JP2020147679A - Coating composition - Google Patents

Abstract

To provide a coating composition suitable for forming a coated film excellent in anti-allergic property, anti-bacterial property and durability.SOLUTION: There are provided a coating composition that contains composite particles (A) of anatase type titanium oxide, silver particles having a particle diameter of 0.3-100 μm and calcium phosphate, a resin (B) and a solvent (C), in which 1-300 pts.mass of the composite particles (A) are contained based on 100 pts.mass of the resin (B), the resin (B) has a water absorption rate of 0-50%, and 0.5-40 pts.mass of the resin (B) in terms of solid content is contained based on 100 pts.mass of the whole coating composition.SELECTED DRAWING: None

Description

The present invention relates to a coating composition. More specifically, the present invention relates to a coating composition containing anatase-type titanium oxide, silver particles having a specific particle size and composite particles (A) of calcium phosphate, a resin (B) and a solvent (C), a coating method, and a coated article.

In recent years, the number of people suffering from pollinosis caused by cedar pollen and allergic diseases such as bronchial asthma caused by house dust caused by mites, pollinosis, allergic rhinitis, and atopic dermatitis has become a serious problem. .. In order to reduce the symptoms of allergic diseases or prevent new sensitization, it is necessary to reduce allergens, which are the causative substances that cause allergic symptoms, and methods such as removal using air conditioners and air purifiers and drugs such as tannic acid There is known a method of denatures and detoxifies allergen proteins. Since various allergens exist in the environment, in order to further enhance the allergen reduction effect, for example, it is necessary to impart anti-allergen properties to the coating film obtained by applying paint to the building interior to enhance the effect of the entire space. Can be considered.
As one of the methods for imparting anti-allergenicity to the coating film, there is a method using photocatalytic action, and Patent Document 1 describes apatite-coated photocatalytic titanium dioxide particles and an average particle size (D50) measured by a laser Doppler method. A coating composition is disclosed, which comprises silver particles having a size of 1 nm to 100 nm.
However, the coating film formed by the coating film described in Patent Document 1 has a problem that the resin is decomposed at an early stage by photocatalytic action and the duration of the effect is short.

JP-A-2009-161708

An object of the present invention is to provide a coating composition suitable for forming a coating film having excellent antiallergenicity, antibacterial property and durability.

As a result of diligent studies to achieve the above object, the present inventors have obtained anatase-type titanium oxide, silver particles having a particle size of 0.3 to 100 μm, composite particles of calcium phosphate (A), and resin (B). A coating composition containing the solvent (C) and 1 to 300 parts by mass of the composite particles (A) based on 100 parts by mass of the resin (B).
The resin (B) has a water absorption rate in the range of 0 to 50%, and is characterized by containing 1 to 40 parts by mass of the resin (B) in terms of solid content based on 100 parts by mass of the entire coating composition. It has been found that the above-mentioned problems can be solved by using the coating composition described above, and the present invention has been completed.
That is, the present invention provides the following coating composition.
(1) A coating composition containing anatase-type titanium oxide, silver particles having a particle diameter of 0.3 to 100 μm, composite particles (A) of calcium phosphate, a resin (B), and a solvent (C).
The composite particles (A) are contained in an amount of 1 to 300 parts by mass based on 100 parts by mass of the resin (B).
The resin (B) has a water absorption rate in the range of 0 to 50%.
A coating composition comprising the resin (B) in an amount of 0.5 to 40 parts by mass based on 100 parts by mass of the entire coating composition.
(2) The coating composition according to (1), wherein the calcium phosphate is hydroxyapatite.
(3) The coating composition according to (1) or (2), wherein the resin (B) is a resin having an acid group.
(4) The coating composition according to any one of (1) to (3), wherein the resin (B) is a water-dispersible resin.
(5) The coating composition according to any one of (1) to (4), which further contains a thickener.
(6) The coating composition according to (5), wherein the thickener is a polyacrylic acid-based thickener and / or a fibrin-based thickener.
(7) The coating composition according to any one of (1) to (6), which further contains a matting agent.
(8) A coating method for coating an object to be coated with the coating composition according to any one of (1) to (7).
(9) A painted article obtained by coating an object to be coated with the coating composition according to any one of (1) to (7).

According to the present invention, it is possible to obtain a coating composition capable of forming a coating film having good storage stability, excellent anti-allergen properties, antibacterial properties and durability, and a good appearance when coated.

(Composite particle (A))
The composite particles used in the present invention include one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles.
The number of titanium oxide particles per composite particle may be one or two or more. The number of titanium oxide particles per composite particle is usually two or more.

The form of the titanium oxide particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particles may contain two or more titanium oxide particles having different morphologies.

The particle size of the titanium oxide particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The titanium oxide particles contained in the composite particles are, for example, nanoparticles or submicron particles.

Examples of the crystal structure of titanium oxide constituting the titanium oxide particles include anatase type, rutile type, brookite type and the like, and among these, anatase type is preferable.

The number of metal particles per composite particle may be one or two or more. The number of metal particles per composite particle is usually two or more.

The form of the metal particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particle may include two or more metal particles having different morphologies.

The particle size of the metal particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The metal particles contained in the composite particles are, for example, nanoparticles or submicron particles.

The metal particles contained in the composite particles are selected from the group consisting of, for example, silver particles, gold particles, platinum particles and copper particles. The metal particles contained in the composite particles are preferably silver particles. The composite particle may contain two or more metal particles of different types.

The number of calcium phosphate particles per composite particle may be one or two or more. The number of calcium phosphate particles per composite particle is usually two or more.

The form of the calcium phosphate particles contained in the composite particles is not particularly limited, and examples thereof include spherical, granular, needle-like, flaky, and indefinite shapes. The composite particles may contain two or more calcium phosphate particles having different morphologies.

The particle size of the calcium phosphate particles contained in the composite particles is not particularly limited as long as it is smaller than the particle size of the composite particles, and can be appropriately adjusted according to the particle size of the composite particles. The calcium phosphate particles contained in the composite particles are, for example, nanoparticles or submicron particles.

Examples of calcium phosphate constituting the calcium phosphate particles include apatite (apatite), tricalcium phosphate, octacalcium phosphate and the like, and among these, apatite is preferable. Examples of apatite include hydroxyapatite, fluorinated apatite, carbonate apatite and the like, and among these, hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) is preferable.

The content of titanium oxide particles, metal particles and calcium phosphate particles per composite particle is not particularly limited, but the lower limit of the content of titanium oxide particles is usually 10 parts by mass with respect to 1 part by mass of metal particles. It is preferably 20 parts by mass, more preferably 25 parts by mass, and even more preferably 30 parts by mass, and the upper limit of the content of the titanium oxide particles is usually 300 parts by mass, preferably 300 parts by mass with respect to 1 part by mass of the metal particles. It is 250 parts by mass, more preferably 200 parts by mass, and even more preferably 180 parts by mass. The lower limit of the content of the calcium phosphate particles is usually 1 part by mass, preferably 2 parts by mass, and more preferably 3 parts by mass with respect to 1 part by mass of the metal particles, and the upper limit of the content of the calcium phosphate particles is. , Usually 100 parts by mass, preferably 80 parts by mass, still more preferably 60 parts by mass, and even more preferably 50 parts by mass.

The particle size of the composite particles measured by the dynamic light scattering method is preferably 100 to 600 nm, more preferably 200 to 500 nm, and even more preferably 250 to 350 nm. The particle size measured by the dynamic light scattering method is a commercially available dynamic light scattering type particle size distribution measuring device, preferably a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.). Measured by.

In the composite particles, it is preferable that one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles are arranged three-dimensionally and randomly.

In one embodiment of three-dimensional and random arrangement, at least one metal particle is attached to at least one titanium oxide particle.

In one embodiment of three-dimensional and random arrangement, one or more particles (titanium oxide) are surrounded by one particle (one particle selected from titanium oxide particles, metal particles and calcium phosphate particles). One or more particles selected from particles, metal particles and calcium phosphate particles) are present. In this embodiment, one or more particles of the same type may be adjacent to one particle, or one or more particles of different types may be adjacent to each other. Adjacent particles are preferably bonded and fixed to each other. Examples of the combination of adjacent particles include titanium oxide particles, metal particles, calcium phosphate particles, titanium oxide particles and metal particles, titanium oxide particles and calcium phosphate particles, metal particles and calcium phosphate particles, and the like.

In one embodiment of three-dimensional and random arrangement, a portion of at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles is exposed on the surface of the composite particles.

In one embodiment of three-dimensional and random arrangement, a portion of at least one titanium oxide particle, a portion of at least one metal particle and a portion of at least one calcium phosphate particle are exposed on the surface of the composite particle. are doing.

In one embodiment of three-dimensional and random arrangement, at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles is present inside the composite particles without being exposed on the surface of the composite particles. There is.

In one embodiment of three-dimensional and random arrangement, at least one particle selected from titanium oxide particles, metal particles and calcium phosphate particles has a membranous morphology and is present on at least a portion of the surface of the composite particles. ing.

In one embodiment of three-dimensional and random arrangement, two or more particles selected from titanium oxide particles, metal particles and calcium phosphate particles have a film-like morphology as one or a series, and the surface of the composite particles. It is present in at least part of.

Whether one particle has a particle morphology, has a membranous morphology, or has a membranous morphology integrally with or in conjunction with another one or more particles is a composite particle. It may be affected by the compounding ratio of particles when producing. Depending on the compounding ratio, one particle may no longer maintain its particle morphology and may take a membranous morphology that is present on at least a portion of the surface of the composite particle. For example, when particle compositing is performed by a mechanical method such as a bead mill or a ball mill, particles (for example, silver particles) composed of a material having a hardness lower than that of other particles take such a film-like form. obtain.
Two or more of the above embodiments relating to three-dimensional and random arrangement may be combined.

As the composite particles, for example, powder of a composite material sold by Shinshu Ceramics Co., Ltd. under the trade name "earthplus" can be used. Earth Plus is a composite material powder in which titanium oxide, silver and hydroxyapatite are composited, and contains one or more titanium oxide particles, one or more silver particles, and one or more hydroxyapatite particles. Contains composite particles consisting of. In the composite particles, one or more titanium oxide particles, one or more silver particles, and one or more hydroxyapatite particles are arranged three-dimensionally and randomly, and at least one silver particle is at least one. It is fixed to the titanium oxide particles of. Further, in the composite particles, a part of at least one titanium oxide particle, a part of at least one silver particle, and a part of at least one hydroxyapatite particle are exposed on the surface of the composite particle. Conceivable.

The composite particles are prepared by mixing titanium oxide powder, metal powder and calcium phosphate powder in a liquid using, for example, a wet mill, and one or more titanium oxide particles contained in the titanium oxide powder and 1 contained in the metal powder. It can be produced by combining one or more metal particles and one or more calcium phosphate particles contained in the calcium phosphate powder. The composite particles thus produced are then used in the present invention without being sintered.

The titanium oxide content (purity) in the titanium oxide powder is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more. The upper limit is, for example, 99% by mass.

The particle size of the titanium oxide particles (primary particles) contained in the titanium oxide powder is not particularly limited, but is, for example, 0.03 to 0.1 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the titanium oxide powder may contain agglomerates (secondary particles) of titanium oxide particles. The particle size of the aggregate of titanium oxide particles is, for example, 1 to 2 μm. The particle size of the titanium oxide particles or aggregates thereof is measured using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

The metal content (purity) in the metal powder is preferably 80% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more. The upper limit is, for example, 99.9% by mass.

The particle size of the metal particles (primary particles) contained in the metal powder is not particularly limited, but is, for example, 1.1 to 1.9 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the metal powder may contain agglomerates of metal particles (secondary particles). By freezing and storing the metal powder until use, it is possible to suppress the aggregation of the metal particles contained in the metal powder. The particle size of the metal particles or their aggregates is calculated, for example, based on the specific surface area.

The calcium phosphate content (purity) in the calcium phosphate powder is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more.

The particle size of the calcium phosphate particles (primary particles) contained in the calcium phosphate powder is not particularly limited, but is, for example, 0.1 to 0.2 μm. Since the wet mill can disperse the particle agglomerates into individual particles, the calcium phosphate powder may contain agglomerates (secondary particles) of calcium phosphate particles. The particle size of the aggregate of calcium phosphate particles is, for example, 4 to 5 μm. The particle size of the calcium phosphate particles or their aggregates is measured by, for example, a laser diffraction / scattering method.

The wet mill disperses and finely pulverizes the particles contained in the titanium oxide powder, the metal powder, and the calcium phosphate powder in a liquid, and uses one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate. It can be compounded with particles. Examples of the wet mill include a bead mill and a ball mill, and among these, a bead mill is preferable. Examples of the material of the pulverizing medium such as beads and balls used in a mill such as a bead mill and a ball mill include alumina, zircon, zirconia, steel and glass, and among these, zirconia is preferable. The size (diameter) of the pulverized media can be appropriately adjusted according to the particle size and the like of the composite particles to be produced, but is usually 0.05 to 3.0 mm, preferably 0.1 to 0.5 mm. As the pulverizing medium, for example, beads or balls having a size of about 0.1 mm and a mass of about 0.004 mg can be used.

The liquid used for mixing is, for example, an aqueous medium such as water. When the liquid used for mixing is water, the total amount of titanium oxide powder, metal powder and calcium phosphate powder is usually 25 to 45 parts by mass, preferably 30 to 40 parts by mass with respect to 65 parts by mass of water. It is adjusted to be a part.

When mixing raw materials containing titanium oxide powder, metal powder, calcium phosphate powder and liquid with a wet mill, various conditions such as total addition amount of raw material powder, liquid flow rate, peripheral speed of blades in cylinder, stirring temperature, stirring The time and the like can be appropriately adjusted according to the particle size and the like of the composite particles to be produced. The total amount of the raw material powder (titanium oxide powder, metal powder and calcium phosphate powder) added is, for example, 4 kg or more, the cylinder volume is, for example, 0.5 to 4 L, and the flow rate of the liquid is, for example, 0.5 to 3 L / min. The peripheral speed of the blade is, for example, 300 to 900 m / min, the liquid temperature is, for example, 20 to 60 ° C., and the mixing time per 1 kg of the raw material powder is, for example, 0.5 to 2 hours. The upper limit of the total amount of the raw material powder added can be appropriately adjusted according to the cylinder volume and the like. The mixing time can be appropriately adjusted according to the total amount of the raw material powder added and the like.

As the raw material, it is preferable to add a dispersant in addition to titanium oxide powder, metal powder, calcium phosphate powder and liquid. Examples of the dispersant include a high molecular weight dispersant, a low molecular weight dispersant, an inorganic dispersant, and the like, and can be appropriately selected depending on the type of liquid used in the wet mixing. When the liquid used at the time of mixing is an aqueous medium such as water, for example, an anionic polymer-type dispersant, a nonionic polymer-type dispersant, or the like can be used as the dispersant, and an anion Examples of the sex polymer type dispersant include a polycarboxylic acid type dispersant, a naphthalin sulfonate formalin condensation type dispersant and the like, and examples of the nonionic polymer type dispersant include polyethylene glycol and the like. .. The amount of the dispersant added can be adjusted as appropriate, but is, for example, 0.1 to 3% by mass, preferably 0. It is 3 to 1% by mass.

Using a wet mill, the titanium oxide powder, metal powder and calcium phosphate powder are mixed in a liquid to form one or more titanium oxide particles contained in the titanium oxide powder and one or more metal particles contained in the metal powder. , A suspension (slurry) of composite particles can be produced by combining with one or more calcium phosphate particles contained in the calcium phosphate powder. Then, by removing the solvent in the suspension by evaporation or the like, an aggregate of composite particles (dry powder) can be produced. An aggregate (dry powder) of composite particles can also be produced from a suspension (slurry) of composite particles by a known granulation method such as a spray-dry granulation method.

The particle size of the aggregate of composite particles measured by the dynamic light scattering method is, for example, 100 to 600 nm, preferably 200 to 500 nm. The median diameter (d50) of the aggregate of composite particles measured by the dynamic light scattering method on a volume basis is, for example, 250 to 350 nm, preferably about 300 nm. For the particle size by the dynamic light scattering method, a commercially available dynamic light scattering type particle size distribution measuring device, preferably a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.) is used. Is measured.

The produced composite particles can be used as they are in the present invention, but the particle size may be adjusted before using them in the present invention. The particle size can be adjusted, for example, by sieving the composite particles in the powder or suspension state.

In the aggregate of composite particles, the number of titanium oxide particles, metal particles, and calcium phosphate particles per composite particle may be the same or different among the composite particles.

In addition to the composite particles containing one or more titanium oxide particles, one or more metal particles, and one or more calcium phosphate particles, the aggregate of the composite particles is used when the composite particles are produced. Other particles that can be by-produced may be mixed. Examples of other particles include a single titanium oxide particle, a single metal particle, a single calcium phosphate particle, a bond between titanium oxide particles (excluding metal particles and calcium phosphate particles), and a bond between metal particles (oxidation). Titanium particles and calcium phosphate particles are not included), conjugates of calcium phosphate particles (excluding titanium oxide particles and metal particles), conjugates of titanium oxide particles and metal particles (excluding calcium phosphate particles), titanium oxide particles Examples thereof include a bond with calcium phosphate particles (excluding metal particles) and a combination of metal particles and calcium phosphate particles (excluding titanium oxide particles).

In the present invention, the blending amount of the composite particles contained in the coating composition is 1 to 300 parts by mass, preferably in the range of 5 to 200 parts by mass, based on 100 parts by mass of the resin (B). , More preferably in the range of 10 to 150 parts by mass. If it is less than 1 part by mass, a coating film having excellent antiallergenic and antibacterial properties cannot be obtained. On the other hand, if it exceeds 300 parts by mass, the unevenness of the coating film becomes conspicuous and the antibacterial property becomes insufficient, which is not preferable.

(Resin (B))
The resin (B) in the coating composition of the present invention is characterized by having a water absorption rate in the range of 0 to 50%, and a water absorption rate in the range of 0.5 to 30% is appropriate. is there. If the water absorption rate exceeds 50%, a coating film having excellent durability, antiallergenicity, and antibacterial property cannot be obtained.

In the present specification, the water absorption rate is measured as follows.
A polypropylene plate (300 x 100 x 5 mm) containing 10% by mass of 2,2,4-trimethylpentanediol monoisobutyrate with respect to the resin solid content was used as a sample, and the dry film thickness was 30 μm. It is uniformly coated so as to be, and dried under the conditions of a temperature of 23 ° C. and a relative humidity of 60% for 7 days to obtain a coating film. Then, a free coating film is arbitrarily cut from the coating film in a 3 cm square, submerged in deionized water at 20 ° C. for 24 hours, wiped off water droplets on the surface, and immediately weighed, and the water absorption rate is determined according to the following formula. To measure.
Water absorption rate (%) = [(BA) / A] x 100
However, A: the mass of the free coating film before submersion (g) B: the mass of the free coating film after submersion (g).

For the resin (B) of the present invention, it is important that the water absorption rate of the formed coating film is within the above range, and the material, manufacturing method, etc. are not particularly limited. Specifically, regardless of water-based, solvent-based, or solvent-free, resins usually used as a coating film-forming component in the coating industry can be exemplified. For example, acrylic resin, silicone resin, polyester resin, and fluorine. Resin, rosin resin, petroleum resin, kumaron resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid Examples thereof include resins such as resins, vinyl resins and amino resins, and two or more of these modified resins. These resins may be used alone or in combination of two or more.

In the present invention, the resin (B) is preferably a resin having an acid group from the viewpoint of storage stability in a paint state and anti-allergen property of the formed coating film. Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a combination thereof.

When the resin (B) is an aqueous resin, the use of a water-dispersible resin is suitable from the viewpoint of paint storage stability. As a water-dispersible resin, the pH is in the range of 7.0 to 12.0, particularly 7.5 to 11.0, and the average particle size is 15 to 500 nm, particularly 20 from the viewpoint of storage stability and durability. Water-dispersible resins in the range of ~ 300 nm are suitable.

In the present specification, pH is a value measured with a pH meter after adjusting the temperature of the sample to 20 ° C. Further, the average particle size of the water-dispersible resin can be measured by using a particle size distribution measuring device based on the Coulter counter method.

A water-dispersible acrylic resin is suitable as the water-dispersible resin. As the water-dispersible acrylic resin, a polymerizable unsaturated monomer is subjected to one step or two or more steps by a method such as emulsion polymerization in water, miniemulsion polymerization in water, suspension polymerization, etc. by a conventional method. It can be synthesized by dividing and copolymerizing.

Examples of the polymerizable unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth) acrylate. , N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (Meta) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecil (meth) ) Acrylate containing a linear or branched alkyl group such as acrylate, icosyl (meth) acrylate, henicosyl (meth) acrylate, docosyl (meth) acrylate; vinyl aromatic compound such as styrene and α-methylstyrene; cyclohexyl (Meta) acrylates having cyclic hydrocarbon groups such as (meth) acrylates and isobornyl (meth) acrylates; 2-hydroxyethyl (meth) acrylicates, 2-hydroxypropyl (meth) acrylates, 3-hydroxypropyl (meth) acrylates. ) Acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate, allyl alcohol, ε-caprolactone modified form of the above hydroxyalkyl (meth) acrylate, polyoxyethylene chain-containing (meth) acrylate having a hydroxyl group at the molecular end. Hydroxyl group-containing polymerizable unsaturated monomer such as (meth) acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate and the like; (meth) achlorine, formyl styrene, carbon number 4 to Carbonyl group-containing polymerizable unsaturated substances such as vinyl alkyl ketone (eg, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc.), acetoacetoxyethyl (meth) acrylate, acetoacetoxyallyl ester, diacetone (meth) acrylamide, etc. Monomer; Aralkyl (meth) acrylate such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxye Alkoxyalkyl (meth) acrylates such as chill (meth) acrylates; perfluoroalkyl (meth) acrylates, N, N-diethylaminoethyl (meth) acrylates; (meth) acrylamides, (meth) acrylonitriles; vinyl acetate, vinyl propionate, etc. Vinyl ester compounds: allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, tri. Methylol propantri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, penta Elythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1,1,1-trishydroxymethyl ethanedi (meth) acrylate, 1,1,1-trishydroxymethyl ethanetri (meth) acrylate, 1,1, Polyvinyl compounds having at least two polymerizable unsaturated groups in one molecule, such as 1-trishydroxymethylpropantri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, and divinylbenzene; glycidyl (meth) acrylate, β-Methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, allylglycidyl ether, etc. Epoxy group-containing polymerizable unsaturated monomer; Isocyanato group-containing polymerizable unsaturated monomer such as isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate; vinyl trimethoxysilane, vinyl triethoxysilane , Γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane and other alkoxysilyl group-containing polymerizable unsaturated monomers; epoxy group-containing polymerizable unsaturated monomers or hydroxyl group-containing polymerizable unsaturated monomers and unsaturated fatty acids. Reaction products with, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth) acrylate, di Examples thereof include oxidatively curable group-containing polymerizable unsaturated monomers such as cyclopentenyl (meth) acrylate, and these can be used alone or in combination of two or more.

As used herein, the polymerizable unsaturated group means an unsaturated group capable of radical polymerization. Examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group. Further, in the present specification, "(meth) acrylate" means acrylate or methacrylate. "(Meta) acrylic acid" means acrylic acid or methacrylic acid. In addition, "(meth) acryloyl" means acryloyl or methacryloyl. In addition, "(meth) acrylamide" means acrylamide or methacrylamide.
Of these, it is preferable to use a carbonyl group-containing polymerizable unsaturated monomer as a part of the polymerizable unsaturated monomer because an antibacterial / anti-allergen coating film having excellent durability can be obtained.

The present invention is characterized in that the content of the resin (B) is 0.5 to 40 parts by mass in terms of solid content based on 100 parts by mass of the entire coating composition, and ranges from 1 to 30 parts by mass. It is more preferable to be inside.
If the content of the resin (B) exceeds 40 parts by mass, the exposure of the composite particles (A) of the formed coating film to the coating film surface is lowered, and the anti-allergenic and antibacterial properties are insufficient, which is not preferable.

In the present specification, the solid content means a residue excluding volatile components, and the residue may be solid or liquid at room temperature. The solid content mass can be calculated by taking the ratio of the amount of residual substance after drying to the mass before drying as the solid content ratio and multiplying the solid content ratio by the sample mass before drying. The solid content ratio can be calculated by collecting about 2.0 g of a sample in an aluminum foil cup having a diameter of about 5 cm and dividing the residue after heating at 110 ° C. for 1 hour by the mass before heating.

Solvent (C)
The solvent (C) in the coating composition of the present invention may be either water or an organic solvent as long as the resin (B) can be diluted, or a combination of these may be used. Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene and mineral spirit; ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate and butyl carbitol acetate; methyl ethyl ketone, Ketone solvents such as methylisobutylketone and diisobutylketone; methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1-hexanol, 1-octanol, 2-octanol, 2-ethylhexanol, 1-decanol, Benzyl alcohol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene glycol mono n-butyl ether, dipropylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene glycol mono Alcohol-based solvents such as 2-ethylhexyl ether and propylene glycol monophenyl ether; ether-based solvents such as ethylbutyl ether, dibutyl ether, diisobutyl ether, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether and dipropylene glycol dimethyl ether. Solvents: Amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N-dimethyl-β-methoxypropionamide; Swazole 310, Swazole manufactured by Cosmo Petroleum Co., Ltd. Examples include aromatic petroleum-based solvents such as 1000 and Swazole 1500, and these organic solvents can be used alone or in admixture of two or more.

Thickener The coating composition of the present invention preferably contains a thickener in addition to the above components (A) to (C) from the viewpoint of antiallergic property, antibacterial property and durability of the obtained coating film.
Examples of the thickener include inorganic thickeners such as silicate, metallic silicate, montmorillonite, and colloidal alumina; a copolymer of (meth) alginic acid and (meth) acrylic acid ester, and poly. Polyacrylic acid-based thickeners such as sodium acrylate; Urethane-associated thickeners; Fibrous thickeners such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose; Protein-based thickeners such as casein, sodium caseate, and ammonium caseate. Sticky agent; Alginic acid-based thickener such as sodium alginate; Polyvinyl-based thickener such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylbenzyl ether copolymer; Pluronic polyether, polyether dialkyl ester, polyether dialkyl ether, polyether epoxy Polyether-based thickeners such as modified products; maleic anhydride-based thickeners such as partial esters of vinyl methyl ether-maleic anhydride copolymers; polyamide-based thickeners such as polyamideamine salts, etc. Therefore, a polyacrylic acid-based thickener and / or a fibrous thickener is preferable. These thickeners can be used alone or in combination of two or more.
When the coating composition of the present invention contains the thickener, the blending amount of the thickener is not particularly limited, but for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the coating composition. It is preferably 0.3 to 5.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass.

Other Ingredients The coating composition of the present invention further includes a cross-linking agent, a coloring pigment, a brightening agent, a matting agent, a film-forming auxiliary, a neutralizing agent, a pigment dispersant, a surface adjusting agent, and a defoaming agent, if necessary. Paint additives such as agents, preservatives, wetting agents, ultraviolet absorbers and light stabilizers may be appropriately added.
Among these, the cross-linking agent is a compound containing at least two functional groups capable of reacting with the functional group of the resin (B), and specifically, for example, a melamine compound, an oxazoline compound, a polyamine compound, a polyamide compound, and the like. Examples thereof include epoxy compounds, isocyanate compounds, aziridine compounds, hydrazine compounds, carbodiimide compounds, and polyvalent metal compounds, and these cross-linking agents may be used alone or in combination of two or more. The amount of the cross-linking agent can be appropriately set according to the type of the cross-linking agent and the like. Among the cross-linking agents, a hydrazine compound is preferable from the viewpoint of forming an anti-allergenic / antibacterial coating film having excellent durability.

Examples of the hydrazine compound include saturated aliphatic carboxylic acid dihydrazide having 2 to 18 carbon atoms such as dihydrazide dihydrazide oxalic acid, dihydrazide malonate, dihydrazide humic acid, dihydrazide glutaric acid, dihydrazide adipic acid, and dihydrazide sebacic acid; Dihydrazide of monoolefinic unsaturated dicarboxylic acid such as acid dihydrazide, itaconic acid dihydrazide; polyhydrazide of carbonic acid such as carbonate dihydrazide; phthalic acid, terephthalic acid or isophthalic acid dihydrazide, and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid, etc. Adipic acid dihydrazide of aromatic polycarboxylic acid; trihydrazide of nitrilotriacetate, trihydrazide citrate, 1,2,4-benzenetrihydrazide and other aliphatic trihydrazides; ethylenediaminetetraacetate tetrahydrazide, 1,4,5,8- Tetrahydrazide such as naphthoic acid tetrahydrazide can be mentioned.

Matting agent Further, in the present invention, it is suitable to add a matting agent in the coating composition from the viewpoint that an even coating film can be formed. Examples of such a matting agent include an organic matting agent and an inorganic matting agent. Examples of the organic matting agent include polymethyl methacrylate particles, silicone particles, polystyrene particles, polycarbonate particles, acrylic styrene particles, benzoguanamine particles, melamine particles, polyolefin particles, polyester particles, polyamide particles, polyimide particles, and ethylene polyfluoride particles. Can be given. These resin particles may be used alone or in combination of two or more. Among them, polymethylmethacrylate particles can be preferably used. The shape of the resin particles is not particularly limited, for example, a spherical shape, a bead-shaped substantially spherical shape, an amorphous shape such as powder, or the like. On the other hand, examples of the inorganic matting agent include silica, mica, alumina, talc, clay, calcium carbonate, barium sulfate and the like.
When the coating composition of the present invention contains the above-mentioned matting agent, the blending amount of the matting agent can be appropriately adjusted depending on the type, for example, 1 to 600 parts by mass with respect to 100 parts by mass of the resin (B). It is preferably 2 to 500 parts by mass, and more preferably 2 to 500 parts by mass.

Painting The surface to be coated with the coating composition of the present invention is not limited, and can be applied to the surface to be coated which requires anti-allergenicity and antibacterial property. Specific examples include paper such as Western paper, Japanese paper, and cardboard, cement, concrete, mortar, plaster, stone, ceramics, porcelain, glass, inorganic materials such as metal, wood, synthetic resin such as vinyl chloride, plastic, non-woven fabric, etc. It can be applied to known materials such as fabrics, fibers and organic-inorganic composites, and can be applied to cloths, boards, blocks, panels, sheets, tiles, bags, industrial products and the like made from these materials. More specific examples of objects to be coated include, for example, automobile parts such as wall surfaces, ceilings, floors, fittings, curtains, carpets, tapestries, magnet sheets, chair upholstery, bedding, car seats, and car mats. Toys such as stuffed animals, pillowcases, shoe inlays, masks, aprons, clothes, lockers, chests of drawers, desks, drawers, trash cans, bookshelves, clogs and other furniture, water accessories, partitions, filters, etc. .. Since the coating film obtained from the coating composition of the present invention has anti-allergenic and antibacterial properties, it can be preferably used for houses, public facilities, warehouses, shelters in the event of a disaster, temporary tents, and the like.
The surface to be coated or the object to be coated may be previously treated with a treatment agent such as a sealer, or may be coated with a known topcoat coloring paint if necessary.
The coating composition of the present invention can be coated by using a coating means known per se, and can be used for substrates such as rollers, air sprays, airless sprays, ricing guns, universal guns, brushes, and roll coaters. It can be appropriately selected accordingly. Further, it may be applied a plurality of times as long as the appearance of the coating film is not impaired.
The coating film to be formed can be dried at room temperature, but it can also be dried by heating or forced drying.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. Both "part" and "%" are based on mass.

Production of composite particles (A) Production example 1: Production of composite particles A In this production example, anatase-type titanium oxide powder, silver powder, and hydroxyapatite powder are used as raw material powders, and one or more anatase-type titanium oxide particles. A composite particle comprising one or more silver particles and one or more hydroxyapatite particles was produced.

In this production example, the composite particles were produced in the same manner as "earthplus" (trademark) manufactured and sold by Shinshu Ceramics Co., Ltd. The production of composite particles was outsourced to Shinshu Ceramics Co., Ltd.

The raw material powders shown in Table 1 were prepared. The particle size of the titanium oxide powder is a value measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and the particle size of the silver powder is a value calculated based on the specific surface area. The particle size of the hydroxyapatite powder is a value measured by a laser diffraction / scattering method. Since the silver powder was stored frozen until use, the aggregation of silver particles contained in the silver powder was suppressed.

Titanium oxide powder by mixing titanium oxide powder, silver powder, hydroxyapatite powder and polycarboxylic acid-based dispersant in water using a commercially available wet bead mill (“Star Mill LME” manufactured by Ashizawa Finetech Co., Ltd.). One or more titanium oxide particles contained in the above, one or more silver particles contained in the silver powder, and one or more hydroxyapatite particles contained in the hydroxyapatite powder are compounded to form a suspension of the composite particles. Slurry) was produced. The wet bead mill used can be finely pulverized while dispersing titanium oxide particles, silver particles and hydroxyapatite particles contained in the raw material powder, and can be finely divided into nanoparticles or submicron particles, and the finely divided particles are combined. Can be transformed into.

The conditions for particle compositing using a wet bead mill are as follows.
Total amount of raw material powder added: 4 kg or more Cylinder volume: 3.3 L
Beads: Zirconia beads (diameter 0.5 mm, mass 0.37 mg)
Liquid flow rate: 2 L / min Peripheral speed of blades in cylinder: 540 m / min Liquid temperature: 35-45 ° C
Mixing time per 1 kg of raw material powder: 30-40 minutes (about 36 minutes)

Production of Composite Particle Slurry (a1) The total amount of titanium oxide powder, silver powder and hydroxyapatite powder was adjusted to 35 parts by mass with respect to 65 parts by mass of water. The blending amount of the polycarboxylic acid-based dispersant was adjusted to 0.5 parts by mass with respect to 35 parts by mass of the total blending amount of titanium oxide powder, silver powder and hydroxyapatite powder, and a 35% product composite particle slurry (a1). ) Was manufactured.

In the production of composite particles, the amount of titanium oxide powder is adjusted to about 160 parts by mass (155 to 165 parts by mass) with respect to 1 part by mass of silver powder, and the amount of hydroxyapatite powder is adjusted to 1 part by mass of silver powder. It was adjusted to about 40 parts by mass (39 to 41 parts by mass).

Composite particles A were produced by drying a suspension of composite particles (slurry of composite particles (a1)). The particle size of the composite particles measured by the dynamic light scattering method was 200 to 500 nm. The median diameter (d50) of the composite particles measured by the dynamic light scattering method on a volume basis was about 300 nm. The particle size by the dynamic light scattering method is determined by a commercially available dynamic light scattering type particle size distribution measuring device, specifically, a dynamic light scattering type nanotrack particle size distribution measuring device "UPA-EX150" (manufactured by Nikkiso Co., Ltd.). ) Was used for measurement.

Manufacture of rutile-type titanium oxide slurry (for comparative example)
Production Example 2: Production of Rutile-type Titanium Oxide Slurry (a2) 101 parts of clean water was added to a stainless steel container, and components having the following composition were added with stirring to obtain a rutile-type titanium oxide slurry (a2). The solid content of this rutile-type titanium oxide slurry (a2) was 50%.
"Ti Pure R-902 +" (Note 1) 100 copies "DISPER BYK-190" (Note 2) 1.8 copies "SN Deformer 317" (Note 3) 0.1 copies (Note 1) "Ti Pure R-902 +" Product name, manufactured by DuPont, rutile-type titanium oxide particles surface-modified with silica and alumina, average particle size 0.405 μm,
(Note 2) "DISPER BYK-190": trade name, manufactured by Big Chemie, solution of high molecular weight block copolymer having pigment affinity group, solid content 40%,
(Note 3) "SN Deformer 317": Product name, manufactured by San Nopco, mineral oil-based defoamer, 100% solid content.

Production of anatase-type titanium oxide slurry (for comparative example)
Production Example 3: Production of Anatase-type Titanium Oxide Slurry (a3) 101 parts of clean water was added to a stainless steel container, and components having the following composition were added with stirring to obtain anatase-type titanium oxide slurry (a3). The solid content of the titanium oxide slurry (a3) was 50%.
"JA-1" (Note 4) 100 copies "DISPER BYK-190" 1.8 copies "SN deformer 317" 0.1 copies (Note 4) "JA-1": Product name, manufactured by TAYCA Corporation, anatase type Titanium oxide particles, average particle diameter 0.18 μm.

Production of resin (B) Production example 4: Production of emulsion (b1) 285 parts of deionized water and 1 part of "Newcol 707SF" (Note 5) were added to a 4-necked flask with a capacity of 2 liters, and after nitrogen substitution, 85. It was kept at ℃. 3% of the pre-emulsion obtained by emulsifying the components having the following composition and 41 parts of 123 parts of the initiator aqueous solution in which 3 parts of ammonium persulfate were dissolved in 120 parts of deionized water were added thereto. From 20 minutes after the addition, the remaining preemulsion and the ammonium persulfate aqueous solution were added dropwise to the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 413 parts n-Butyl acrylate 240 parts 2-Ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 25 parts Acrylic acid 2 parts Neucol 707SF 66 parts After dropping, this After keeping the temperature at 85 ° C. for another 2 hours, the temperature was lowered to 40-60 ° C. Then, the pH was adjusted with aqueous ammonia to obtain an emulsion (b1) having a solid content of 50%. The average particle size of the emulsion (b1) was 175 nm and the pH was 8.3. When the water absorption rate of the emulsion (b1) was measured according to the description in the specification, it was 20%.
(Note 5) "Newcol 707SF": Trade name, manufactured by Nippon Emulsifier, anionic surfactant having a polyoxyethylene chain, non-volatile content 30%.

Production Example 5: Production of Emulsion (b2) In the above Production Example, an emulsion (b2) having no acid group was obtained in the same manner except that the monomer composition was as follows. The average particle size of the emulsion (b2) was 175 nm and the pH was 7.1. The water absorption rate of the emulsion (b2) was measured according to the description and found to be 18%.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 415 parts n-Butyl acrylate 240 parts 2-Ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 25 parts Neucol 707SF 66 parts.

Production Example 6: Production of Emulsion (b3) An emulsion (b3) was obtained in the same manner except that the monomer composition was as follows in the above Production Example. The average particle size of the emulsion (b3) was 150 nm and the pH was 8.2. The water absorption rate of the emulsion (b3) was measured according to the method described in the specification and found to be 52%.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 405 parts n-Butyl acrylate 240 parts 2-Ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-Hydroxyethyl acrylate 25 parts Acrylic acid 10 parts Neucol 707SF 99 parts.

Production Example 7 (organic solvent system): Production of acrylic resin solution (b4) Add 400 parts of "Swazole 1000" (Note 6) to a 4-necked flask with a capacity of 2 liters, replace with nitrogen, and raise to 120 ° C. with stirring. I warmed it up. Then, the following monomer composition and initiator solution were added dropwise over 3 hours, respectively.
Monomer composition 150 parts of styrene Methyl methacrylate 124 parts 2-ethylhexyl acrylate 75 parts i-butyl methacrylate 140 parts 2-hydroxyethyl acrylate 10 parts Acrylic acid 1 part
Initiator solution 25 parts of tertiary butyl peroxide 50 parts of Swazole 1000 (Note 6) "Swazole 1000": Trade name, manufactured by Maruzen Petrochemical Co., Ltd., aromatic hydrocarbon solvent.
After the dropping, this was kept at 120 ° C. for another 2 hours, then lowered to 40 to 60 ° C., and diluted with "Swazole 1000" until the resin solid content became 50% to obtain an acrylic resin solution (b4). The water absorption rate of the acrylic resin solution (b4) was measured according to the method described in the specification and found to be 2%.

Production of paint composition Example 1: Production of paint A-1 Anatase-type titanium oxide, which is obtained by sequentially charging the following components into a stainless steel container while stirring and mixing them with a homodisper manufactured by PRIMIX until uniform. A paint (A-1) containing composite particles of silver and hydroxyapatite was obtained.
Clean water 81.7 parts 50% emulsion (b1) 10.0 parts 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate 0.5 parts adipic acid dihydrazide 0.1 parts primal ASE-60 (Note) 7) 3.1 parts 2-amino-2-methyl-1-propanol 0.3 parts 35% composite particle slurry (a1) 2.9 parts techpolymer MBX-8 (Note 8) 1.1 parts TEGO Wet280 (Note) 9) 0.2 part BYK-028 (Note 10) 0.2 part ACTICIDE MB (Note 11) 0.2 part (Note 7) "Primal ASE-60": Product name, DOWN CHEMICAL CO. Made by 28% polyacrylic acid thickener,
(Note 8) "Techpolymer MBX-8": Trade name, manufactured by Sekisui Plastics Co., Ltd., crosslinked polymethyl methacrylate, average particle size 8 μm,
(Note 9) "TEGO Wet280": Trade name, manufactured by EVONIK INDUSTRIES AG, polyether-modified siloxane copolymer,
(Note 10) "BYK-028": Product name, manufactured by Big Chemie, silicone defoamer,
(Note 11) "ACTICIDE MB": Trade name, made by THOR GMBH, 5% composite isothiazolinone-based preservative.

Examples 2 to 12 and Comparative Examples 1 to 6: Production of Paints (A-2) to (A-18) In Example 1 above, a paint was prepared in the same manner as in Example 1 except that the compounding composition was shown in Table 2 below. (A-2) to (A-18) were obtained. Table 2 also shows the performance evaluation of the obtained paint. The numerical values in Table 2 are the amounts actually blended.

(Note 12) "Polydurex H7300": Product name, manufactured by Asahi Kasei Corporation, silicone-modified acrylic emulsion, solid content 42.5%, pH 9.0, water absorption rate 12%,
(Note 13) "Superflex 150": Product name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., polyurethane dispersion, solid content 30%, average particle size 30 nm, pH 8-10, water absorption rate 10%,
(Note 14) "AL-15F": Product name, manufactured by Sumitomo Seika Chemical Co., Ltd., hydroxyethyl cellulose.
(Note 15) Tancal Slurry Each component shown below was sequentially charged into a stainless steel container while stirring, and stirring was continued with a homodisper manufactured by PRIMIX until uniform to obtain a 24% product Tancal slurry.
Deionized water 70 parts DISPER BYK-190 (Note 2) 4 parts BYK-028 (Note 10) 2 parts Super S (Note 16) 24 parts (Note 16) "Super S": Product name, manufactured by Maruo Calcium Co., Ltd. Quality Calcium carbonate, specific gravity 2.7, oil absorption 23 (ml / 100g).

Preparation of test coating plate A test coating plate was prepared by the following three methods according to the test method.
Coating board production example 1
On a slate plate (150 x 70 x 4 mm), "EP Sealer Transparent" (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) is roller-coated so that the coating amount is 100 g / m ² , and then dried. "Vini Deluxe 300" (manufactured by Kansai Paint Co., Ltd., JIS K5663 Class 1 compatible acrylic emulsion paint) is coated with a paint toned to 19-90B based on a color sample issued by the Japan Paint Industry Association, and the amount applied is 100 g / Roller coating to m ² and drying under conditions of temperature 20 ° C. and relative humidity 60% for 1 day, then roller coating to a coating amount of 100 g / m ² and temperature 20 ° C. A plate to be coated is obtained by drying under the condition of a relative humidity of 60% for one day, and the coating compositions (A-1) to (A-18) are coated on the plate so that the coating amount is 30 g / m ^2. Painted with. Then, it was dried for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 60% to obtain each test plate, which was subjected to the following performance test.

Coating board production example 2
"Raw glue pack wallpaper" (manufactured by Asahipen Corporation, vinyl chloride wallpaper) is pasted on a slate plate (150 x 70 x 4 mm), dried and fixed for 7 days under the conditions of temperature 20 ° C and relative humidity 60%. The coated plate was used as a plate to be coated, and the coating compositions (A-1) to (A-18) were coated on the plate with a roller so that the coating amount was 30 g / m ² . Then, it was dried for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 60% to obtain each test plate, which was subjected to the following performance test.

Coating board production example 3
"Transparency A4 size clear type for PPC / laser" (PET film manufactured by Kiso Kasei Sangyo Co., Ltd.) is used as a plate to be coated, and each coating composition (A-1) to (A-18) is coated on it with a dry film thickness. It was painted so as to be 2 to 4 μm. Then, it was dried for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 60% to obtain each test plate, which was subjected to the following performance test.

Performance test (* 1) Storage stability Each paint produced in Examples and Comparative Examples was placed in a closed container and stored in a constant temperature room at 40 ° C. for 30 days, and then the liquid state was evaluated according to the following criteria.
⊚: No precipitate in the liquid,
◯: Precipitates and suspended matter are very slightly seen in the liquid, but they are restored by stirring.
Δ: Precipitates or suspended matter are found in the liquid, and they cannot be restored even if stirred.
X: A considerable amount of precipitate or suspended matter is observed in the liquid.

(* 2) Appearance of coating film The initial coating film of each test coating film obtained in the coating plate production example 1 and the coating plate production example 2 was visually observed and evaluated according to the following criteria.
⊚: A uniform coating film is formed on the plate to be coated, and the coating film smoothness is also good.
◯: The coating film is uniform on the plate to be coated, but the coating film is slightly uneven.
Δ: Some unevenness is seen in the coating film on the plate to be coated, and the overcoated part can be seen when viewed from a close distance.
X: The coating film is uneven on the plate to be coated, and the overcoated portion is conspicuous from a distance.

(* 3) Anti-allergen property test The following allergen inactivation test was conducted to evaluate the anti-allergen property of the coated plate.
Allergen inactivation test Each test coating plate obtained in Coating Plate Preparation Example 3 was cut out to a size of 40 mm × 40 mm, and this was used as a sample, and an allergen solution of Japanese cedar pollen Cry j1 (cedar pollen extract, product No. 10103, manufactured by ITEA Co., Ltd.). Was added to a predetermined amount of the sample so that the initial amount of the allergen was 240 ng. Then, the reaction was carried out at 4 ° C. for 24 hours while irradiating a fluorescent lamp having an illuminance of 1000 ± 250 lpx. After the reaction, the allergen solution was recovered, and the allergen concentration was quantified by an enzyme-linked immunosorbent assay (ELISA method). The control was treated in the same manner except that no sample was added. Each sample and control were carried out at n = 3, average values were obtained, and the allergen reduction rate by the sample was calculated as follows.
Allergen reduction rate (%) = (YX) / Y × 100
X: Average value (ng) of allergen amount after reaction with the sample
Y: Average value of control allergen amount (ng)
From the calculated allergen reduction rate, the anti-allergen property of each test coating plate was evaluated as follows.
⊚: The allergen reduction rate was 99% or more, showing excellent anti-allergen properties.
◯: The allergen reduction rate was 90% or more, showing anti-allergen properties.
Δ: The allergen reduction rate was 70% or more, showing a slight anti-allergen property.
X: The allergen reduction rate was less than 70% and showed no anti-allergen property.

(* 4) Antibacterial property The antibacterial property was tested based on JIS Z2801: 2010 (film adhesion method). Each test coating plate obtained in Coating Plate Preparation Example 3 was cut out to a size of 50 mm × 50 mm, and this was used as a sample, and Escherichia coli was ingested as a test strain and 0.4 mL of Escherichia coli solution was ingested into the sample. Moreover, a polyethylene film was used as a control. The obtained antibacterial activity value was evaluated as the antibacterial property of each test coating plate as follows.
◯: The antibacterial activity value was 2.0 or more and had excellent antibacterial properties.
X: The antibacterial activity value was less than 2.0 and did not have antibacterial activity.

(* 5) Durability Each test coating plate obtained in the coating plate production example 2 was subjected to JIS K5600-7-7 (general paint test method-7: long-term durability of coating film-Section 7: accelerated weather resistance and promotion. According to the light resistance (xenon lamp method)), the durability test of the coating film was performed for 1000 hours, and then the coated surface condition was visually observed and evaluated according to the following criteria.
◎: Good, no change compared to the initial stage
◯: A little unevenness of the coating film is seen compared to the initial stage.
Δ: The coating film is uneven compared to the initial stage, and the chalking is less than △ 2.0 based on the initial stage.
X: Chalking is -2.0 or more based on the initial stage compared to the initial stage, or the coating film is peeled off or dropped from the plate to be coated.

It is possible to provide a coating composition capable of forming a coating film having good storage stability, excellent anti-allergenicity, antibacterial property and durability, and having a good appearance when coated.

Claims (9)

A coating composition containing anatase-type titanium oxide, silver particles having a particle diameter of 0.3 to 100 μm, and composite particles (A) of calcium phosphate, a resin (B), and a solvent (C).
The composite particles (A) are contained in an amount of 1 to 300 parts by mass based on 100 parts by mass of the resin (B).
The resin (B) has a water absorption rate in the range of 0 to 50%.
A coating composition comprising the resin (B) in an amount of 0.5 to 40 parts by mass based on 100 parts by mass of the entire coating composition. The coating composition according to claim 1, wherein the calcium phosphate is hydroxyapatite. The coating composition according to claim 1 or 2, wherein the resin (B) is a resin having an acid group. The coating composition according to any one of claims 1 to 3, wherein the resin (B) is a water-dispersible resin. The coating composition according to any one of claims 1 to 4, further comprising a thickener. The coating composition according to claim 5, wherein the thickener is a polyacrylic acid-based thickener and / or a fibrin-based thickener. The coating composition according to any one of claims 1 to 6, further comprising a matting agent. A coating method for coating an object to be coated with the coating composition according to any one of claims 1 to 7. A painted article obtained by coating an object to be coated with the coating composition according to any one of claims 1 to 7.