JP7074556B2 - Coating film and water-based composition - Google Patents

Description

The present invention relates to a coating film and an aqueous composition.

By forming a coating film on various base materials using a coating material, it is possible to impart physical properties that cannot be expressed by each base material alone, and it has been sold and developed as various high value-added products. ..
In particular, by coating with a hydrophilic coating, antifouling and anti-fog properties can be imparted, so that it can be used in a wide range of applications such as building materials and window glass, and automobile bodies such as automobile bodies and headlamp covers. In the field, it is expected that the coating film will exhibit its function.

However, in a coating film having hydrophilicity, microorganisms such as bacteria, molds, and algae usually easily propagate, which not only causes poor appearance and deterioration of the coating film, but also may cause a foul odor due to bacteria, etc. Contamination due to reproduction of algae is attracting attention as a problem to be solved, and various techniques have been proposed.

For example, a hydrophilic coating film having antifungal properties has been proposed by adding a compound exhibiting antifungal properties to a hydrophilic polymer (see, for example, Patent Document 1).
Further, as a photocatalytic coating film exhibiting antifouling property, a coating film containing a photocatalyst combined with an antibacterial metal has been further proposed (see, for example, Patent Documents 2 and 3).

Japanese Unexamined Patent Publication No. 2009-256571 Japanese Patent No. 5343176 Japanese Patent No. 5361513

However, in the hydrophilic coating film proposed in Patent Document 1, the polymer as a binder component of the coating film is easily deteriorated by ultraviolet rays in an outdoor environment, so that the hydrophilicity and antifouling property of the coating film are lowered. It is easy to use, and there is a problem that the antifungal agent may be decomposed or flow out due to rainwater, and the effect may not last for a long period of time.

Further, in the photocatalyst coating film disclosed in Patent Document 2 and Patent Document 3, decomposition and outflow due to rainwater are suppressed by using a poorly water-soluble antibacterial metal-containing compound, but titanium oxide and the antibacterial thereof are suppressed. Since the interaction with the sex metal-containing compound is weak such as van der Waals force, it is difficult to suppress the detachment of the antibacterial metal-containing compound exposed on the surface of the coating film for a long period of time, and as a result, it is difficult to suppress the detachment. It has a problem that the effect on bacteria and the like may not last for a long time.

Therefore, in the present invention, a coating film that maintains antifouling, algae-proof, and antifungal properties for a long period of time even when exposed to an outdoor environment such as ultraviolet light or rainwater, and a coating film thereof. It is an object of the present invention to provide an aqueous composition for forming a coating film.

As a result of diligent studies to solve the above-mentioned problems of the prior art, the present inventors have found that the antibacterial metal-containing compound remains in a specific amount or more after the accelerated weather resistance test and in a specific range ratio in the coating film. The present invention has been completed by finding that the above-mentioned problems of the prior art can be solved by the coating film having voids and that the coating film can be provided by an aqueous composition containing antibacterial metal particles, colloidal silica and a specific compound. I came to let you.
That is, the present invention is as follows.

[1]
A coating film containing an antibacterial metal-containing compound,
The aqueous composition forming the coating film is
water and,
Antibacterial metal particles A and
A functional group B1 that interacts with the antibacterial metal particles A in the molecule, a silanol group, and a shiroki.
A functional group that is at least one selected from the group consisting of functional groups that interact with a sun bond.
Compound B containing B2 and
Colloidal silica C and
, Containing,
The ratio of the mass of the antibacterial metal particles A to the mass of the colloidal silica C is 0.0.
It is 1 to 10.0%,
The ratio of the mass of the compound B to the mass of the antibacterial metal particles A [(mass of compound B) / (mass of antibacterial metal particles A)] × 100 (%) is 1 to 300%.
The compound B is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. A hydrolyzate of a compound selected from the group consisting of triethoxysilane, or at least one selected from the group consisting of a compound in which these are partially condensed.
The total mass of the antibacterial metal-containing compound in the coating film after 2500 hours in the exposure test conforming to JIS K 5600-7-7 is the total mass.
It is 5% or more with respect to the total mass of the antibacterial metal-containing compound in the coating film before the exposure test.
There are voids in the coating film,
The porosity of the coating film is 1 to 30%.
Coating film.
[2]
The ratio of the average particle size of the antibacterial metal particles A to the average particle size of the colloidal silica C in the aqueous composition , (average particle size of the antibacterial metal particles A) / (average particle size of the colloidal silica C) is , 0.01 to 10, the coating film according to the above [1] .
[3]
The coating film according to the above [1] or [2] , wherein the content of the colloidal silica C in the water-based composition is 50 to 99% with respect to the total solid content contained in the water-based composition.
[4]
The coating film according to any one of [1] to [3] above, wherein the antibacterial metal particles A are at least one selected from the group consisting of gold, silver, and copper, and compounds thereof.
[5]
The coating film according to any one of the above [1] to [4] , wherein the aqueous composition further contains particles D having photocatalytic activity.
[6]
The coating film according to the above [5] , wherein the particles D having photocatalytic activity are at least one selected from the group consisting of titanium oxide, tungsten oxide, and silica-coated titanium oxide.

According to the present invention, a coating film that maintains antifouling, algae-proof, and antifungal properties for a long period of time even when exposed to an outdoor environment such as ultraviolet light or rainwater, and a coating film thereof. It is possible to provide an aqueous composition that forms a coating film.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and carried out within the scope of the gist thereof.

[Coating film]
The coating film of the present embodiment is a coating film containing an antibacterial metal-containing compound, and the antibacterial metal in the coating film after 2500 hours have passed in an exposure test according to JIS K 5600-7-7. The total content mass of the contained compound is 5% or more with respect to the total content mass of the antibacterial metal-containing compound in the coating film before the exposure test, voids are present in the coating film, and the coating film is present. The void ratio is 1 to 30%.

(Antibacterial metal-containing compound)
The coating film of the present embodiment contains an antibacterial metal-containing compound.
The antibacterial metal-containing compound means a compound containing a metal having a growth-inhibiting function against Escherichia coli cells, and the antibacterial metal-containing compound includes a known metal simple substance, a salt thereof, an oxide thereof, and a nitride thereof. Examples thereof include antibacterial metal-containing compounds such as substances, and metal complexes.
Examples of the element used for the antibacterial metal-containing compound include metal elements having a minimum growth inhibition concentration (MIC) of 20 mM or less for Escherichia coli cells, and specifically, elements such as gold, silver, copper, and zinc. Can be mentioned.
Compounds using these metal elements include, for example, gold chloride acid, silver nitrate, silver chloride, silver bromide, silver iodide, copper sulfate pentahydrate, copper nitrate, copper nitride, copper iodide, and copper hydroxide. , Salts such as copper oxide, cuprous oxide, copper acrylate, zinc nitrate, complexes such as copper pyrithione, copper phthalocyanine, zinc pyrithione, and combinations of cyclic compounds such as porphyrin and crown ether and metal ions.
Among these antibacterial metal-containing compounds, the inclusion of the antibacterial metal particles A described later is preferable because the deterioration of the antibacterial metal-containing compound itself and the outflow due to rainwater or the like are small.

The coating film of the present embodiment is characterized in that the antibacterial metal-containing compound exhibits a specific residual rate after a predetermined exposure test.
That is, the coating film of the present embodiment was tested for 2500 hours in an exposure test based on JIS K 5600-7-7, and the content of the antibacterial metal-containing compound in the coating film after the test was before the test. The ratio to the antibacterial metal-containing compound is 5% or more.
Since the exposure test based on JIS K 5600-7-7 is a standard used for the long-term durability test of the coating film, does the test show whether the coating film has more algae-proof and antifungal properties for a long period of time? It is preferable as an accelerated test for verification. Further, the exposure time of 2500 hours is a determination time for evaluating the weather resistance in the standard for building finish coating materials defined in JIS A 6909, and is preferable as a time for determining the durability of the coating film.

The antibacterial metal-containing compound has a problem that the coating film resin is deteriorated and a highly soluble metal salt or the like is extracted by rainwater or the like, and the content in the coating film easily decreases after a long period of time. have.
Therefore, in the present embodiment, the residual rate of the antibacterial metal-containing compound after the exposure test is specified to be 5% or more.
As a method for adjusting the residual amount of the antibacterial metal-containing compound, specifically, as a method for increasing the residual amount in the coating film, for example, an organic resin such as an acrylic resin may be previously contained with the antibacterial metal-containing compound. , A method of blending a polymer side chain functional group with an antibacterial metal-containing compound in an aqueous composition for forming a coating film, metal ions in inorganic particles such as zeolite and mesoporous silica. Etc., and a method of preparing an aqueous composition using the antibacterial metal particles A, the compound B, and the colloidal silica C, which will be described later, are effective.

In the coating film of the present embodiment, the total mass of the antibacterial metal-containing compound in the coating film after the exposure test is divided by the total mass of the antibacterial metal-containing compound in the coating film before the exposure test. Indication, [(total content of antibacterial metal-containing compound after exposure test) / (total content of antibacterial metal-containing compound before exposure test)] × 100, that is, residual rate after exposure test 5% or more.
The total content mass means the total amount of a plurality of antibacterial metal-containing compounds when they are contained.
When the residual rate of the antibacterial metal-containing compound is 5% or more, the algae-proof and antifungal properties are maintained. It is preferably 10% or more, more preferably 20% or more. The upper limit is not particularly limited, but is preferably 100%.

(Gap)
The coating film of the present embodiment has voids in the coating film.
The coating film of the present embodiment has a porosity of 1 to 30%.
The porosity is the volume fraction occupied by the air contained in the coating film, and can be measured by the method described in Examples described later.
It is preferable that the voids exist immediately after the coating film is formed, and it is preferable that the voids are present even after the exposure test according to JIS K 5600-7-7 described above.

The presence of 1% or more voids in the coating film ensures a sufficient specific surface area of the voids in the coating film, thereby causing metal ions released from the antibacterial metal-containing compound and the multi-layer coating film. In this case, the chemicals and the like from the lower layer of the coating film of the present embodiment diffuse in the voids and are easily extracted on the surface of the coating film, which is preferable because the algae-proof and antifungal properties are further improved.
Further, the presence of 1% or more of voids is preferable because distortion due to expansion and contraction of heat and moisture of the coating film is absorbed and cracks are reduced.
When the porosity is 30% or less, the specific surface area of the voids in the coating film is appropriately suppressed, whereby the proportion of the space in the coating film where the constituents do not come into contact with each other is suppressed and contained in the coating film. It is preferable because the bonds and interactions between the solids to be formed or between the underlying base material and the coating film and the coating film constituent components of the present embodiment can be sufficiently exhibited and the adhesion of the coating film is improved.

The porosity in the coating film can be controlled by selecting the shape of a plurality of particles contained in the coating film, adjusting the particle size ratio and its mixing ratio, and adjusting the film forming conditions. ..
Specifically, particles having non-spherical morphology such as pearly or linear are blended, the glass transition temperature and the minimum film forming temperature of the organic resin to be blended, and the blending ratio of the resin are adjusted, and further. The temperature can be controlled within a predetermined numerical range by an operation of sintering a coating film obtained by drying an aqueous composition and intentionally decomposing an organic substance.

The coating film of the present embodiment has a porosity of 1 to 30%, preferably 5 to 28%, and more preferably 10 to 25%.

[Aqueous composition]
The water-based composition of the present embodiment is the water-based composition for forming the coating film of the present embodiment described above.
water and,
Antibacterial metal particles A and
A compound B having a functional group B1 in the molecule that interacts with the antibacterial metal particles A and a functional group B2 that is at least one selected from the group consisting of a silanol group and a functional group that interacts with a siloxane bond.
Colloidal silica C and
, Containing,
The ratio of the mass of the antibacterial metal particles A to the mass of the colloidal silica C is 0.01 to 10.0%.

The coating film in the present embodiment can be obtained by a known coating method using the aqueous composition of the present embodiment.
Further, depending on the type of the coating film in the base material and the lower layer of the coating film, pretreatment such as heating or corona treatment may be carried out. Further, the aqueous composition of the present embodiment may be applied a plurality of times to form a coating film as a multi-layer coating film, or a coating film composed of another composition may be formed on the surface of the coating film.

(Antibacterial metal particles A)
The antibacterial metal particle A refers to, for example, a metal particle having a minimum inhibitory concentration (MIC) of 20 mM or less of a metal ion with respect to Escherichia coli cells.
The minimum inhibitory concentration (MIC) is the minimum concentration of a drug (here, a metal ion) required to inhibit the growth of bacteria.

In the aqueous composition of the present embodiment, the ratio of the mass of the antibacterial metal particles A to the mass of colloidal silica C, [(mass of antibacterial metal particles A) / (mass of colloidal silica C)] × 100 (%). That is, the mass of the antibacterial metal particles A is divided by the mass of colloidal silica C, and the value expressed in% is preferably 0.01 to 10.0%.
When the mass ratio of the antibacterial metal particles A is 0.01% or more, algae-proof and antifungal properties can be exhibited, and when it is 10% or less, the coating film derived from the antibacterial metal-containing compound is colored. Is preferable because it reduces.

The ratio of the mass of the antibacterial metal particles A to the mass of colloidal silica C in the aqueous composition of the present embodiment is more preferably 0.01% or more, 0.05% or more, 0.1% or more, 0. .5% or more, 1.0% or more, 1.5% or more, 2.0% or more, 2.5% or more, 3.0% or more, 3.5% or more, 10.0% or less, 9 5.5% or less, 9.0% or less, 8.5% or less, 8.0% or less, 7.5% or less, 7.0% or less, 6.5% or less, 6.0% or less, 5.5 % Or less, 5.0% or less.
The specific numerical range is preferably 0.01 to 10.0%, more preferably 0.05% to 0.05% from the viewpoint of the balance between algae resistance, mold resistance, and coloration of the coating film. It is in the range of 8.0%, more preferably 0.1 to 5.0%.

In the aqueous composition of the present embodiment, the average particle size of the antibacterial metal particles A is the ratio of the average particle size of the colloidal silica C to (the average particle size of the antibacterial metal particles A) / (the average particle size of the colloidal silica C). The diameter) is preferably 0.01 to 10.0.
The ratio of the average particle diameter is 0.01 or more, for example, the average particle diameter of the antibacterial metal particles A is constant and the average particle diameter of colloidal silica C is kept small to 0.01 or more in the coating film. Since the specific surface area of the colloidal silica C is secured, the hydrophilicity of the coating film, that is, the antifouling property is good, which is preferable.
Further, the transparency of the coating film is made by setting the average particle size ratio to 10.0 or less, for example, the particle size of colloidal silica C is constant and the particle size of the antibacterial metal particles A is suppressed to 10.0 or less. It is preferable because the coloring property derived from metal is suppressed.

The ratio of the average particle diameters (average particle diameter of antibacterial metal particles A) / (average particle diameter of colloidal silica C) is 0.01 or more, 0.02 or more, 0.03 or more, 0.04 or more, 0. 0.05 or more, 1.0 or more, 2.0 or more are preferable, 10.0 or less, 9.0 or less, 8.0 or less, 7.0 or less, 6.0 or less, 5.0 or less, 4.0 or less. , 3.0 or less is preferable.
The specific numerical range of this ratio (average particle size of antibacterial metal particles A) / (average particle size of colloidal silica C) is 0.01 from the viewpoint of the balance between transparency, colorability, and hydrophilicity of the coating film. It is preferably ~ 10.0, more preferably 0.01 to 5.0, still more preferably 0.02 to 3.0.

Examples of the antibacterial metal particles A include heavy metals such as silver, gold, palladium, platinum, cobalt, nickel, copper, zinc, lead, and manganese.
Among these, the antibacterial metal particles A preferably include gold, silver, copper, platinum, and zinc, and more preferably gold, silver, and copper, from the viewpoint of safety and practicality. Can be mentioned. These heavy metals may be one kind or a combination of two or more kinds.

Examples of the existing form of the antibacterial metal particles A include the form of the single metal, the form of the metal compound, the form of an ionic state, the form of being complexed with another compound, and the like. Among these, the single metal. In particular, the form of a metal simple substance or a metal compound that is sparingly soluble in water is preferable.
This is because the simple substance of the metal or the antibacterial metal-containing compound is sparingly soluble in water, so that the metal ions themselves generated by the dissolution of the metal are reduced by absorbing light, and as a result, the color of the coating film changes over time. This is because the possibility of change can be reduced. Further, when the metal simple substance or the antibacterial metal-containing compound is sparingly soluble in water, it is suppressed from flowing out due to moisture such as rain in an outdoor environment, thereby sustaining the effect of the present invention. be able to.

The component of the antibacterial metal particles A is preferably one or more selected from the group consisting of gold, silver, copper, gold compounds, silver compounds and copper compounds.
Examples of the components of the antibacterial metal particles A include, in the case of gold, for example, gold alone, in the case of silver, silver alone and its compounds, for example, silver oxide and silver chloride, and in the case of copper. , Copper alone and its compounds, such as copper oxide and copper hydroxide.

Various chemical reactions can be used as a method for producing the antibacterial metal particles A, and among them, a condition in which a water-soluble antibacterial metal-containing compound containing a metal ion as a precursor is dissolved in water and the metal ion is present. Below, a method of adding a water-soluble reducing agent to generate antibacterial metal particles A by a reduction reaction is preferable because a high yield can be achieved and the reaction time can be shortened.

(Compound B)
The aqueous composition of the present embodiment is at least one of the functional groups selected from the group consisting of a functional group B1 that interacts with the antibacterial metal particles A in the molecule, a silanol group, and a functional group that interacts with a siloxane bond. Contains compound B containing the group B2.

By containing the compound B, when the coating film is formed, the antibacterial metal particles A and the functional group B1 interact with each other, and the functional group B2 interacts with colloidal silica C or the like described later, and the antibacterial metal particles. The action of immobilizing A in the coating film is improved. Therefore, it is suppressed that the antibacterial metal particles A fall off from the surface of the coating film, the cross section of the crack, etc. due to external factors such as rainwater and expansion and contraction of the coating film, and as a result, the algae-proof and antifungal properties are maintained for a long period of time. ..
Further, with respect to a coating film formed of an inorganic compound, the inclusion of this compound B has the effect of improving the interaction between the inorganic compound and the antibacterial metal particles A and improving the toughness of the coating film. The crack resistance of the coating film is improved.

In the compound B, examples of the functional group B1 that interacts with the antibacterial metal particles A include an aromatic group and a polar group, and examples of the aromatic group include a phenyl group, a naphthyl group, an imidazole group and the like. Be done. Examples of the polar group include an epoxy group, a thiol group, an amino group and the like.
In particular, it is preferable to use a thiol group or an amino group having a strong interaction with a metal because the effect of immobilizing the antibacterial metal particles A on the coating film is enhanced.

Further, the compound B contains, in its molecule, a functional group B2 which is at least one selected from the group consisting of a silanol group and a functional group that interacts with a siloxane bond.
Examples of the functional group B2 include a silanol group and an amide group. In particular, the silanol group is preferable from the viewpoint of strong hydrogen bond with the silanol group of colloidal silica, good compatibility with water, and solubility and dispersibility.
The silanol group may be an alkoxysilane group before hydrolysis or may be condensed to form a siloxane bond. In particular, from the viewpoint of further enhancing the above-mentioned immobilization effect by interacting with both the antibacterial metal particles A and the colloidal silica C, the compound B contains a thiol group or an amino group as the functional group B1 and is used as the functional group B2. It is preferably a silane compound containing at least one selected from the group consisting of a silanol group and a functional group that interacts with a siloxane bond.

Examples of Compound B having a thiol group or an amino group and having a silanol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-aminopropyltri. Hydrolyzates such as methoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, or compounds in which they are partially condensed can be mentioned.

The ratio of the mass of compound B to the mass of antibacterial metal particles A in the aqueous composition of the present embodiment [(mass of compound B) / (mass of antibacterial metal particles A)] × 100 (%), that is, The mass of the compound B is divided by the mass of the antibacterial metal particles A, and the value expressed in% is preferably in the range of 1 to 300%.
When it is 1% or more, it is preferable because the immobilization effect of the antibacterial metal particles A on the coating film and the crack resistance are exhibited, and when it is 300% or less, the surplus that does not interact with the antibacterial metal particles A is exhibited. Compound B is reduced, which is preferable because the storage stability of the aqueous composition is improved and the void ratio of the coating film is prevented from being lowered.

The ratio of the mass of the compound B to the mass of the antibacterial metal particles A is preferably 1% or more, 2% or more, 3% or more, 4% or more, 5% or more, preferably 300% or less, 290% or less, and 280%. Below, 270% or less, 260% or less, 250% or less, 230% or less, 210% or less, 200% or less are preferable.
The specific numerical range is preferably 1 to 300% from the viewpoint of the balance between the effect of immobilizing the antibacterial metal particles A in the coating film and the storage stability of the aqueous composition. It is more preferably 2 to 280%, still more preferably 4 to 250%.

(Coloidal Silica C)
Examples of the colloidal silica C include acidic colloidal silica using water as a dispersion medium, basic colloidal silica, and the like.

Examples of acidic colloidal silica include Snowtex (registered trademark) -O manufactured by Nissan Chemical Industries, Ltd., Snowtex-OS manufactured by Nissan Chemical Industries, Ltd., Adeleite (registered trademark) AT-20Q manufactured by Asahi Denka Kogyo Co., Ltd., and Clevosol manufactured by Clariant Japan. (Registered trademark) 20H12, Clevosol 30CAL25 and the like can be mentioned.

Examples of the basic colloidal silica include silica stabilized by adding alkali metal ion, ammonium ion, amine and the like, and specifically, Snowtex-NS and Snowtex-20 manufactured by Nissan Chemical Industry Co., Ltd. , Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, Snowtex-K, Snowtex-XL, Snowtex-YL ,; Asahi Denka Kogyo Examples thereof include Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, and Adelite AT-40 manufactured by the same company.

As the colloidal silica, one of these or a combination of two or more thereof may be used.

The content of colloidal silica C in the aqueous composition is preferably 50 to 99% with respect to the mass of the total solid content contained in the aqueous composition.
When it is 50% or more, not only the hydrophilicity is exhibited and the antifouling property is improved, but also the interaction with the above-mentioned compound B is improved and the antibacterial metal particles A are easily immobilized in the coating film. Therefore, long-term algae resistance and mold resistance are improved.
Further, when it is 99% or less, the content of the antibacterial metal particles A and other components such as synthetic resin and surfactant is relatively increased, and only long-term algae resistance and antifungal property are exhibited. This is preferable because it is advantageous in forming a coating film.

The ratio of the mass of colloidal silica C in the aqueous composition to the mass of the total solid content contained in the aqueous composition is preferably 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 99. % Or less, 95% or less, 90% or less, 85% or less, 80% or less are preferable.
The specific numerical range is preferably 50 to 99%, more preferably 55 to 98%, still more preferably 60, from the viewpoint of the balance between hydrophilicity, algae resistance, mold resistance, and film formation property. It is ~ 95%.

In the specification of the present application, the "total solid content" means the total mass of the non-volatile components contained in the aqueous composition. In addition, the non-volatile content is measured by using a method based on JIS K 5601-1-2.

(Particle D having photocatalytic activity)
The aqueous composition in the present embodiment may further contain photocatalytic particles D having photocatalytic activity.
By including the photocatalytic particles D, it is possible to further improve the antifouling property by utilizing the organic matter decomposition and superhydrophilicity known as photocatalytic action.

Examples of the particles D having photocatalytic activity include titanium oxide (TIO ₂ ), zinc oxide (ZnO), strontium titanate (SrTiO ₃ ), gallium phosphate (GaP), and barium titanate (eg, BaTIO ₃ , BaTIO ₄ ). , BaTi ₄ O ₉ etc.), potassium niobate (K ₂ NbO ₃ ), niobide pentoxide (Nb ₂ O ₅ ), iron oxide (eg Fe ₂ O ₃ ), tungsten oxide (eg WO ₃ ), oxidation Examples thereof include tin (for example, SnO ₂ ) and copper oxide (for example, Cu ₂ O).
Further, for the purpose of improving the dispersion stability in the dispersion medium, the above particles can be used by modifying and coating the surface with silicon dioxide (silica), aluminum oxide (alumina) or the like.

Among these, as the photocatalyst particles D having photocatalytic activity, it is preferable to use at least one of titanium oxide, tungsten oxide, and silica-coated titanium oxide from the viewpoint of safety and cost. The crystal structure of titanium oxide includes, for example, anatase type, rutile type, brookite type and the like, and any of them may be used.

Antibacterial metal particles A may be supported on the surface of the particles D having photocatalytic activity.
It is known that some of the antibacterial metal particles A interact with a photocatalytic compound to exhibit physical properties such as visible light responsiveness, and exhibit antibacterial properties even in an indoor environment where there is little ultraviolet light.

(Other ingredients)
The aqueous composition of the present embodiment contains synthetic resins, emulsion particles, defoaming agents, coloring agents, coupling agents, thickening agents, crosslinking agents, freeze stabilizers, matting agents, and the like, as long as the effects are not lost. Cross-linking reaction catalysts, pigments, curing catalysts, cross-linking agents, fillers, anti-skinning agents, dispersants, wetting agents, light stabilizers, antioxidants, UV absorbers, rhology control agents, defoaming agents, film-forming aids. Contains other ingredients such as rust preventives, dyes, plastics, lubricants, reducing agents, preservatives, antifungal agents, deodorants, anti-yellowing agents, antistatic agents or antistatic agents. May be good.

The coating film and the aqueous composition of the present embodiment can be formed on a base material or a coating film, and the base material and the coating film can be applied to various materials.

The present invention will be specifically described with reference to the following Production Examples, Examples, and Comparative Examples, but these do not limit the scope of the present invention.
Various physical properties were measured by the methods shown below.

1. 1. Quantification of antibacterial metal and calculation of residual rate of antibacterial metal in antibacterial metal-containing compound in coating film after JIS K 5600-7-7 test In each example after JIS K 5600-7-7 test The quantification of the antibacterial metal of the antibacterial metal-containing compound in the coating film of No. 1 was carried out as follows. As the metal element analyzed in each example, the element of the antibacterial metal particle A contained in each coating film, that is, any element of gold or silver copper was analyzed.
A commercially available white enamel paint (water-based ceramic silicon manufactured by SK KAKEN Co., Ltd.) is applied on a polypropylene plate (P310A manufactured by Takiron Co., Ltd., 2 x 70 x 150 mm) using a spray, and dried at room temperature for 2 days. A coating of .15 g was formed.
Then, each aqueous composition was applied onto the white enamel coating film using a spray, dried and cured at room temperature for 7 days to form a 5 mg coating film, and two test pieces were prepared.
For one of the specimens, the white enamel coating and the coating containing each aqueous composition were peeled off from the polypropylene substrate, the mass thereof was weighed, and the mixture was dissolved by acid and ultrasonic waves, and then inductively coupled. The amount of antibacterial metal-containing compound was quantified by analyzing the amount of metal contained in the coating film using a plasma mass spectrometer (ICPMS-2030 manufactured by Shimadzu Corporation), and the obtained value (μg /). g) was defined as the antibacterial metal-containing compound content M0 before the test.
In addition, the other single test piece not subjected to the above analysis was subjected to a 2500-hour exposure test in accordance with JIS K 5600-7-7. Then, the amount of the antibacterial metal-containing compound was quantified using the above-mentioned measuring method and equipment, and the obtained value (μg / g) was defined as the amount of the antibacterial metal-containing compound M1 after the test, and the following formula (1) was used. ) Was used to calculate the residual ratio (%) of the antibacterial metal-containing compound in the coating film.

2. 2. Measurement of Porosity in Coating Film The porosity in coating film (volume fraction occupied by air) was determined as follows.
Each aqueous composition was spin-coated on a glass substrate (5 × 5 cm) and dried at room temperature to form a coating film.
After that, the refractive index for each wavelength of 230 to 800 nm was measured using a reflection spectroscopic film thickness meter (FE-3000 manufactured by Otsuka Denshi), and the glass was measured on the back side of the glass substrate using the reflection spectroscopic film thickness meter. The refractive index of the substrate was measured.
Next, the intensity of the reflected light interfering between the glass substrate and the coating film at intervals of 2 nm between 230 and 800 nm on the coating film side is measured, and the refractive index and interference of the glass substrate for each measured wavelength are measured. Using the intensity of the reflected light, the refractive index and film thickness of the coating film were calculated and searched to fit the measured values by the minimum square method, and the refractive index α1 (nm) of the coating film was obtained.
Furthermore, using the following formula (2), the refractive index α2 assuming that no voids exist in the coating film was obtained.
The following values were obtained for the theoretical refractive index of each compound used in each example.
Particle A: Gold = 0.34, Silver = 0.12, Copper oxide = 2.71
Compound B: 3-mercaptopropyltrimethoxysilane = 1.44, 3-aminopropyltrimethoxysilane = 1.42, phenyltrimethoxysilane = 1.46
Silica C: Colloidal silica = 1.45
Particle D: Titanium oxide = 2.25

The porosity α3 in the coating film was obtained by using the following mathematical formula (3) for α1 and α2 obtained above.

3. 3. Measurement of average particle size (average particle size of antibacterial metal particles A)
The average particle size of the antibacterial metal particles A was determined by the following method. Each aqueous composition containing the antibacterial metal particles A was dropped onto the collodion membrane.
Then, after drying under vacuum conditions for 1 hour, the surface was observed with a scanning transmission electron microscope, 50 arbitrary antibacterial metal particles A observed were selected, and their number average particle diameters were calculated.
(Average particle size of colloidal silica C)
The average particle size of colloidal silica C is diluted by adding water so that the solid content in the sample is 0.1 to 20% by mass, and a wet particle size analyzer (NanotracWave-EX150 manufactured by Microtrac Bell) is used. The cumulative 50% diameter when measured using and displayed as a volume distribution was taken as the average particle diameter.

4. Antifouling property The antifouling property of the coating film was evaluated as follows.
A white enamel finishing material for outer walls (water-based ceramic silicone manufactured by SK KAKEN Co., Ltd.) is applied on an alumite sulfate base material (JIS H 4000 (A1100P) 1 x 70 x 150 mm manufactured by Testpiece Co., Ltd.) so that the film thickness becomes 100 μm after drying. Then, it was cured at room temperature for 2 days. The composition of each example was spray-coated on the coating film, dried and cured at room temperature for 7 days to obtain a coating film of about 5 mg, and a test piece was prepared.
The color difference of the obtained test piece before and after painting was measured, and the color difference before painting was used as a standard and evaluated as ΔE.
The lower the color difference ΔE, the less the change in appearance, that is, the better the weather resistance. As for the color difference, the color difference from the standard plate was determined using a color guide (manufactured by BYK Gardener).
[Evaluation criteria]
◯: The color difference ΔE was less than 1.6.
Δ: The color difference ΔE was less than 1.6 to 3.0.
X: The color difference ΔE was 3.0 or more.

5. Low colorability The low colorability of the coating film was evaluated as follows.
A white enamel finishing material for outer walls (water-based ceramic silicone manufactured by SK KAKEN Co., Ltd.) is applied on an alumite sulfate base material (JIS H 4000 (A1100P) 1 x 70 x 150 mm manufactured by Testpiece Co., Ltd.) so that the film thickness becomes 100 μm after drying. Then, it was cured at room temperature for 2 days. After curing, the color difference before painting was measured, the composition of each example was spray-coated on the coating film, dried and cured at room temperature for 7 days to obtain a coating film of about 5 mg, and a test piece was prepared. ..
The color difference of the obtained test piece was measured, the color difference before painting was used as a standard, and the state change before and after painting was evaluated as ΔE.
The lower the color difference ΔE, the less the change in appearance, that is, the better the weather resistance. As for the color difference, the color difference from the standard plate was determined using a color guide (manufactured by BYK Gardener).
[Evaluation criteria]
◯: The color difference ΔE was less than 1.6.
Δ: The color difference ΔE was less than 1.6 to 3.0.
X: The color difference ΔE was 3.0 or more.

6. Anti-algae and anti-fungal (long-term)
A white enamel finishing material for outer walls (water-based ceramic silicone manufactured by SK KAKEN Co., Ltd.) is applied on an alumite sulfate base material (JIS H 4000 (A1100P) 1 x 70 x 150 mm manufactured by Testpiece Co., Ltd.) so that the film thickness becomes 100 μm after drying. Then, it was cured at room temperature for 2 days.
The aqueous composition of each example was spray-coated on the coating film, dried and cured at room temperature for 7 days to obtain a coating film of about 5 mg, and a test piece was prepared.
After that, after conducting a 2500-hour exposure test in accordance with JIS K 5600-7-7, the test piece was exposed outdoors at 90 ° north surface on the land where there was a forest in the vicinity of Choshi City, Chiba Prefecture, and the lawn was growing. The test was carried out.
Judgment was made one year after exposure.
[Evaluation criteria]
◯: No growth of algae or mold was observed by visual observation.
Δ: No growth of algae and mold was observed by visual observation, but growth was observed by loupe observation at a magnification of 7 times.
X: Growth of algae and mold was observed by visual observation.

7. Crack resistance of the coating film The stain resistance of the coating film was evaluated as follows. A white enamel finishing material for outer walls (water-based ceramic silicone manufactured by SK KAKEN Co., Ltd.) is applied on an alumite sulfate base material (JIS H 4000 (A1100P) 1 x 70 x 150 mm manufactured by Testpiece Co., Ltd.) so that the film thickness becomes 100 μm after drying. Then, it was cured at room temperature for 2 days.
The aqueous composition of each example was spray-coated on the coating film, dried and cured at room temperature for 7 days to obtain a coating film of about 5 mg, and a test piece was prepared.
The obtained test piece was placed outdoors in Kawasaki Ward, Kawasaki City, with the coating film on the south surface and perpendicular to the ground, and exposed for one year.
One year later, a 100-fold magnified observation was carried out with a microscope (VHX-5000 manufactured by KEYENCE CORPORATION), and the evaluation was made according to the following criteria.
[Evaluation criteria]
◯: The maximum width of cracks observed in the visual field was less than 1.5 μm.
Δ: The maximum width of cracks observed in the visual field was in the range of 1.5 to less than 3.0 μm.
X: The maximum width of cracks observed in the visual field was 3.0 μm or more.

8. Synthesis of particles D with photocatalytic activity (silica-modified rutile-type titanium dioxide)
The particles D having photocatalytic activity (photocatalytic particles D) used in the production examples described later were synthesized as follows.
700 mL of an aqueous solution of titanium tetrachloride having a concentration of 200 g / L as TiO ₂ and an aqueous solution of sodium hydroxide having a concentration of 100 g / L as Na ₂ O were added in parallel into water so as to maintain the pH of the system at 5-9.
Then, after adjusting the pH of the system to 7, it was filtered and washed until the conductivity of the filtrate became 100 μS / cm to obtain titanium oxide wet cake 1 having a solid content concentration of 28.3% by mass.
The titanium oxide wet cake 1 had a rutile-type structure, and the average particle size thereof was 8 nm.
The obtained rutile-type titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry. 1 L of this slurry is placed in a 3 L flask, 1 L of 1N nitric acid is added so that the molar ratio of titanium oxide to nitric acid (titanium oxide / nitric acid) is 1, and the mixture is heated to a temperature of 95 ° C. The temperature was maintained for 2 hours for acid heat treatment.
Next, the slurry after the acid heat treatment was cooled to room temperature, neutralized (pH = 6.7) with 28% aqueous ammonia, filtered, and then washed until the conductivity of the filtrate became 100 μS / cm. , Titanium oxide wet cake 2 having a solid content concentration of 25% by mass was obtained.
A 10% by mass sodium hydroxide aqueous solution was added to the obtained titanium oxide wet cake 2, repulped, and then dispersed in an ultrasonic cleaner for 3 hours to have a pH of 10.5 and a solid content concentration of 10% by mass. An alkaline titanium oxide sol was obtained.
2 L of this alkaline titanium oxide sol was placed in a 3 L flask, heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L was added as SiO ₂ , and then the temperature was raised to 90 ° C. After aging for 1 hour, 10% sulfuric acid was added to adjust the pH to 6, and the surface of titanium oxide was surface-treated with a hydrous oxide of silicon.
The obtained titanium oxide sol was cooled to room temperature, 5.4 L of pure water was added, impurities were removed and concentrated using a desalting and concentrating device, and the pH was 7.3 and the solid content concentration was 29% by mass. A neutral rutile type titanium oxide sol was obtained.
It contained 15% by mass of silicon hydrous oxide with respect to TiO ₂ based on SiO ₂ .
The average particle size of titanium oxide in this sol was 50 nm.

[Production Example 1] Gold-supported titanium oxide (A-1)
400 g of an aqueous dispersion (solid content: 2% by mass) of the photocatalyst particles D synthesized by the method described in 8 above was placed in a 500 mL flask and heated to 65 ° C.
When the temperature reached 65 ° C., 3.83 g of an aqueous solution of chloroauric acid tetrahydrate (concentration: 1% by mass) was added, and the mixture was stirred for 10 minutes. Then, 0.79 g of an aqueous tannic acid solution (concentration: 1% by mass) was added. After the addition, the mixture was stirred for 1 hour while being maintained at 65 ° C., then heated to 80 ° C., and after reaching 80 ° C., 0.12 g of 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 6 hours. did.
After 6 hours, the mixture was cooled to room temperature to obtain gold-supported titanium oxide (A-1).
The average particle size of the antibacterial metal particles in the obtained composite was 8 nm.

[Production Example 2] Silver-supported titanium oxide (A-2)
The aqueous solution of gold tetrachloride tetrahydrate (concentration: 1% by mass) used in the above [Production Example 1] was adjusted to 3.78 g of an aqueous solution of silver nitrate (concentration: 5% by mass), and an aqueous solution of tannic acid (concentration: 1% by mass). Was synthesized by the same method as in [Production Example 1] except that the amount of 3-mercaptopropyltrimethoxysilane was 0.24 g, and silver-supported titanium oxide (A-2) was obtained. .. The average particle size of the antibacterial metal-bearing particles in the obtained composite was 4 nm.

[Production Example 3] Copper oxide-supported titanium oxide (A-3)
The silver nitrate aqueous solution (concentration: 5% by mass) used in the above [Production Example 2] was 6.24 g of copper sulfate pentahydrate (concentration: 5% by mass), and the amount of the tannic acid aqueous solution (concentration: 1% by mass) added. Was synthesized in the same manner as in [Production Example 2] except that the concentration was 10.60 g and the amount of 3-mercaptopropyltrimethoxysilane was 0.16 g to obtain copper oxide-supported titanium oxide (A-3). The average particle size of the antibacterial metal particles in the obtained composite was 5 nm.

[Production Example 4] Silver colloid (A-4)
400 g of ion-exchanged water was placed in a 500 mL flask and heated to 80 ° C. When the temperature reached 80 ° C., 1.25 g of an aqueous silver nitrate solution (concentration: 5% by mass) was added, and the mixture was stirred for 5 minutes. Then, 1.04 g of an aqueous tannic acid solution (concentration: 1% by mass) and 1.75 g of an aqueous solution of sodium citrate dihydrate (concentration: 10% by mass) were added at the same time.
After the addition, the mixture was stirred for 1 hour while being maintained at 80 ° C., cooled to 25 ° C., and after reaching 25 ° C., 1.02 g of an aqueous ammonia solution (concentration: 1% by mass) was added and stirred for 5 minutes.
Then, 4.0 mg of 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred for 6 hours to obtain a silver colloid (A-4).
The average particle size of the antibacterial metal particles in the obtained composite was 8 nm.

[Production Example 5] Copper oxide colloid (A-5)
400 g of ion-exchanged water and 2.96 g of an aqueous solution of sodium citrate dihydrate (concentration: 10% by mass) were placed in a 500 mL flask and heated to 80 ° C.
When the temperature reached 80 ° C., 23.20 g of an aqueous ammonia solution (concentration: 5% by mass) was added, and the mixture was stirred for 5 minutes. Then, 3.20 g of an aqueous solution of copper sulfate pentahydrate (concentration: 5% by mass) was added, and after stirring for 5 minutes, 16.37 g of an aqueous solution of tannic acid (concentration: 1% by mass) was added.
After the addition, the mixture was stirred for 1 hour while being maintained at 80 ° C., cooled to 25 ° C., and after reaching 25 ° C., the mixture was stirred for 5 minutes. Then, 2.0 mg of 3-mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred for 6 hours to obtain a copper oxide colloid (A-5).
The average particle size of the antibacterial metal particles in the obtained composite was 11 nm.

[Production Example 6] Silver colloid (A-6)
Silver was synthesized by the same method as in [Production Example 4] except that 3-Aminopropyltrimethoxysilane (KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.) was used as 3-mercaptopropyltrimethoxysilane in [Production Example 4]. A colloid (A-6) was obtained.
The average particle size of the antibacterial metal particles in the obtained composite was 8 nm.

[Production Example 7] Silver colloid (A-7)
400 g of ion-exchanged water was placed in a 500 mL flask and heated to 80 ° C.
When the temperature reached 80 ° C., 1.25 g of an aqueous silver nitrate solution (concentration: 5% by mass) was added, and the mixture was stirred for 5 minutes.
Then, 1.04 g of an aqueous tannic acid solution (concentration: 1% by mass) and 1.75 g of an aqueous solution of sodium citrate dihydrate (concentration: 10% by mass) were added at the same time.
After the addition, the mixture was stirred for 1 hour while being maintained at 80 ° C., and then cooled to room temperature to obtain a silver colloid (A-7).
The average particle size of the antibacterial metal particles in the obtained composite was 4 nm.

[Production Example 8] Silver colloid (A-8)
The silver colloid (A) was synthesized by the same method as in [Production Example 4] except that 3-mercaptopropyltrimethoxysilane in [Production Example 4] was changed to phenyltrimethoxysilane (KBM-103 manufactured by Shin-Etsu Chemical Co., Ltd.). -8) was obtained.
The average particle size of the antibacterial metal particles in the obtained composite was 8 nm.

[Production Example 9] Silver colloid (A-9)
A silver colloid (A-9) was obtained by synthesizing in the same manner as in [Production Example 4] except that the amount of 3-mercaptopropyltrimethoxysilane added in [Production Example 4] was 0.32 mg. ..
The average particle size of the antibacterial metal particles in the obtained composite was 4 nm.

[Example 1]
137.1 g of gold-supported titanium oxide (A-1) produced in Production Example 1 and water-dispersed colloidal silica having an average particle diameter of 10 nm, which is a basic colloidal silica (Snowtex NS manufactured by Nissan Chemical Industries, Ltd., solid content 20). Weight%) 123.4 g, 1.5 g of fluorocarbon surfactant (Megafuck F-444 manufactured by DIC), which is a perfluoroalkylethylene oxide adduct, and ion-exchanged water to reduce the solid content to 0.1% by mass. An aqueous composition was prepared by blending 140 g of the adjusted fading dye (methylene blue manufactured by Kishida Chemical Co., Ltd.), adding it to ion-exchanged water so that the total mass became 1000 g, and stirring the mixture.
A photocatalytic coating film was prepared from this aqueous composition according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 2]
The water-based composition is the same as in [Example 1] except that the gold-supported titanium oxide (A-1) in [Example 1] is the silver-supported titanium oxide (A-2) produced in Production Example 2. I made a thing.
A photocatalytic coating film was prepared from this aqueous composition according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 3]
Water-based in the same manner as in [Example 1], except that the gold-supported titanium oxide (A-1) in [Example 1] was replaced with the copper-supported titanium oxide (A-3) produced in Production Example 3. A composition was prepared.
A photocatalytic coating film was prepared from this aqueous composition according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 4]
550 g of silver colloid (A-4) produced in Production Example 4 and water-dispersed colloidal silica having an average particle diameter of 10 nm, which is a basic colloidal silica (Snowtex NS manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass) 123 .53 g, acrylic-silicone emulsion (G639S manufactured by Asahi Kasei Co., Ltd.) diluted to 30% by mass with ion-exchanged water, 8.97 g, and perfluoroalkylethylene oxide adduct (Surflon S-232 manufactured by AGC Seimi Chemical Co., Ltd.). ) 10.33 g and 140 g of a fading dye (methylene blue manufactured by Kishida Chemical Co., Ltd.) whose solid content is adjusted to 0.1% by mass with ion-exchanged water are mixed, and the mixture is added with ion-exchanged water so that the total amount becomes 1000 g and stirred. By doing so, an aqueous composition was prepared.
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 5]
An aqueous composition was prepared in the same manner as in [Example 4], except that the silver colloid (A-4) in [Example 4] was the silver colloid (A-5) prepared in Production Example 5. ..
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 6]
An aqueous composition was prepared in the same manner as in [Example 4], except that the silver colloid (A-4) in [Example 4] was the silver colloid (A-6) prepared in Production Example 6. ..
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 7]
550 g of copper oxide colloid (A-5) produced in Production Example 5 and water-dispersed colloidal silica having an average particle diameter of 10 nm, which is a basic colloidal silica (Snowtex NS manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass). 96.08 g, 27.27 g of acrylic-silicone emulsion (G612 manufactured by Asahi Kasei Co., Ltd.) diluted to 30% by mass with ion-exchanged water, and a perfluoroalkylethylene oxide adduct (Surflon S-manufactured by AGC Seimi Chemical Co., Ltd.). 232) Add 10.33 g and 140 g of a fading dye (methylene blue manufactured by Kishida Chemical Co., Ltd.) whose solid content is adjusted to 0.1% by mass with ion-exchanged water, and add with ion-exchanged water so that the total amount becomes 1000 g. An aqueous composition was prepared by stirring.
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 8]
An aqueous composition was prepared in the same manner as in [Example 7] except that the amount of colloidal silica was 109.80 g and the amount of acrylic-silicone emulsion was 18.12 g in [Example 7].
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Example 9]
550 g of copper oxide colloid (A-5) produced in Production Example 5 and water-dispersed colloidal silica having an average particle diameter of 5 nm, which is a basic colloidal silica (Snowtex NXS manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass). 36.60 g, water-dispersed colloidal silica with an average particle diameter of 22 nm (Snowtex N40 manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass) 48.04 g, which is a basic colloidal silica, and ion-exchanged water have a concentration of 30. 8.97 g of acrylic-silicone emulsion (G639S manufactured by Asahi Kasei Co., Ltd.) diluted to mass%, 10.33 g of (Surflon S-232 manufactured by AGC Seimi Chemical Co., Ltd.), which is a perfluoroalkylethylene oxide adduct, and solid with ion-exchanged water. An aqueous composition was prepared by blending 140 g of a fading dye (methylene blue manufactured by Kishida Chemical Co., Ltd.) whose amount was adjusted to 0.1% by mass, adding it to ion-exchanged water so that the total amount became 1000 g, and stirring the mixture.
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[ Reference Example 10]
The silver colloid (A-4) produced in Production Example 7 was prepared from the silver colloid (A-4) in [Example 4].
An aqueous composition was prepared in the same manner as in [Example 4] except that A-7).
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[ Reference Example 11]
An aqueous composition was prepared in the same manner as in [Example 4], except that the silver colloid (A-4) in [Example 4] was the silver colloid (A-8) prepared in Production Example 8 . ..
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[ Reference Example 12]
An aqueous composition was prepared in the same manner as in [Example 4], except that the silver colloid (A-4) in [Example 4] was the silver colloid (A-9) prepared in Production Example 9 . ..
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Comparative Example 1]
The silver colloid (A-4) produced in Production Example 4 was concentrated 10-fold by vacuum distillation.
Polyvinyl alcohol powder (PVA217 manufactured by Kuraray Co., Ltd.) was slowly added to 549 g of this 10-fold concentrated colloidal solution with stirring.
After addition, 13.73 g of water-dispersed colloidal silica (Snowtex NS manufactured by Nissan Chemical Industry Co., Ltd., solid content: 20% by mass) having an average particle diameter of 12 nm and a fluorocarbon surfactant (Surflon S-232 manufactured by AGC Seimi Chemical Co., Ltd.) 10 Mix .33 g and 140 g of fading dye (“Methylene Blue” manufactured by Kishida Chemical Co., Ltd.) whose solid content is adjusted to 1.0% by mass with ion-exchanged water, add to ion-exchanged water so that the total amount becomes 1000 g, and stir. By doing so, an aqueous composition was prepared.
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

[Comparative Example 2]
An aqueous composition was prepared in the same manner as in [Example 4], except that the silver colloid (A-4) was an aqueous solution of copper sulfate pentahydrate (concentration: 100 ppm) in [Example 4].
A coating film of this aqueous composition was prepared according to each of the above methods, and various evaluation results are shown in Table 3.

The coating film and the water-based composition of the present invention have industrial applicability as a coating material for building exteriors, interior materials, exterior display applications, automobiles, displays and the like.

Claims (6)

A coating film containing an antibacterial metal-containing compound,
The aqueous composition forming the coating film is
water and,
Antibacterial metal particles A and
A functional group B1 that interacts with the antibacterial metal particles A in the molecule, a silanol group, and a shiroki.
A functional group that is at least one selected from the group consisting of functional groups that interact with a sun bond.
Compound B containing B2 and
Colloidal silica C and
, Containing,
The ratio of the mass of the antibacterial metal particles A to the mass of the colloidal silica C is 0.0.
It is 1 to 10.0%,
The ratio of the mass of the compound B to the mass of the antibacterial metal particles A [(mass of compound B) / (mass of antibacterial metal particles A)] × 100 (%) is 1 to 300%.
The compound B is 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. A hydrolyzate of a compound selected from the group consisting of triethoxysilane, or at least one selected from the group consisting of a compound in which these are partially condensed.
The total mass of the antibacterial metal-containing compound in the coating film after 2500 hours in the exposure test conforming to JIS K 5600-7-7 is the total mass.
It is 5% or more with respect to the total mass of the antibacterial metal-containing compound in the coating film before the exposure test.
There are voids in the coating film,
The porosity of the coating film is 1 to 30%.
Coating film. The ratio of the average particle size of the antibacterial metal particles A to the average particle size of the colloidal silica C in the aqueous composition , (average particle size of the antibacterial metal particles A) / (average particle size of the colloidal silica C) is , 0.01 to 10, according to claim 1 . The coating film according to claim 1 or 2 , wherein the content of the colloidal silica C in the water-based composition is 50 to 99% with respect to the total solid content contained in the water-based composition. The coating film according to any one of claims 1 to 3 , wherein the antibacterial metal particles A are at least one selected from the group consisting of gold, silver, and copper, and compounds thereof. The coating film according to any one of claims 1 to 4 , wherein the aqueous composition further contains particles D having photocatalytic activity. The coating film according to claim 5 , wherein the particles D having photocatalytic activity are at least one selected from the group consisting of titanium oxide, tungsten oxide, and silica-coated titanium oxide.