral properties, and good antibacterial and antiviral durability. Can contribute to the formation. The coating composition of the present invention allows the formation of various articles having a coating layer.

Claims (16)

It contains an inorganic binder (A), a photocatalytic titanium oxide (B) and an alcohol (C).
The inorganic binder (A) is an acidic type and is of an acidic type.
The mass ratio [(B) / (A)] of the photocatalytic titanium oxide (B) to the inorganic binder (A) is in the range of 0.5 to 5.0.
Antibacterial / antiviral coating composition. The antibacterial / antiviral coating composition according to claim 1, wherein the inorganic binder (A) contains a silicon compound-based binder. The antibacterial / antiviral coating composition according to claim 1 or 2, wherein the inorganic binder (A) contains at least one selected from the group consisting of colloidal silica and alkyl silicates. The antibacterial / antiviral coating composition according to any one of claims 1 to 3, wherein the photocatalytic titanium oxide (B) contains silver and copper and tetraammonium hydroxide. The antibacterial / antiviral coating composition according to any one of claims 1 to 4, wherein the alcohol (C) contains an alcohol having 1 to 7 carbon atoms. The antibacterial / antiviral coating composition according to any one of claims 1 to 5, wherein the alcohol (C) is at least one selected from the group consisting of ethanol, isopropanol, normal propanol and propylene glycol. The antibacterial / antiviral coating composition according to any one of claims 1 to 6, further comprising water. The antibacterial / antiviral coating composition according to any one of claims 1 to 7, further comprising a surfactant. The antibacterial / antiviral coating composition according to claim 8, wherein the surfactant is a nonionic surfactant. The antibacterial / antiviral coating composition according to any one of claims 1 to 9, further comprising a decolorizing dye. An antibacterial / antiviral coating layer formed by the antibacterial / antiviral coating composition according to any one of claims 1 to 10. An article comprising a base material and the antibacterial / antiviral coating layer according to claim 11 on the surface of the base material. The antibacterial / antiviral coating composition according to any one of claims 1 to 10 is applied to an object to be coated, and the weight of the antibacterial / antiviral coating composition after drying is 0.02 to 0.20 g / m. A method for forming an antibacterial / antiviral coating layer, which comprises a step of forming an antibacterial / antiviral coating layer by painting so as to be ² . To form the antibacterial / antiviral coating layer, the antibacterial / antiviral coating composition is subjected to dip coating, brush coating, cloth coating, roller coating, roll coater coating, spray coating, curtain flow coater coating, roller coating. The method for forming an antibacterial / anti-virus coating layer according to claim 13, which is performed by coating by at least one method selected from the group consisting of curtain coater coating and die coating. The method for forming an antibacterial / antiviral coating layer according to claim 14, wherein the spray coating is an aerosol spray coating or a non-aerosol spray coating. The method for forming an antibacterial / antiviral coating layer according to claim 14, wherein the coating using the cloth is performed by impregnating the cloth with the antibacterial / antiviral coating composition and wiping the surface of the object to be coated. ..