JP2018145359A - Aqueous composition, aqueous coating material, coating film, composite coating film, and coated product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition that is excellent in suitability for spraying and wettability of a coating liquid on the assumption of coating at a construction site and can form a coating film capable of maintaining appearance, contamination resistance and resistance to contamination by organisms at a high level over a long period of time without impairing appearance even when applied to a deep-color base material.SOLUTION: An aqueous composition comprises (D) a fluorocarbon surfactant, (A) a mineral oil-based defoaming agent and (B) silicon dioxide and has a mass ratio of the fluorocarbon surfactant (D) and the mineral oil-based defoaming agent (A) (the fluorocarbon surfactant (D)/the mineral oil-based defoaming agent (A))=2/1 to 100/1.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous composition, an aqueous paint, a coating film, a composite coating film, and a coated product.

The surface of outdoor structures such as building exteriors, bridges, tanks, etc. are painted with paint, etc., but the paint film surface is dirt, smoke, sand, etc. in the air, dirt components eluted from sealing materials, and buildings It is polluted by pollutants discharged from the discharge outlets, organisms represented by algae mold and the like. Such contamination of the coating film is usually dark or green, which significantly impairs the aesthetics of buildings and outdoor structures.
As an aqueous topcoat coating agent composition that suppresses contamination of the coating film as described above, it comprises an undercoat layer and an overcoat layer provided on the undercoat layer, and the undercoat layer comprises a silicone-modified resin and an organic antifungal agent. There has been proposed a multi-coat paint body in which the overcoat layer is a layer containing photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone (see, for example, Patent Document 1). In addition, an aqueous coating agent composition containing an anti-algae and fungicide in an aqueous dispersion of a copolymer having a specific composition has also been proposed (for example, see Patent Document 2).

Japanese Patent No. 4092434 JP-A-2016-808

The techniques described in Patent Documents 1 and 2 are techniques excellent in biofouling resistance since the undercoat layer contains a fungicide.
However, Patent Documents 1 and 2 have a problem that there is room for improvement with respect to sprayability assuming painting at a building site and wettability of a coating liquid onto a base material.

  Therefore, in the present invention, in view of the circumstances of the prior art described above, the sprayability and wettability of the coating liquid assuming on-site coating is excellent, and even when a dark base material is used, the appearance is not impaired, and it is long-lasting. Another object of the present invention is to provide an aqueous composition capable of forming a coating film capable of maintaining the appearance, stain resistance and biofouling resistance at a high level.

As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have
A fluorocarbon surfactant (D), a mineral oil-based antifoaming agent (A), and silicon dioxide (B), and the fluorocarbon surfactant (D) and the mineral oil-based antifoaming agent (A) By using an aqueous composition having a mass ratio of a specific numerical range, it has been found that the above-mentioned problems of the prior art can be solved, and the present invention has been completed.
That is, the present invention is as follows.

[1]
A fluorocarbon surfactant (D);
A mineral oil-based antifoaming agent (A),
Silicon dioxide (B),
Containing,
The mass ratio of the fluorocarbon surfactant (D) and the mineral oil-based antifoaming agent (A) is:
(Fluorocarbon surfactant (D) / mineral oil-based antifoaming agent (A)) = 2/1 to 100/1.
[2]
The aqueous composition according to [1], further including an inorganic oxide (C) having photocatalytic activity.
[3]
The aqueous composition according to [1] or [2], further including a fading dye (E).
[4]
An aqueous paint containing the aqueous composition according to any one of [1] to [3].
[5]
A coating film obtained from the water-based paint described in [4].
[6]
A substrate;
The coating film according to [5] formed on at least a part of the surface of the base material,
A coated product.
[7]
An overcoat layer obtained from the coating film according to [5],
Having at least two subbing layers,
The undercoat layer contains a polymer and an algal and / or antifungal agent;
Composite coating.
[8]
A substrate;
The composite coating film according to [7],
A coated product.
[9]
The coated product according to [6] or [8], wherein the substrate is an organic substrate.

  According to the present invention, it is excellent in sprayability and wettability of a coating liquid assuming on-site coating, and does not impair the appearance even with a dark-colored substrate, and has a long-term appearance, contamination resistance, and biological contamination resistance. A composition capable of forming a coating film that can be maintained at a high level can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
In addition, the following this embodiment is an illustration for demonstrating this invention, and is not the meaning which limits this invention to the following content. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Aqueous composition]
The aqueous composition of this embodiment is
A fluorocarbon surfactant (D);
A mineral oil-based antifoaming agent (A),
Silicon dioxide (B),
Containing,
The mass ratio between the fluorocarbon surfactant (D) and the mineral oil defoamer (A) is (fluorocarbon surfactant (D) / mineral oil defoamer (A)) = 2/1. 100/1.
The water-based paint and the coating film obtained from the water-based composition of the present embodiment are excellent in sprayability and wettability of the coating liquid assuming on-site coating, and without damaging the appearance even with a dark base material, over a long period of time, Appearance, contamination resistance, and biological contamination resistance can be maintained at a high level.
Here, “sprayability” refers to the occurrence of crater-like irregularities on the surface of the coating film when sprayed onto a predetermined substrate using the coating liquid containing the aqueous composition of the present embodiment. Slightly, the smaller the dent of the coating film derived from the repellency of the coating liquid, the better the characteristics.

(Mineral oil-based antifoaming agent (A))
The water-based composition of the present embodiment contains a mineral oil-based antifoaming agent (A) (hereinafter sometimes referred to as “component (A)”).
By containing the mineral oil-based antifoaming agent (A), wettability to an organic base material and the like is further improved when coating is performed using the aqueous composition of the present embodiment or an aqueous paint containing the same. Troubles on appearance such as craters (sprayability) due to entrainment of bubbles and bubbles can be further suppressed.
A mineral oil-based antifoaming agent is an antifoaming agent containing mineral oil in an antifoaming component called a carrier.
The nucleating agent is not particularly limited, and for example, inorganic hydrophobic silica, organic metal soap, amide wax, or the like can be used.
Although it does not specifically limit as a mineral oil-type antifoamer, A commercial item can also be used.
Examples of the hydrophobic silica-type mineral oil-based antifoaming agent include, but are not limited to, Nopco 8034, Nopco 8034-L, SN deformer AP, SN deformer H-2, SN deformer TP-33, SN deformer VL, SN deformer 113, SN deformer 154, SN deformer 154S, SN deformer 313, SN deformer 314, SN deformer 316, SN deformer 317, SN deformer 318, SN deformer 319, SN deformer 321, SN deformer 323, SN deformer 364, SN deformer 414, SN deformer 456, SN deformer 474, SN deformer 476-L, SN deformer 480, SN deformer 777, SN deformer -1341, SN deformer 1361 (manufactured by San Nopco) BYK-1740 (manufactured by BYK), and the metal soap type mineral oil-based antifoaming agent is not limited to the following, for example, Nopco DF -122, Nopco DF-122-NS, Nopco NDW, Nopco NXZ, SN deformer 122-SV, SN deformer 269, SN deformer 1010 (manufactured by San Nopco), and the amide wax type mineral oil-based antifoaming agent For example, but not limited to, Nopco 267-A, Nopco DF-124-L, SN deformer TP-39, SN deformer 477T, SN deformer 477-NS, SN deformer 479, SN deformer 1044, SN Deformer 1320, SN deformer 340, SN DEFOAMER 1360, SN Defoamer 5100 (manufactured by San Nopco Limited) and the like.
These may be used alone or in combination of two or more. Preferably, a hydrophobic silica type mineral oil-based antifoaming agent is included.

Although content of (A) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.001 mass%-5.000 mass%, More preferably, it is 0.0020 mass%-4.5000. It is mass%, More preferably, it is 0.0025-4,000 mass%. By making content of (A) component into the said range, the water-based coating material and coating film which were further excellent in the external appearance in a dark base material, a weather resistance, stain resistance, sprayability, and wettability can be obtained.
Although content of (A) component in a coating film is not specifically limited, Preferably it is 0.024 mass%-1.250 mass%, More preferably, it is 0.040 mass%-1.200 mass%, More preferably It is 0.0625-1.000 mass%. (A) By making content of said component into the said range, the sprayability of the aqueous composition which obtains a coating film, wettability will be made favorable, and the appearance in a dark-colored base material, a weather resistance, and stain resistance will be further excellent. A coated film can be obtained.

(Silicon dioxide (B))
The aqueous composition of the present embodiment contains silicon dioxide (B).
In the present specification, silicon dioxide (B) is sometimes simply referred to as component (B).
The silicon dioxide (B) is preferably colloidal silica. Examples of the colloidal silica include colloidal silica which is a dispersion of silica water or a water-soluble solvent having silicon dioxide as a basic unit.
The manufacturing method of colloidal silica is not specifically limited, For example, it can also prepare with a sol-gel method. For preparation by the sol-gel method, Werner Stober et al .; Journal of Colloid And Interface Science, vol. 26, pp. 62-69 (1968) and Rickey D. Badley et al .; Lang muir 6, 792-801 (1990), “Color Material Association Journal”, 61 [9] 488-493 (1988), and the like can be referred to.

Although the number average particle diameter of (B) component is not specifically limited, Preferably it is 1-100 nm, More preferably, it is 4-30 nm, More preferably, it is 8-25 nm.
By making the number average particle diameter of the component (B) 1 nm or more, the storage stability of the aqueous composition is further improved. (B) By making the number average particle diameter of a component 100 nm or less, the external appearance in the case of using a dark base material further improves. The number average particle diameter can be measured using a wet particle size analyzer.

Colloidal silica may be acidic or basic in the state of an aqueous dispersion.
Commercially available products can also be used as the acidic colloidal silica using water as a dispersion medium. Examples of such commercially available products include, but are not limited to, “Snowtex (trademark) -OXS”, “Snowtex-OS”, “Snowtex-O” manufactured by Nissan Chemical Industries, Ltd. “Snowtex-O-40”, “Snowtex-OL” and “Snowtex-OYL”, “Adelite ™ AT-20Q” manufactured by ADEKA, “Crebosol ™ 20H12” manufactured by Clariant Japan, and “Clevozole 30CAL25” and the like.
Examples of basic colloidal silica include, but are not limited to, colloidal silica stabilized by the addition of alkali metal ions, ammonium ions, amines, and the like. A commercial item can also be used for these. Examples of such commercially available products include, but are not limited to, “Snowtex-XS”, “Snowtex-S”, “Snowtex-30”, “Snowtex” manufactured by Nissan Chemical Industries, Ltd. -50 "," Snowtex-20L "," Snowtex-XL "," Snowtex-YL "," Snowtex-ZL "," Snowtex-NXS "," Snowtex-NS "," Snowtex- "N", "Snowtex-N40", "Snowtex-CXS", "Snowtex-C", "Snowtex-CM", "Snowtex-PS-S" and "Snowtex PS-M"; manufactured by ADEKA “Adelite AT-20”, “Adelite AT-30”, “Adelite AT-20N”, “Adelite AT-30N”, “Adela” "AT-20A", "Adelite AT-30A", "Adelite AT-40" and "Adelite AT-50";"Clevosol30R9","Clebosol30R50","Crebosol50R50" manufactured by Clariant Japan, DuPont "Ludox (trademark) HS-40", "Ludox HS-30", "Ludox LS", and "Ludox SM-30".
Commercially available products can also be used as colloidal silica using a water-soluble solvent as a dispersion medium. Examples of such commercially available products include, but are not limited to, “MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm)”, “IPAST (particle size) manufactured by Nissan Chemical Industries, Ltd. “10-15 nm isopropyl alcohol dispersion type)”, “EG-ST (ethylene glycol dispersion type with particle diameter of 10-15 nm)”, “EG-ST-ZL (ethylene glycol dispersion type with particle diameter of 70-100 nm)”, “ NPC-ST (ethylene glycol monopropyl ether dispersion type having a particle diameter of 10 to 15 nm) ”and the like.
The colloidal silica mentioned above may be used alone or in combination of two or more. Furthermore, alumina, sodium aluminate, or the like may be included as a minor component. Colloidal silica may contain an inorganic base (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia) or an organic base (such as tetramethylammonium) as a stabilizer.

Although content of (B) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.3-8.0 mass%, More preferably, it is 0.7-7.5 mass%. More preferably, it is 1.0-7.0 mass%.
By setting the content of the component (B) in the aqueous composition within the above range, a coating film with further improved appearance, weather resistance, stain resistance, sealing stain resistance, and bio stain resistance on a dark-colored substrate is obtained. Can be obtained.
Content of (B) component in the coating film obtained from the aqueous composition of this embodiment becomes like this. Preferably it is 46.25 mass%-99.85 mass%, More preferably, it is 50.00 mass%-99. It is 85 mass%, More preferably, it is 60.00 mass%-99.85 mass%.
By making content of (B) component in a coating film into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, stain resistance, and bio-contamination resistance can be obtained.

(Inorganic oxide having photocatalytic activity (C))
The aqueous composition of the present embodiment preferably further contains an inorganic oxide (C) having photocatalytic activity. Thereby, photocatalytic activity and hydrophilicity can be expressed by irradiating light to a coating film.
In the present specification, the inorganic oxide (C) having photocatalytic activity is sometimes simply referred to as the component (C).
The inorganic oxide (C) having photocatalytic activity is not particularly limited as long as it is an inorganic oxide having photocatalytic activity.
The component (C), but are not limited to, for _{example, TiO 2, ZnO, SrTiO 3} , BaTiO 3, BaTiO 4, BaTi 4 O 9, K 2 NbO 3, Nb 2 O 5, Fe 2 O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, RuO ₂ , CeO ₂ ; Ti, Nb, Ta, and Layered oxides having at least one element selected from the group consisting of V (for example, JP-A-62-074452, JP-A-02-172535, JP-A-07-024329, JP-A-08-089799) , JP 08-089800, JP 08-089804, JP 09-248465, JP 10-099694, JP 10-244165 Etc.) and the like.
The component (C) is preferably TiO ₂ (titanium oxide) from the viewpoints of chemical stability, toxicity, environment, and the like. Titanium oxide may have any crystal structure of anatase type, rutile type or brookite type.

The component (C) is an inorganic oxide having photocatalytic activity, and is preferably an inorganic oxide having photocatalytic activity obtained by modifying the particle surface.
By modifying the particle surface, the generation amount of active oxygen species such as H ₂ O ₂ and .OH can be suppressed, and damage to the underlying coating film can be further suppressed.
Examples of the substance that modifies the particle surface include, but are not limited to, silica, aluminum, copper oxide, iron oxide, and the like. Among these, silica is preferable. The same effect can be obtained by modifying the particle surface with a metal such as Fe, Cu, Al or Pt, or a complex such as chloroplatinic acid.
The method for modifying the surface of the component (C) will be described with titanium oxide as an example.
The method for modifying the surface of titanium oxide is not particularly limited, and examples thereof include a method in which a silicon compound is added to a slurry of titanium oxide and a hydrous oxide of silicon is precipitated through steps such as neutralization. It is done.
It does not specifically limit as a silicon compound, For example, water-soluble alkali metal silicate salts, such as sodium silicate, can be used. Among these, sodium silicate is preferable from the viewpoint that it is colorless and the titanium oxide sol is not colored.
The amount of silicon treated with a hydrous oxide is preferably 3 to 25% by mass, more preferably 4 to 23% by mass, and still more preferably 5 to 20% by mass with respect to titanium oxide.
Since the modification treatment amount is equal to or more than the lower limit value, an increase in the amount of active oxygen species can be suppressed, so that damage to the base coating film can be prevented. Moreover, since the modification treatment amount is equal to or less than the upper limit, aggregation of titanium oxide can be suppressed and an increase in the viscosity of the sol can be suppressed, so that dispersibility and transparency are further improved.

As the component (C), an inorganic oxide whose particle surface having photocatalytic activity is modified, and an inorganic oxide in which a metal element such as gold, silver, copper, or iron is supported on the inorganic oxide. It can also be used.
The method for supporting the metal on the component (C) is not particularly limited. For example, titanium chloride whose surface is modified is added with copper chloride dihydrate, silver nitrate, tetrachloroauric acid tetrahydrate, and the like. The method obtained by making it react with trisodium citrate dihydrate, tannic acid, etc. is mentioned. As a metal carrying amount, it is preferable that a metal is 0.1-5 mass% with respect to a titanium oxide, It is more preferable that it is 0.1-4.8 mass%, 0.1-4.6 mass % Is more preferable.
When the carrying amount is within the above range, it is possible to suppress the precipitation of the metal-carrying titanium oxide and obtain a coating film having excellent biofouling resistance.

Content of (C) component in the aqueous composition of this embodiment becomes like this. Preferably it is 0 mass%-2.5 mass%, More preferably, it is 0.16-1.4 mass%, More preferably It is 0.24 mass%-1.4 mass%.
By making content of (C) component into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, stain resistance, and bio-contamination resistance can be obtained.
Although content of (C) component in the coating film obtained from the aqueous composition of this embodiment is not specifically limited, Preferably it is 0 mass%-35.0 mass%, More preferably, it is 4.0-35. It is 0.0 mass%, More preferably, it is 4.0 mass%-33.0 mass%, More preferably, it is 6.0 mass%-33.0 mass%, More preferably, it is 6.0 mass%-29. 0% by mass.
By making content of (C) component into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, stain resistance, and bio-contamination resistance can be obtained.

(Fluorocarbon surfactant (D))
The aqueous composition of the present embodiment contains a fluorocarbon surfactant (D).
In the present specification, the fluorocarbon surfactant (D) is sometimes simply referred to as the component (D).
(D) By containing a component, the wettability to the organic base material etc. at the time of coating using the aqueous composition of this embodiment and the aqueous coating material containing the same is further improved, due to entrapment of bubbles and bubbles. Troubles on the appearance of craters and the like can be further suppressed. Furthermore, the uniformity of the coating film is further improved.
Although it is not certain as these reasons, it is presumed that the surface tension of the aqueous composition can be reduced by containing the component (D). In addition, the effect | action of this embodiment is not limited to these.

Although it does not specifically limit as (D) component, Amphoteric surfactant is preferable.
The amphoteric surfactant is not particularly limited, and examples thereof include nonionic amphoteric surfactants, anionic amphoteric surfactants, and cationic amphoteric surfactants. Preferable specific examples include amphoteric surfactants having a C 3-20 perfluoroalkyl group.
Examples of amphoteric surfactants having a C 3-20 perfluoroalkyl group include, but are not limited to, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkylamine oxides, perfluoroalkyls. Examples thereof include ethylene oxide adducts, perfluoroalkyl compounds having an anionic group and a cationic group. Among these, from the viewpoint of lowering the surface tension of the paint, perfluoroalkylethylene oxide adducts and perfluoroalkyl compounds having an anionic group and a cationic group are preferred.
The perfluoroalkyl sulfonate is not limited to the following, and examples thereof include ammonium salts and potassium salts of perfluorooctane sulfonic acid.
As a perfluoroalkyl carboxylate, a commercial item can also be used, for example. Examples of such commercially available products include, but are not limited to, “Surflon S-211” manufactured by AGC Seimi Chemical Co., Ltd.
As the perfluoroalkylamine oxide, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, “Surflon S-241” manufactured by AGC Seimi Chemical Co., Ltd.
As a perfluoroalkyl ethylene oxide adduct, a commercial item can also be used, for example. Examples of such commercially available products include, but are not limited to, “Megafac F-444” manufactured by DIC, “Surflon S-242” manufactured by AGC Seimi Chemical, and the like.
As a perfluoroalkyl compound having an anionic group and a cationic group, for example, a commercially available product can be used. Examples of such commercially available products include, but are not limited to, “Surflon S-231”, “Surflon S-232”, “Surflon S-233” manufactured by AGC Seimi Chemical Co., Ltd., and the like.
These may be used alone or in combination of two or more.

Although content of (D) component in an aqueous composition is not specifically limited, Preferably it is 0.0001 mass%-0.70 mass%, More preferably, it is 0.005 mass%-0.7 mass%, More preferably, it is 0.007 mass%-0.7 mass%, More preferably, it is 0.007 mass%-0.4 mass%.
By setting the content of the component (D) within the above range, an aqueous composition having excellent wettability and sprayability can be obtained, and appearance, weather resistance, stain resistance, and biological contamination on a dark base material A coating film with even better properties can be obtained.
Although content of (D) component in a coating film is not specifically limited, Preferably it is 0.125 mass%-17.5 mass%, More preferably, it is 0.125 mass%-10.0 mass%, Furthermore, Preferably it is 0.175 mass%-10.0 mass%.
By setting the content of the component (D) within the above range, an aqueous composition having excellent wettability and sprayability can be obtained, and appearance, weather resistance, stain resistance, and biological contamination on a dark base material A coating film with even better properties can be obtained.

In the aqueous composition of this embodiment, the mass ratio of the fluorocarbon surfactant (D) and the mineral oil-based antifoaming agent (A) in the aqueous composition is (fluorocarbon surfactant (D) / mineral oil-based Foaming agent (A)) = 2/1 to 100/1.
In the present specification, the mass ratio of the fluorocarbon surfactant (D) and the mineral oil-based antifoaming agent (A) may be simply referred to as (D) / (A).
When the aqueous composition of the present embodiment has the mass ratio of (D) / (A) within the above range, the organic group in the coating using the aqueous composition of the present embodiment and the aqueous paint containing the aqueous composition. The wettability to the material and the like is further improved, and troubles in appearance such as a crater (sprayability) due to entrainment of bubbles and bubbles can be further suppressed.
The mass ratio of (D) / (A) of the aqueous composition of the present embodiment is 2/1 to 100/1, preferably 2/1 to 90/1, more preferably 2.3 / 1. ~ 90/1.

(Fading dye (E))
The aqueous composition of the present embodiment preferably further contains a fading dye (E).
In the present specification, the fading dye (E) is sometimes simply referred to as the component (E).
When the aqueous composition of this embodiment contains a fading pigment (E), troubles such as forgetting to paint, overlapping painting, and uneven coating can be prevented.
(E) As a component, the thing which loses color by irradiation of sunlight and does not impair the design of the base is preferable. Although the time until the color loss varies depending on the season, the direction of irradiation, etc., it is usually preferable that the period until the color loss is visually confirmed is 20 days or less, more preferably 10 days or less, and still more preferably 3 Less than a day.
The component (E) is not particularly limited as long as it has the property of being decolored by the irradiation of sunlight. 1 type selected from the group consisting of Phloxin, Rose Bengal, Acid Red, and First Green FCF. Among these, methylene blue is preferable from the viewpoint of good color developability and fast decolorization rate.
These may be used alone or in combination of two or more.

Although content of (E) component in the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.0005-0.04 mass%, More preferably, it is 0.001-0.035 mass%. Yes, and more preferably 0.005 to 0.03% by mass. By making content of (E) component in an aqueous composition into the said range, the color development property and fading property of a coating film improve further. Color development here refers to the property of coloring to the extent that the painted and unpainted surfaces are visually distinguished from the difference in color, and fading is the color that does not impair the design of the base material. Refers to the nature of
Although content of (E) component in the coating film obtained from the aqueous composition of this embodiment is not specifically limited, Preferably it is 0.01-1.0 mass%, More preferably, it is 0.05-0. 0.9 mass%, more preferably 0.1-0.8 mass%. By making content of (E) component into the said range, the coating film which was further excellent in the external appearance in a dark-colored base material, a weather resistance, stain resistance, and bio-contamination resistance can be obtained.

The solid content (solid content) in the aqueous composition of the present embodiment is not particularly limited, but is preferably 0.5 to 10.0% by mass, more preferably from the viewpoint of the uniformity of the coating film. Is 1.0-8.0 mass%, More preferably, it is 1.5-6.0 mass%.
By setting the solid content in the aqueous composition to the lower limit value or more, wettability, sprayability, stain resistance, and biofouling resistance are further improved. Transparency improves further by making content of solid content in an aqueous composition into the said upper limit or less.
Solid content here can be calculated | required by the method as described in the Example mentioned later. Furthermore, depending on the application of the coating film, it may be required that the coating film has a small film thickness. Even in such a case, since the solid content in the aqueous composition is less than or equal to the above upper limit value, a coating having excellent physical properties such as weather resistance, stain resistance, and biofouling resistance can be achieved while having a thin film thickness. It can be a membrane. When the solid content in the aqueous composition is equal to or higher than the lower limit, it is possible to shorten the drying time required for forming the coating film, and to further improve the work efficiency.

[Water-based paint]
The aqueous paint of this embodiment contains the aqueous composition of this embodiment mentioned above.
The water-based paint of this embodiment can be obtained, for example, by mixing other components as necessary with the above-described water-based composition.
Examples of the other components include, but are not limited to, for example, a freezing stabilizer, a matting agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, an antiskinning agent, a dispersant, Wetting agents, light stabilizers, antioxidants, UV absorbers, film-forming aids, rust inhibitors, plasticizers, thickeners, lubricants, reducing agents, antiseptics, antifungal agents, algaeproofing agents, deodorants Agents, yellowing inhibitors, antistatic agents, charge control agents and the like.
These may be used alone or in combination of two or more.

Examples of the pigment include inorganic oxides that do not have photocatalytic activity. Although not limited to the following, for example, copper oxide (II) (manufactured by CIK Nanotech, “CUAP15WT% -G180”), zinc oxide, aluminum oxide, and the like can be given.
Although content of the pigment in the coating film obtained from the water-based coating material of this embodiment is not specifically limited, Preferably it is 0.01-5.0 mass%, More preferably, it is 0.02-4.5 mass%. It is. By setting the pigment content in the above range, it is possible to obtain a coating film having excellent appearance on a dark base material and excellent biofouling resistance.

  The water-based paint of the present embodiment can be applied by a suitable method depending on the application and the material to be applied. Examples of the application method include, but are not limited to, spray spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, and gravure printing. Method and flexographic printing method.

[Coating]
The coating film of this embodiment is obtained from the water-based paint of this embodiment.
Specifically, it is obtained by applying the water-based paint to a predetermined application target and then drying to remove volatile components. Under the present circumstances, you may further perform the heat processing by the temperature of about 40-120 degreeC, an ultraviolet irradiation process, etc. as needed.

[Composite coating]
The composite coating film of this embodiment has at least two layers of an overcoat layer obtained from a water-based paint containing the aqueous composition of the present embodiment and an undercoat layer, and the undercoat layer is It contains a polymer and an algal and / or antifungal agent.
The composite coating film of this embodiment is obtained by, for example, applying the water-based paint containing the water-based composition to the surface of the undercoat layer and drying it.
The undercoat layer preferably contains a polymer and one or more kinds of antialgal and / or antifungal agents.

(Polymer contained in undercoat layer)
The undercoat layer constituting the composite coating film of this embodiment contains a polymer. Thereby, the composite coating film excellent in a weather resistance can be formed. In addition, the effect | action of this embodiment is not limited to these.
Although it does not specifically limit as a polymer, For example, the polymer obtained by methods, such as emulsion polymerization, can be used. Examples of the polymer include, but are not limited to, a polymer obtained by performing any one of radical polymerization, anionic polymerization, and cationic polymerization in an aqueous medium.
Specific examples of the polymer include poly (meth) acrylate polymers, polyvinyl acetate polymers, vinyl acetate- (meth) acrylic polymers, ethylene vinyl acetate polymers, silicone polymers, fluorine. Polymer, polybutadiene polymer, styrene butadiene polymer, NBR polymer, polyvinyl chloride polymer, chlorinated polypropylene polymer, polyethylene polymer, polystyrene polymer, vinylidene chloride polymer, Homopolymers or copolymers represented by polystyrene- (meth) acrylate polymers, styrene-maleic anhydride polymers, silicone-modified (meth) acrylic polymers, fluorine- (meth) acrylic polymers Modifications typified by (meth) acrylic-silicone polymers, epoxy- (meth) acrylic polymers, etc. Polymers.
These may be used alone or in combination of two or more.
“(Meth) acrylate” means “acrylate” and “methacrylate” corresponding to it, and “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

  The above-mentioned polymer homopolymers, copolymers, modified copolymers, etc. (hereinafter, these may be collectively referred to as “polymers”) are preferably obtained in the form of an aqueous dispersion. Suitable examples of these polymers include emulsions, and specific examples thereof include, but are not limited to, acrylic emulsions, acrylic silicon emulsions, silicone emulsions, and the like. Although these are not limited to the following, For example, it can obtain by emulsion polymerization, such as monomers, such as (meth) acrylic acid ester, and the hydrolyzable silicon compound mentioned later.

In addition to the polymer, the undercoat layer included in the composite coating film of this embodiment may further include a compound having a functional group that reacts with a functional group included in the polymer.
Examples of such compounds include, but are not limited to, for example, (poly) isocyanate compounds, (poly) epoxy compounds, amino compounds, (poly) carboxy compounds, (poly) hydroxy compounds, glycol compounds, silanols. Examples thereof include compounds, silyl compounds, alkoxy compounds, (meth) acrylate compounds and the like.
These may be used alone or in combination of two or more.

The polymer can use a vinyl monomer as a polymerization monomer.
The vinyl monomer that can be used in the production of the polymer is not limited to the following, but examples thereof include (meth) acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, carboxyl group-containing vinyl compounds. A vinyl monomer containing a functional group such as a hydroxyl group-containing vinyl compound, a glycidyl group-containing vinyl compound, a vinyl compound having a secondary and / or tertiary amide group, and an anionic vinyl compound.

The (meth) acrylic acid ester is not limited to the following. For example, the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 50 carbon atoms and an ethylene oxide group having 1 to 100 carbon atoms ( And poly) oxyethylene di (meth) acrylate. Specific examples of these include, but are not limited to, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate. , Methyl cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.
Examples of (poly) oxyethylene di (meth) acrylate include, but are not limited to, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate.

Examples of the aromatic vinyl compound include, but are not limited to, styrene, α-methylstyrene, p-tert-butylstyrene, chlorostyrene, vinyltoluene, and the like.
Examples of the vinyl cyanide compound include, but are not limited to, (meth) acrylonitrile, α-chloroacrylonitrile, and the like.
Examples of the carboxyl group-containing vinyl compound include, but are not limited to, for example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or itaconic acid, maleic acid, fumaric acid. Examples thereof include half esters of dibasic acids such as acids. By using a vinyl monomer containing a carboxyl group, the carboxyl group can be introduced into the polymer. Thereby, it is estimated that the stability as an emulsion can be further improved and a high resistance to an external dispersion breaking action can be imparted to the coating film. In addition, the effect | action of this embodiment is not limited to these. A part or all of the carboxyl group to be introduced can be neutralized with amines such as ammonia, triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. The amount of the carboxyl group-containing vinyl monomer used in the total amount of vinyl monomers used for producing the polymer is preferably 0 to 50% by mass from the viewpoint of water resistance.

Examples of the hydroxyl group-containing vinyl compound include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. Hydroxyalkyl esters of (meth) acrylic acid such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono (Poly) oxyethylene mono (meth) acrylate having 1 to 100 butyl fumarate, allyl alcohol or ethylene oxide groups; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, further , And (trade name manufactured by Daicel Chemical Industries caprolactone addition monomer) "PLACCEL FM, FA monomer", and other alpha, hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid.
Examples of (poly) oxyethylene mono (meth) acrylate include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, methoxy Examples include (meth) acrylic acid diethylene glycol, (meth) acrylic acid tetraethylene glycol, and methoxy (meth) acrylic acid tetraethylene glycol.
Examples of (poly) oxypropylene mono (meth) acrylate include, but are not limited to, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate Methoxy (meth) acrylic acid dipropylene glycol, (meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid tetrapropylene glycol, and the like.
The proportion of the hydroxyl group-containing vinyl monomer in the total amount of vinyl monomers used in the production of the polymer is not limited to the following, but is preferably 0 to 95% by mass from the viewpoint of the water resistance of the coating film. is there.

Examples of the glycidyl group-containing vinyl compound include, but are not limited to, glycidyl (meth) acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.
The vinyl compound having a secondary and / or tertiary amide group is not limited to the following, and examples thereof include N-alkyl-substituted (meth) acrylamide and N-alkylene-substituted (meth) acrylamide.
Examples of N-alkyl-substituted (meth) acrylamides include, but are not limited to, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethylacrylamide, N-methyl-N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-methyl-Nn-propyl (meth) acrylamide, N-methyl-N-isopropyl (meth) acrylamide, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, N-acryloylhexahydroazepine, N- (meth) acryloylmorpholine, N-vinylpyrrolidone, N- Vinyl caprolactam, N, N'-methyle Bis (meth) acrylamide, N-vinylacetamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide and the like.

The said polymer can use vinyl monomers other than the vinyl monomer mentioned above as a polymerization monomer.
Examples of vinyl monomers other than the vinyl monomers described above include, but are not limited to, olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride Haloolefins such as vinylidene chloride, vinyl chloride, tetrafluoroethylene and chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl pivalate, Carboxylic acid vinyl esters such as vinyl 2-ethylhexanoate, vinyl versatate, vinyl laurate; isopropenyl acetate such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl Vinyl ethers such as ruether; aromatic vinyl compounds such as styrene and vinyl toluene; allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl ether and allyl phenyl ether; 4- (meth) acryloyloxy- 2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, Examples include perfluoropropylmethyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, and allyl (meth) acrylate.
These may be used alone or in combination of two or more.

When the polymer is produced by a polymerization reaction, a chain transfer agent may be used for the purpose of controlling the molecular weight of the polymerization product of the vinyl monomer used.
Examples of the chain transfer agent include, but are not limited to, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan. Thiocarboxylic acids such as thiomalic acid or salts thereof or alkyl esters thereof; polythiols; disulfides such as diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide; thioglycol, α-methylstyrene dimer, etc. Examples include allyl compounds.
These may be used alone or in combination of two or more.

The polymer is preferably produced by a polymerization reaction between the vinyl monomer and the hydrolyzable silicon compound described above.
In such a case, the hydrolyzable silicon compound used for producing the polymer is not limited to the following, but for example, a compound represented by the following formula (1), a silane coupling agent, and these The condensate of is mentioned as a preferable thing.
SiWxRy (1)
In said formula (1), W is a C1-C20 alkoxy group, a hydroxyl group, a C1-C20 acetoxy group, a halogen atom, a hydrogen atom, a C1-C20 oxime group, an enoxy group, an aminoxy group. And at least one selected from the group consisting of amide groups.
R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a C 6 to 20 carbon atom substituted with a halogen atom. Represents at least one group selected from the group consisting of aryl groups.
x is an integer from 1 to 4, y is an integer from 0 to 3, and satisfies the relationship x + y = 4.
When there are a plurality of Ws, and when there are a plurality of Rs, each W and R may be the same as or different from each other.
The compound represented by the formula (1) is not limited to the following, and examples thereof include silicon alkoxide represented by the formula (1).

Examples of the silane coupling agent include, but are not limited to, hydrolyzable groups (for example, alkoxy groups having 1 to 20 carbon atoms, hydroxyl groups, acetoxy groups having 1 to 20 carbon atoms, halogen atoms, hydrogen atoms) A functional group (for example, vinyl polymerizable group) having reactivity with an atom, at least one selected from the group consisting of an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group, and other compounds. , Epoxy group, amino group, methacryl group, thiol group, isocyanate group, etc.) and the like, and hydrolyzable silicon compounds (silane coupling agents).
By using such a silane coupling agent as the hydrolyzable silicon compound, the polycondensate of the hydrolyzable silicon compound and the vinyl monomer can be chemically bonded to each other. Thereby, compatibility improves further and the transparency of a coating film improves further.
Among the silane coupling agents described above, a silane coupling agent having at least a vinyl polymerizable group and / or a thiol group is preferable, and a silane coupling agent having at least a vinyl polymerizable group is more preferable.
Since the vinyl polymerizable group and the thiol group have high reactivity with the vinyl monomer described above, a chemical bond can be efficiently formed by copolymerization reaction or chain transfer reaction with the vinyl monomer. Therefore, by using a silane coupling agent having a vinyl polymerizable group or a thiol group, it can be efficiently combined with other components (for example, a vinyl monomer) constituting the polymer. By using such a polymer in which a hydrolyzable silicon compound (or a polymerization product thereof) and / or a vinyl monomer (or a polymerization product thereof) is combined by a chemical bond, weather resistance and strength are improved. Thus, a composite coating film with further improved and the like can be obtained. In addition, the effect | action of this embodiment is not limited to these.

Examples of the silane coupling agent having a vinyl polymerizable group include, but are not limited to, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3 -(Meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltri Preferred examples include methoxysilane and 2-trimethoxysilylethyl vinyl ether.
Although it does not limit to the following as a silane coupling agent which has a thiol group, For example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. are mentioned as a preferable thing.

The hydrolyzable silicon compound and the silane coupling agent represented by the formula (1) are not limited to the following, but examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra Tetraalkoxysilanes such as isopropoxysilane and tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-o Tiltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyl Limethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meta ) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropylto Trialkoxysilanes such as lysopropoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyl Dimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n- Pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane Dialkoxy such as di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane Silanes; monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane.
Among these, tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes are preferable, tetraethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, dimethyldimethoxysilane. Is more preferable.
These silicon alkoxides and silane coupling agents represented by the formula (1) may be used alone or in combination of two or more. Among these, from the viewpoint of improving the performance of the aqueous composition and the resulting coating film, it is preferable to use the silicon alkoxide represented by the formula (1) and a silane coupling agent in combination, tetraethoxysilane, methyltrimethoxy. More preferably, at least one selected from the group consisting of silane, phenyltrimethoxysilane and dimethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane are used in combination.

In producing the polymer, a titanium alkoxide, a zirconium alkoxide, a condensation product or a chelated product thereof can be used in combination with the hydrolyzable silicon compound.
By using these compounds in combination, it is possible to obtain a coating film with better water resistance and the like.
Examples of the titanium alkoxide include, but are not limited to, tetramethoxy titanium, tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec- Examples include butoxy titanium and tetra-tert-butoxy titanium.
Examples of the zirconium alkoxide include, but are not limited to, tetramethoxy zirconium, tetraethoxy zirconium, tetra-i-propoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec- Examples include butoxyzirconium and tetra-tert-butoxyzirconium.

When the polymer is produced, a chelating agent that forms a chelate by coordinating with the free metal ion of the metal compound may be used in combination.
Preferred chelating agents include, but are not limited to, for example, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; ethyl acetoacetate and the like It is done.
The molecular weight of the chelating agent is not limited to the following, but is preferably 10,000 or less.
By using these chelating agents, the polymerization rate of the hydrolyzable silicon compound or the like can be controlled, and the polymerization stability in the presence of water and an emulsifier is further improved.
Although the compounding quantity of a chelating agent is not specifically limited, It is preferable that it is a ratio of 0.1 mol-2 mol with respect to 1 mol of free metal ions to coordinate.

Examples of the emulsifier that can be used in the production of the polymer include, but are not limited to, alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, Acidic emulsifiers such as polyoxyethylene distyryl phenyl ether sulfonic acid; alkali metal (Li, Na, K etc.) salts of the acidic emulsifiers; ammonium salts of the acidic emulsifiers; anionic surfactants such as fatty acid soaps; Quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium salt, imidazolinium salt type cationic surfactants; polyoxyethylene alkylaryl ether, polyoxy Chirensorubitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymer, nonionic surface active agent polyoxyethylene distyryl phenyl ether; reactive emulsifier or the like having a radical polymerizable double bond.
Among these emulsifiers, a reactive emulsifier having a radical polymerizable double bond (hereinafter sometimes simply referred to as a reactive emulsifier) is preferable. By using such a reactive emulsifier, the water dispersion stability of the polymer becomes very good and the water resistance of the resulting coating film is further improved.

Examples of the anionic reactive emulsifier include, but are not limited to, ethylenically unsaturated monomers having a sulfonic acid group, a sulfonate group, or a sulfate ester group and salts thereof. A compound having an acid group or a group (ammonium sulfonate group or alkali metal sulfonate group) which is an ammonium salt or an alkali metal salt thereof is preferable.
Examples of the anionic reactive emulsifier include, for example, alkylallylsulfosuccinate (eg, Sanyo Kasei Co., Ltd., “Eleminol (trademark) JS-20”, Kao Corporation, “Latemuru (trademark) S-120”, “Latemuru). S-180A "," Latemul S-180 "and the like), polyoxyethylene alkylpropenyl phenyl ether sulfate ester salt (for example," Aqualon (trademark) HS-10 "manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and the like. ), Α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SE-10N manufactured by ADEKA) And the like.), Ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxye Len (for example, “Aqualon KH-1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), styrene sulfonate (for example, “Spinomer (trademark) NaSS” manufactured by Tosoh Organic Chemical Co., Ltd.), α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene sulfate ester salt (for example, “ADEKA rear soap (trademark) SR-1025” manufactured by ADEKA) ), Sulfate ester of polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example, “Latemul (trademark) PD-104” manufactured by Kao Corporation) and the like.
Among these, ammonium-α-sulfonato-ω-1- (allyloxymethyl) alkyloxypolyoxyethylene, α- [2-[(allyloxy) -1- (alkyloxymethyl) ethyl] -ω-polyoxyethylene Sulfuric acid ester salts are preferred.

  Further, the nonionic reactive emulsifier is not limited to the following, and examples include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene. (For example, (Adeka Soap NE-20, “Adekalia Soap NE-30”, “Adekalia Soap NE-40”, etc., manufactured by ADEKA Corporation) and the like), polyoxyethylene alkylpropenyl phenyl ether (for example, Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., “AQUALON RN-10”, “AQUALON RN-20”, “AQUALON RN-30”, “AQUALON RN-50”, etc.), α- [2-[(allyloxy) ) -1- (alkyloxymethyl) ethyl] -ω-hydroxypolyoxyethylene (for example, “Adekalyazo” manufactured by ADEKA) (Trademark) ER-10 "), polyoxyethylene polyoxybutylene (3-methyl-3-butenyl) ether (for example," Latemul (trademark) PD-420 "manufactured by Kao Corporation) And the like.

  The amount of the above-mentioned emulsifier is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of polymer raw materials (for example, hydrolyzable silicon compound and vinyl monomer). By making the usage-amount of an emulsifier into the said range, superposition | polymerization stability improves further and the water resistance of a coating film becomes much better.

The polymerization of the vinyl monomer and the hydrolyzable silicon compound is preferably carried out in the presence of a polymerization catalyst.
The polymerization catalyst for the vinyl monomer is not particularly limited, but a radical polymerization catalyst that causes addition polymerization of the vinyl monomer by radical decomposition itself by heat or a reducing substance is preferable.
Examples of such radical polymerization catalyst include, but are not limited to, persulfates, peroxides, azobis compounds, and the like. These may be water-soluble or oil-soluble.
Examples of the radical polymerization catalyst include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, 2, 2 -Azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
Although the compounding quantity of a radical polymerization catalyst is not specifically limited, Preferably it is 0.001-5 mass parts with respect to 100 mass parts of total amounts of a vinyl monomer. In addition, when acceleration of the polymerization rate and efficient polymerization at a low temperature (for example, 70 ° C. or lower) are desired, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite is used as a radical polymerization catalyst. It is preferable to use together.

The polymerization catalyst for the hydrolyzable silicon compound is not limited to the following. For example, hydrogen halides such as hydrochloric acid and hydrofluoric acid; carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid; sulfuric acid Sulfonic acids such as p-toluenesulfonic acid; acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylenealkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid Acidic or weakly acidic inorganic salts; acidic compounds such as phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine The Basic compounds such as zabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; dibutyltin octylate, dibutyltin dilaurate, etc. The tin compound is mentioned.
Among these, as the polymerization catalyst for the hydrolyzable silicon compound, acidic emulsifiers are preferable from the viewpoint of having a function as an emulsifier as well as a polymerization catalyst. As the acidic emulsifier, an alkylbenzene sulfonic acid having 5 to 30 carbon atoms (for example, dodecylbenzene sulfonic acid) is more preferable.

Polymerization of the vinyl monomer and the hydrolyzable silicon compound can be carried out separately, but it is preferable because complexization can be achieved efficiently by carrying out the polymerization simultaneously.
Suitable methods for obtaining the polymer include, for example, so-called emulsion polymerization in which the emulsifier polymerizes the vinyl monomer and the hydrolyzable silicon compound in the presence of a sufficient amount of water to form micelles. .
The specific method of emulsion polymerization is not particularly limited. For example, the vinyl monomer and the hydrolyzable silicon compound are dropped into the reaction vessel as they are or in an emulsified state, all at once or in a divided manner or continuously. And a method of polymerizing at a reaction temperature of about 30 to 150 ° C. in the presence of a polymerization catalyst, preferably under a pressure of atmospheric pressure to 10 MPa.
The reaction temperature and reaction pressure are not limited to the above conditions depending on the reaction conditions and the like.
Although the solid content in the emulsion obtained by emulsion polymerization is not particularly limited, it is preferably 0.1 to 70% by mass, more preferably 1 to 55% by mass.
When it is desired to further control the particle size during emulsion polymerization, it is preferable to employ a seed polymerization method in which emulsion particles are preliminarily present in the aqueous phase for polymerization. The pH of the polymerization system in this case is not particularly limited, but is preferably 1.0 to 10.0, and more preferably 1.0 to 6.0. This pH can be adjusted using a pH buffer such as disodium phosphate, sodium tetraborate (borax, etc.), sodium hydrogen carbonate, ammonia and the like.

  The method for producing the polymer is not particularly limited. For example, after polymerizing the hydrolyzable silicon compound and the vinyl monomer in the presence of a solvent, if necessary, in the presence of water and an emulsifier, a polymerization product is obtained. A method of further adding water until an emulsion is obtained can also be employed. From the viewpoint of easy control of the particle size of the obtained polymer, it is preferable to obtain the polymer by emulsion polymerization.

The content of the polymer in the undercoat layer of the composite coating film of the present embodiment is not particularly limited, but is preferably 0.1 to 80% by mass, more preferably 1.0 to 75% by mass, and further Preferably it is 5.0-70 mass%.
By setting the content of the polymer in the undercoat layer of the composite coating film of the present embodiment within the above range, the composite coating having further improved appearance, weather resistance, stain resistance, and biofouling resistance on the dark base material. A membrane can be obtained.

(Algae and fungicides contained in the undercoat layer)
The undercoat layer constituting the composite coating film of the present embodiment further contains an algal and / or antifungal agent.
Thereby, the composite coating film which is excellent in bio-contamination resistance can be formed also in the place where light, such as sunlight, is hard to be irradiated. In addition, the effect | action of this embodiment is not limited to these.
The algae and / or antifungal agent is not limited to the following, but includes, for example, organic iodine compounds, alcohol compounds, nitrile compounds, disulfide compounds, thiocarbamate compounds, nitrogen-containing ring compounds, etc. Is mentioned. Among these, a nitrogen-containing ring compound is preferable. Examples of nitrogen-containing ring compounds include thiazoline compounds, isothiazoline compounds, triazine compounds, and imidazole compounds. Among these, at least one selected from the group consisting of isothiazoline compounds, triazine compounds, and imidazole compounds is preferable, and at least one selected from the group consisting of isothiazoline compounds and triazine compounds is more preferable.
Examples of particularly excellent algae-proofing properties include triazine compounds.
Examples of particularly excellent antifungal properties include thiazoline compounds, isothiazoline compounds, imidazole compounds, and the like.
In the undercoat layer of the composite coating film of the present embodiment, a material having both an antialgal property and an antifungal property may be used. For example, an isothiazoline compound containing a chlorine atom in the molecule, etc. Is mentioned.
These may be used alone or in combination of two or more.

A commercial item can also be used as a thiazoline type compound. Examples of such commercially available products include “Milcut-180” and “Biocut-LC3” manufactured by Nippon Soda Co., Ltd., “Amorden ALK” manufactured by Yamato Chemical Co., Ltd. and the like.
A commercial item can also be used as an isothiazoline type compound. Examples of such commercially available products include “Biocut-TR120” manufactured by Nippon Soda Co., Ltd., “PROXEL GXL”, “PROXEL BDN” manufactured by Arch Chemicals, “KLARIX 4000”, “ROZONE 2000” manufactured by Dow Chemical. , “ROCIMA 252”, “ROCIMA 200”, “ROCIMA 345”, “ROCIMA 350”, “ROCIMA 553”, “BIOBAN 551S”, “Skane M-8”, and the like.
A commercial item can also be used as a triazine type compound. Examples of commercially available products include “Biocut-N35”, “DP-2159”, and “DP-2615” manufactured by Nippon Soda Co., Ltd. “DP-2619”, “DP-2623”, “Amorden NBP-8”, “Amorden NBPconc” manufactured by Daiwa Chemical Industries, “San Aruga 1907” manufactured by Sankyo Kasei Co., Ltd., and the like.
A commercial item can also be used as an imidazole compound. Examples of commercially available products include “Biocut-N35”, “Biocut-AF40” and “DX-2” manufactured by Nippon Soda Co., Ltd., “ROCIMA 363” manufactured by Dow Chemical Company, and the like.

  The content of the algae and / or antifungal agent in the undercoat layer is not particularly limited, but is preferably 0.01% by mass to 30.0% by mass, more preferably 0.01% by mass to 15.0%. It is mass%, More preferably, it is 0.1 mass%-15.0 mass%. By setting the content of the anti-algae and / or anti-fungal agent in the undercoat layer to be equal to or higher than the lower limit, the bio-fouling resistance of the composite coating is further improved, and by setting the content to the upper limit or less, the composite coating This further improves the weather resistance.

In the composite coating film of this embodiment, other antibacterial agents may be used in combination as long as the effects of this embodiment are obtained.
Examples of other antibacterial agents include, but are not limited to, silver compounds, copper compounds, and zinc compounds.

In the undercoat layer of the composite coating film of the present embodiment, for example, in addition to the polymer and the antialgae and / or antifungal agent described above, other components can be mixed as necessary.
Examples of the other components include, but are not limited to, for example, a freezing stabilizer, a matting agent, a crosslinking reaction catalyst, a pigment, a curing catalyst, a crosslinking agent, a filler, an antiskinning agent, a dispersant, Wetting agent, light stabilizer, antioxidant, UV absorber, film forming aid, rust inhibitor, plasticizer, thickener, lubricant, reducing agent, preservative, deodorant, anti-yellowing agent, static Examples thereof include an antistatic agent and a charge control agent.
These may be used alone or in combination of two or more.

The composite coating film of this embodiment has at least two layers of a top coating layer that is a coating film obtained from the water-based paint containing the water-based composition of this embodiment and the above-described undercoat layer.
In the composite coating film of this embodiment, an overcoat layer may be formed directly on the undercoat layer, or a multilayer structure through other predetermined layers, or other predetermined layers are formed under the undercoat layer. It may be a multilayered structure. It is preferable that the top coat layer, which is a coating film obtained from the water-based paint containing the water-based composition of the present embodiment, is in the uppermost layer.
The undercoat layer of the composite coating film can be obtained by applying it by a suitable method depending on its use, the material to be applied, and the like.
Examples of the application method include, but are not limited to, spray spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, and gravure printing. Method, flexographic printing method, wire bar coating method and the like.
The topcoat layer is formed on the undercoat layer or other predetermined layer, for example, spray spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, gravure. It can be formed by applying a printing method or a flexographic printing method, whereby the composite coating film of this embodiment can be produced.

[Coated products]
The coated product of this embodiment comprises a base material and the coating film formed on at least a part of the surface of the base material.
The coated product of the present embodiment can be obtained, for example, by applying a water-based paint containing the above-described water-based composition of the present embodiment to the surfaces of various substrates and drying.
Moreover, the coating product of this embodiment can also be set as the form which comprises a base material and the composite coating film of this embodiment mentioned above. The coated product comprising the composite coating film is formed by applying an undercoat layer containing the polymer and the anti-algae and / or anti-fungal agent on the surface of various substrates and drying, and then further undercoat layer It is obtained by applying the above-described water-based paint of this embodiment to the surface of the film and drying it.

The base material used in the coated product of the present embodiment is not particularly limited as long as a coating film can be formed on the surface thereof, and may be either an organic base material or an inorganic base material. From the viewpoint of improving the properties, an organic substrate is preferable.
Examples of the material for the base material include, but are not limited to, organic base materials such as synthetic resins and natural resins; and inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete.
These may be used alone or in combination of two or more.

Examples of the synthetic resin include, but are not limited to, thermoplastic resins and curable resins (thermosetting resins, photocurable resins, moisture curable resins, and the like).
Examples of synthetic resins include, but are not limited to, silicone resins, acrylic resins, methacrylic resins, fluororesins, alkyd resins, aminoalkyd resins, vinyl resins, polyester resins, styrene-butadiene resins, polyolefin resins, Polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, Examples thereof include phenol resin, melamine resin, epoxy resin, urethane resin, and silicone-acrylic resin.
Examples of natural resins include, but are not limited to, cellulose resins, isoprene resins such as natural rubber, and protein resins such as casein.
When the base material is a resin base material using the above-described synthetic resin, natural resin, or the like, surface treatment such as corona discharge treatment, flame treatment, or plasma treatment may be performed as necessary.

The coated product of the present embodiment includes a base material and the coating film formed on the base material, and the coating film is useful as a coating or the like.
The coating film obtained from the water-based paint of this embodiment is excellent in spray characteristics and wettability of the coating liquid assuming on-site coating, and does not impair the appearance even with a dark-colored base material. In addition, the biocontamination resistance can be maintained at a high level.
From this point of view, the coated product of the present embodiment is not limited to the following, for example, building materials, building exterior, building interior, window frame, window glass, various lenses, structural members, building equipment such as houses, Covers and window glass for vehicular lamps, exteriors of machinery and equipment, dust covers and coatings, display devices, covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, etc. , Exteriors and paintings of bridges, guardrails, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, etc., exterior parts of electronic and electrical equipment used outside, especially transparent materials, plastic houses, greenhouses, etc. Is mentioned.

As a manufacturing method of the coated product of this embodiment, for example, the water-based paint of this embodiment (or the water-based composition of this embodiment) described above is applied to at least a part of the surface of the substrate, and as necessary. Although the method of forming a coating film by performing drying etc. is mentioned, it is not limited to this.
For example, after applying the coating film of this embodiment on a base material, the coating film may be peeled off from the base material and adhered to another base material. Or after apply | coating the coating film of this embodiment on a base material, you may make it adhere | attach on another base material in the state closely_contact | adhered with the base material.

  You may mix | blend the water-system composition of this embodiment with various water-system paints. Such a water-based paint can form a coating film excellent in appearance, stain resistance, sealing stain resistance, biofouling resistance, transparency and weather resistance. Thus, the coating film of this embodiment is excellent in spray characteristics and wettability of the coating liquid assuming on-site coating, and does not impair the appearance even with a dark base material, and has a long-term appearance and stain resistance. Since the biofouling resistance can be maintained at a high level and further excellent in transparency and weather resistance, it can be used in a wide range of applications including exterior paints for buildings.

  Hereinafter, the present embodiment will be specifically described with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples.

The base material used in the measurement of the characteristics described later was manufactured as follows.
[Preparation of 7cm x 15cm base material pre-coated with enamel paint]
(Preparation of pigment dispersion)
Dispersant (BASF Japan, “Pig. Disperser MD20”) 5.35 g, ammonia water 0.5 g, propylene glycol 23.5 g, water 147.5 g, titanium oxide (chlorine method rutile titanium oxide; manufactured by Ishihara Sangyo Co., Ltd.) , "Typaque CR-97") 333.5 g, antifoaming agent (modified silicone type; manufactured by San Nopco, "SN Deformer 1310") 2.85 g of a blended tabletop sand mill (campe papio, batch type tabletop sand mill) For 20 minutes to obtain a pigment dispersion.

(Production of enamel paint that does not contain an anti-algal and fungicidal agent)
10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, “CS-12”) was added to 109.0 g of the polymer emulsion obtained in [Production Example 1] described later. , 10.0 g of a mixed solution of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, thickener (Adecanol UH-438, manufactured by Asahi Denka Kogyo Co., Ltd. The enamel paint X was obtained by adding 0.5 g of a 10% by weight aqueous solution of “)” and mixing for 1 hour.
(Preparation of a 7 cm × 15 cm base material pre-coated with an enamel paint X not containing an anti-algal and anti-fungal agent)
The enamel paint X obtained as described above was applied to a 7 cm × 15 cm sulfate alumite plate using a wire coater No. 50 and dried at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm × 15 cm base material pre-coated with the enamel paint X.

(Production of enamel paint containing anti-algae and fungicides)
10.0 g of 2,2,4-trimethyl-1,3-butanediol isobutyrate (manufactured by Chisso Corporation, “CS-12”) was added to 109.0 g of the polymer emulsion obtained in [Production Example 1] described later. , 10.0 g of a mixed solution of 50 parts by mass of ethylene glycol monobutyl ether and 50 parts by mass of water, 51.4 g of the pigment dispersion obtained as described above, thickener (Adecanol UH-438, manufactured by Asahi Denka Kogyo Co., Ltd. )) 10 g% aqueous solution 0.5 g, anti-algal fungicide N-35 (Nippon Soda Co., Ltd., solid content 35% by mass) 0.9 g, anti-algae fungicide AF-40 (Nippon Soda Co., Ltd., solid content) 40 mass%) 0.4 g was added and mixed for 1 hour to obtain an enamel paint Y.
(Preparation of 7 cm × 15 cm base material pre-coated with enamel paint Y containing anti-algal and anti-fungal agents)
The enamel paint Y obtained as described above was applied to a 7 cm × 15 cm alumite sulfate plate with a wire coater No. 50 and dried at a temperature of 23 ° C. and a relative humidity of 50% for 48 hours to obtain a 7 cm × 15 cm base material pre-coated with the enamel paint Y.

Various physical properties were measured by the following 1-3.
(1. Content and solid content of each component)
A sample (2.0 g) was placed in an aluminum dish and heated at 150 ° C. for 1 hour. The mass of the sample before and after heating was measured, and the solid content (mass%) was calculated from the difference. Based on this method, the content of each component and the solid content in the aqueous composition were measured.

(2. Number average particle size)
Ion exchange water was added and diluted so that the loading index was 1.5 to 3.0, and measurement was performed using a wet particle size analyzer (manufactured by Nikkiso Co., Ltd., “Microtrac UPA-9230”). The measurement conditions are shown below.
-Loading index: 1.5-3.0
・ Measurement time: 60 seconds ・ Number of measurements: 3 times

(3. Glass transition temperature)
Using Seiko Instruments Inc., “DCS 6220”, the glass transition temperature was determined from the inflection point of the obtained DSC curve. Measurement conditions are shown below.
Measurement cell: Aluminum container Preparation of measurement sample: 40 mg of emulsion as a measurement sample was put in an aluminum container and dried at 130 ° C. for 1 hour.

Various characteristics were measured by the following 4-9.
(4. Color difference before and after painting)
JISK5600 paint general test method Coverage rate test paper (manufactured by Nippon Test Panel Co., Ltd.) is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^{2 on} the black background part (L * value 7). Used to paint. The coated test paper was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. The color difference before and after coating was measured using a “color guide” manufactured by BYK Gardner. If the color difference is 3.4 or less, it indicates that there is little change in the color difference on the dark background, which is good.

(5. Pollution resistance)
A 7 cm × 15 cm base material previously coated with an enamel paint containing an algal / antifungal agent prepared as described above is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^2. Used to paint. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. The test plate was affixed to a fence facing a general road (traffic volume of about 500 to 1000 vehicles / day) and allowed to stand for 6 months or 1 year.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result evaluated only with the base material previously coated with the enamel paint was an evaluation of “x” for 6 months and 1 year.
[Evaluation criteria]
○: Dirt was hardly confirmed.
Δ: Although some contamination was confirmed, there was no practical problem.
X: A large amount of dirt was confirmed.

(6. Biofouling resistance (enamel paint that does not contain anti-algal and anti-fungal agents))
Sprayed onto the 7 cm × 15 cm base material previously coated with the enamel paint not containing the anti-algal and anti-fungal agent prepared as described above so that the coating amount of the aqueous composition is 17.0 g / m ^2. Painted with The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. In June, Kasama City, Ibaraki Prefecture, affixed to the fence facing the north side of the building, where the surrounding trees are thick, tilted 45 ° from the horizontal plane, with the painted side facing up, and for one year from June Left to stand.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result evaluated only with the base material which applied the enamel paint which does not contain an algae mold prevention agent beforehand was "x" evaluation.
[Evaluation criteria]
○: Almost no algae or mold stains were observed.
Δ: Although some algae and mold stains were confirmed, there was no practical problem.
X: A large amount of algae and mold stains were confirmed.

(7. Biofouling resistance (enamel paint containing anti-algal and anti-fungal agents))
A 7 cm × 15 cm base material previously coated with an enamel paint containing an algal / antifungal agent prepared as described above is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^2. Used to paint. The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate. In June, Kasama City, Ibaraki Prefecture, affixed to the fence facing the north side of the building, where the surrounding trees are thick, tilted 45 ° from the horizontal plane, with the painted side facing up, and for one year from June Left to stand.
The degree of contamination of the test plate after standing was visually evaluated based on the following criteria.
In addition, the result evaluated only with the base material previously coated with the enamel paint containing the algal / antifungal agent was an evaluation of “◯”.
[Evaluation criteria]
○: Almost no algae or mold stains were observed.
Δ: Although some algae and mold stains were confirmed, there was no practical problem.
X: A large amount of algae and mold stains were confirmed.

(8. Wettability)
A 7 cm × 15 cm base material previously coated with an enamel paint containing an algal / antifungal agent prepared as described above is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^2. Applied.
The time until the applied aqueous composition spreads wet on the substrate was measured and evaluated according to the following criteria.
[Evaluation criteria]
A: Wet spread in 3 minutes or less.
○: Wet and spread in more than 3 minutes and less than 4 minutes.
Δ: Wet spread in more than 4 minutes and less than 5 minutes.
X: Wet and did not spread in 5 minutes or less.

(9. Sprayability)
100 g of the aqueous composition was placed in a 100 mL plastic container and shaken strongly for 30 seconds.
Thereafter, the plastic container containing the aqueous composition was allowed to stand for 10 minutes.
A 7 cm × 15 cm base material previously coated with an enamel paint containing an algal / antifungal agent prepared as described above is sprayed so that the coating amount of the aqueous composition is 17.0 g / m ^2. Used to paint.
The coated substrate was kept horizontal and allowed to stand for 48 hours at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux to obtain a test plate.
The appearance of the test plate after standing was visually evaluated based on the following criteria.
[Evaluation criteria]
○: Almost no craters or repelling were observed.
Δ: Although some craters and repelling were confirmed, there was no practical problem.
X: Many craters and repelling were confirmed.

In the following Production Example 1, a polymer emulsion for the enamel paint was produced.
[Production Example 1]
(Synthesis of polymer emulsion)
In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 292.0 g of ion-exchanged water, a reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 8 0.0 g was added, and the temperature in the reactor was heated to 80 ° C. with stirring. In this reactor, 10.0 g of a 2% by mass ammonium persulfate aqueous solution was added, and 5 minutes later, 10.0 g of methyl methacrylate, 5.0 g of cyclohexyl methacrylate, 75.0 g of n-butyl acrylate, methacrylic acid 5.0 g, 10.0 g of 2-hydroxyethyl methacrylate, reactive emulsifier (manufactured by ADEKA, “ADEKA rear soap SR-1025”; solid content 25% by mass aqueous solution) 4.0 g, 2% by mass ammonium persulfate aqueous solution 15 An emulsion mixture composed of 0.0 g and ion-exchanged water 49.0 g was added dropwise over 60 minutes with the temperature in the reactor kept at 80 ° C. Thereafter, the temperature in the reactor was maintained at 80 ° C. and stirring was continued for 60 minutes.
Next, 70.0 g of methyl methacrylate, 90.0 g of cyclohexyl methacrylate, 232.0 g of n-butyl acrylate, 8.0 g of methacrylic acid, a reactive emulsifier (manufactured by ADEKA, “Adekari Soap SR-1025”; solid 25 wt% aqueous solution) 16.0 g, 2 wt% aqueous ammonium persulfate solution 60.0 g, ion-exchanged water 196.0 g emulsified mixed solution, 3-methacryloxypropyltrimethoxysilane 1.0 g, dimethyldimethoxysilane 20 0.0 g and a mixed liquid composed of 20.0 g of methyltrimethoxysilane were dropped from a separate dropping tank over 160 minutes. Thereafter, the temperature in the reactor was maintained at 80 ° C., and stirring was continued for 120 minutes.
After cooling to room temperature, the hydrogen ion concentration of the reaction solution in the reactor was measured and found to be pH 2.2. A 25% mass aqueous ammonia solution was added to the reaction solution to adjust the pH to 8.0, and then the reaction solution was filtered through a 100-mesh wire mesh to obtain the above-described polymer emulsion for enamel paint.
The obtained polymer emulsion had a solid content of 44.5% by mass. About the polymer contained in this polymer emulsion, the glass transition temperature calculated | required from the inflection point of the DSC curve based on the method mentioned above was -5 degreeC.

In the following Production Examples 2 to 8, inorganic oxides having photocatalytic activity were produced.
[Production Example 2]
(Synthesis of inorganic oxide (C-1) having photocatalytic activity)
<Silica-modified rutile titanium oxide>
700 mL of a titanium tetrachloride aqueous solution having a concentration of 200 g / L as TiO ₂ and an aqueous sodium hydroxide solution having a concentration of 100 g / L as Na ₂ O were added to the reactor while maintaining the pH of the reaction solution at 5 to 9. . Then, after adjusting the pH of the reaction liquid to 7, it was filtered and washed until the electric conductivity of the filtrate became 100 μS / cm to obtain a titanium oxide wet cake 1 having a solid content of 28.3 mass%. This titanium oxide wet cake 1 contained fine particles having a rutile structure, and the number average particle diameter of the primary particles thereof was 8 nm.
The obtained titanium oxide wet cake 1 was diluted with pure water to prepare a 1 mol / L slurry.
1 L of this slurry was charged into a 3 L flask, and 1N nitric acid was added so that the molar ratio of titanium oxide / nitric acid was 1/1, and the mixture was heated to a temperature of 95 ° C. and maintained at this temperature for 2 hours. Then, acid heat treatment was performed. The slurry after the acid heat treatment was cooled to room temperature, neutralized to pH 6.7 using 28% aqueous ammonia, and filtered. Then, it wash | cleaned until the electrical conductivity of a filtrate was set to 100 microsiemens / cm, and obtained the titanium oxide wet cake 2 whose solid content is 25 mass%.
The obtained titanium oxide wet cake 2 is repulped by adding an aqueous solution of sodium hydroxide having a concentration of 10% by mass, and then dispersed for 3 hours by an ultrasonic cleaner to have a pH of 10.5 and a solid content of 10% by mass. An alkaline titanium oxide sol was obtained.
2 L of this alkaline titanium oxide sol was charged into a 3 L flask, the flask was heated to a temperature of 70 ° C., 69.4 mL of a sodium silicate aqueous solution having a concentration of 432 g / L as SiO ₂ was added, and then the temperature was raised to 90 ° C. After warming and maintaining for 1 hour, 10% sulfuric acid was added to adjust the pH to 6 to obtain a titanium oxide sol whose surface was 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, pH 7.3, solid content 29 mass%, conductivity A neutral rutile type titanium oxide sol of 1.18 mS / cm was obtained.
The neutral rutile titanium oxide sol contained 15 mass% of silicon hydrous oxide of SiO ₂ basis relative to TiO _2. The number average particle diameter of the primary particles of titanium oxide in the sol was 9 nm.

[Production Example 3]
(Synthesis of inorganic oxide (C-2) having photocatalytic activity)
<Silica modified anatase type titanium oxide>
Aggregated metatitanic acid produced by heating and hydrolyzing a titanium sulfate solution obtained by reacting titanium ore with sulfuric acid was made into an aqueous slurry of 30% by mass in terms of TiO ₂ . Ammonia water was added to the slurry to neutralize to pH 7, and then sulfate ions were removed by filtration and washing to obtain a dehydrated cake.
The resulting dehydrated cake was peptized by adding nitric acid to obtain an acidic titanium oxide sol having a pH of 1.5 comprising titanium oxide fine particles having an anatase type crystal structure (number average particle diameter of primary particles: 7 nm).
The obtained acidic titanium oxide sol is diluted with pure water to make 600 mL of titanium oxide sol having a TiO ₂ equivalent concentration of 200 g / L, then heated to 70 ° C., and sodium silicate having a SiO ₂ equivalent concentration of 432 g / L. 20.8 mL of aqueous solution was added to the reactor simultaneously with 20% sulfuric acid. Thereafter, it was aged for 30 minutes.
Next, 10% aqueous sodium hydroxide solution was added to adjust the pH of the reaction solution to 8, and then the pH of the reaction solution was adjusted to 6 with 2% aqueous sulfuric acid solution. Obtained.
This wet cake was repulped into pure water and then ultrasonically dispersed to obtain anatase-type titanium oxide sol (solid content 20% by mass, pH 7.5) stable in the neutral range.
In this, the aggregated silica was deposited in a porous state on the surface of the titanium oxide fine particles, and the content thereof was 7 parts by mass in terms of SiO _{2 with} respect to 100 parts by mass of TiO ₂ .

[Production Example 4]
(Synthesis of inorganic oxide (C-3) having photocatalytic activity)
<Copper-supported silica-modified rutile titanium oxide>
In a reactor having a reflux condenser, a thermometer, and a stirring device, 386.4 g of ion-exchanged water and 13.6 g of silica-coated titanium oxide were charged, and the temperature in the reactor was heated to 80 ° C. with stirring.
In this reactor, 0.3 g of copper chloride dihydrate and 4.0 g of ion-exchanged water were added, and 0.3 g of trisodium citrate dihydrate, 0.1 g of tannic acid and ion-exchanged water 13. 2 g was charged. The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain copper-supported silica-modified titanium oxide. This copper-supporting silica-modified titanium oxide had a solid content of 2.0% and a pH of 5.3.

[Production Example 5]
(Synthesis of inorganic oxide (C-4) having photocatalytic activity)
<Silver supported silica modified rutile titanium oxide>
Into a reactor having a reflux condenser, a thermometer and a stirrer, 386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) are added, and the temperature in the reactor is increased to 80 ° C. with stirring. Warm up. Into this reactor, 0.1 g of silver nitrate and 2.4 g of ion-exchanged water were added, and 0.2 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 7.8 g of ion-exchanged water were added.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered through a nylon mesh having a mesh size of 74 μm to obtain silver-supported silica-modified titanium oxide. The silver-supported silica-modified titanium oxide had a solid content of 2.0% and a pH of 6.9.

[Production Example 6]
(Synthesis of inorganic oxide (C-5) having photocatalytic activity)
<Gold-supported silica-modified rutile titanium oxide>
Into a reactor having a reflux condenser, a thermometer and a stirrer, 386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) are added, and the temperature in the reactor is increased to 80 ° C. with stirring. Warm up. In this reactor, 0.1 g of tetrachloroauric acid tetrahydrate and 3.8 g of ion-exchanged water were added, and 0.01 g of tannic acid and 1.2 g of ion-exchanged water were added.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 60 minutes.
After cooling to room temperature, the mixture was filtered with a nylon mesh having a mesh size of 74 μm to obtain gold-supported silica-modified titanium oxide. The gold-supported silica-modified titanium oxide had a solid content of 2.0% and a pH of 7.2.

[Production Example 7]
(Synthesis of inorganic oxide (C-6) having photocatalytic activity)
<Silver copper supported silica modified rutile titanium oxide>
Into a reactor having a reflux condenser, a thermometer and a stirrer, 386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) are added, and the temperature in the reactor is increased to 80 ° C. with stirring. Warm up. Into this reactor, 0.1 g of silver nitrate and 2.4 g of ion-exchanged water were added, and further 0.1 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 7.1 g of ion-exchanged water were added. The reactor temperature was maintained at 80 ° C. and stirring was continued for 45 minutes. Next, 0.02 g of tannic acid and 1.6 g of ion exchange water were added, and 0.1 g of copper chloride dihydrate and 2.0 g of ion exchange water were added.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 45 minutes.
After cooling to room temperature, the mixture was filtered with a nylon mesh having an aperture of 74 μm to obtain silver- and copper-supported silica-modified titanium oxide. The silver copper-supporting silica-coated titanium oxide had a solid content of 2.0% and a pH of 5.7.

[Production Example 8]
(Synthesis of inorganic oxide (C-7) having photocatalytic activity)
<Silver gold supported silica modified rutile titanium oxide>
Into a reactor having a reflux condenser, a thermometer and a stirrer, 386.4 g of ion-exchanged water and 13.6 g of inorganic oxide (C-1) are added, and the temperature in the reactor is increased to 80 ° C. with stirring. Warm up. Into this reactor, 0.1 g of silver nitrate and 2.4 g of ion-exchanged water were added, and 0.1 g of trisodium citrate dihydrate, 0.1 g of tannic acid and 6.9 g of ion-exchanged water were added.
The reactor temperature was maintained at 80 ° C. and stirring was continued for 45 minutes.
Next, 0.1 g of tetrachloroauric acid tetrahydrate and 3.8 g of ion-exchanged water were added. The reactor temperature was maintained at 80 ° C. and stirring was continued for 45 minutes.
After cooling to room temperature, the mixture was filtered with a nylon mesh having an aperture of 74 μm to obtain silver- and gold-supported silica-modified titanium oxide. The silver-gold supported silica-modified titanium oxide had a solid content of 2.0% and a pH of 6.5.

[Example 1]
17.151 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) having a number average particle size of 8 nm was added to an inorganic oxide (C-1 1.613 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 000 g, 0.002 g of a mineral oil-based antifoaming agent (A-1) (manufactured by San Nopco, “SN deformer AP”), 10.000 g of ethanol, and 70.234 g of ion-exchanged water, An aqueous composition (F-1) having a solid content of 4.0% by mass was obtained.
Next, one side of a 7 cm × 15 cm substrate (enamel paint) pre-coated with a black background portion (L * value 7) of a concealment rate test paper (manufactured by Nippon Test Panel Co., Ltd.) and an enamel paint that does not contain an anti-algal and anti-fungal agent ) And an aqueous composition (F-1) on one side of the 7 cm x 15 cm base material (the surface pre-coated with the enamel paint) pre-coated with the enamel paint containing the anti-algal and anti-fungal agent. The coating was applied using a spray so that the amount was 17 g / m ² .
A test paper (G-1) in which the coated base material is kept horizontal and left to stand at a temperature of 23 ° C., a relative humidity of 50%, and an illuminance of 20000 lux for 48 hours, and a coating film is formed on the black background portion of the concealment rate test paper. And a test plate (H-1) in which a coating film containing no anti-algae fungicide is formed on the base material, and a test plate (I) in which a coating film containing the anti-algae fungicide is formed on the base material (I -1) was obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-1), the coating film and the test paper (G-1), and the coating film and the test plate (H-1, I-1).

[Example 2]
13.283 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm was added to an inorganic oxide (C-1 ) 3.926 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. By mixing and stirring 600 g, 0.045 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), 10.000 g of ethanol, and 71.147 g of ion-exchanged water, An aqueous composition (F-2) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, the test paper (G-2) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-2) and a test plate (I-2) on which a coating film containing an anti-algal and anti-fungal agent was formed were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-2), the coating film and the test paper (G-2), and the coating film and the test plate (H-2, I-2).

Example 3
A water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) was added to 16.764 g of an inorganic oxide (C-1 ) 2.202 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. By mixing and stirring 060 g, mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN deformer VL”), ethanol 100.000 g, and ion-exchanged water 70.971 g, An aqueous composition (F-3) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-3) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-3) and a test plate (I-3) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-3), the coating film and the test paper (G-3), and the coating film and the test plate (H-3, I-3).

Example 4
14.705 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm was added to an inorganic oxide (C-1 ) 1.790 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. By mixing and stirring 000 g, 0.040 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), 10.000 g of ethanol, and 68.465 g of ion-exchanged water, An aqueous composition (F-4) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-4) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-4) and a test plate (I-4) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-4), the coating film and the test paper (G-4), and the coating film and the test plate (H-4, I-4).

Example 5
6.980 g of water-dispersed colloidal silica (B-3) having a number average particle size of 25 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex O-40”; solid content: 40% by mass) and an inorganic oxide (C -1) 2.876 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol By mixing and stirring 3.7000 g, 0.004 g of mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), 10.000 g of ethanol, and 76.440 g of ion-exchanged water. An aqueous composition (F-5) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-5) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-5) and a test plate (I-5) in which a coating film containing an anti-algal and anti-fungal agent was formed on the base material were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-5), the coating film and the test paper (G-5), and the coating film and the test plate (H-5, I-5).

Example 6
A water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) is added to 17.544 g of an inorganic oxide (C-1 1.650 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. By mixing and stirring 088 g, 0.004 g of mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), ethanol 100.000 g, and ion-exchanged water 70.714 g, An aqueous composition (F-6) having an amount of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-6) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-6) and the test plate (I-6) on which the coating film containing the anti-algal and anti-fungal agent was formed were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-6), the coating film and the test paper (G-6), and the coating film and the test plate (H-6, I-6).

Example 7
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20% by mass) to 19.4000 g, and ethanol to 10.0% by mass 1.000 g of prepared fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) and mineral oil-based antifoaming agent (A-1) (manufactured by San Nopco, “SN Deformer AP”) ) 0.020 g, ethanol 10.000 g, and ion-exchanged water 69.580 g were mixed and stirred to obtain an aqueous composition (F-7) having a solid content of 4.0% by mass.
In the same manner as in Example 1, a test paper (G-7) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no algal / antifungal agent on the substrate were formed. The test plate (H-7) and the test plate (I-7) on which the coating film containing the anti-algal and anti-fungal agent was formed were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-7), the coating film and the test paper (G-7), and the coating film and the test plate (H-7, I-7).

Example 8
16.061 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm is added to an inorganic oxide (C-2 3.290 g (solid content 20 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol 000 g, 0.030 g of a mineral oil-based antifoaming agent (A-1) (manufactured by San Nopco, “SN deformer AP”), 10.000 g of ethanol, and 69.620 g of ion-exchanged water, An aqueous composition (F-8) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-8) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-8) and the test plate (I-8) in which the coating film containing the anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-8), the coating film and the test paper (G-8), and the coating film and the test plate (H-8, I-8).

Example 9
Water-dispersed colloidal silica (B-1) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex OS”; solid content 20% by mass) is added to 15.520 g of an inorganic oxide (C-1 2.676 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. 000 g, 0.020 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), 10.000 g of ethanol, and 70.784 g of ion-exchanged water, An aqueous composition (F-9) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-9) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent on the base material were formed. Test plate (H-9) and a test plate (I-9) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-9), the coating film and the test paper (G-9), and the coating film and the test plate (H-9, I-9).

Example 10
16.544 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm was added to an inorganic oxide (C-1 1.556 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 000 g, 0.020 g of mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), and a fading dye (E-) having a solid content adjusted to 1.0% by mass with ion-exchanged water 2) (Hodogaya Chemical Co., Ltd., “Acid Red”) 1.200 g, ethanol 10.000 g, and ion-exchanged water 69.160 g were mixed and stirred to obtain a solid content of 4.0% by mass. To give the system composition (F-10).
In the same manner as in Example 1, a test paper (G-10) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-10) and the test plate (I-10) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-10), the coating film and the test paper (G-10), and the coating film and the test plate (H-10, I-10).

Example 11
17.460 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm is added to an inorganic oxide (C-1 1.338 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol 000 g, 0.020 g of a mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), 10.000 g of ethanol, and 70.182 g of ion-exchanged water are mixed and stirred. An aqueous composition (F-11) having a mass of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-11) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-11) and a test plate (I-11) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate was obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-11), the coating film and the test paper (G-11), and the coating film and the test plate (H-11, I-11).

Example 12
15.279 g of water-dispersed colloidal silica (B-2) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) having a number average particle diameter of 8 nm was added to 15.279 g of inorganic oxide (C-1 ) 2.801 g (solid content 29% by mass), fluorocarbon surfactant (D-2) (manufactured by AGC Seimi Chemical Co., “Surflon S-232”; solid content 30% by mass) 0.333 g, mineral oil system Anti-foaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”) 0.020 g and fading dye (E-1) (Kishida Chemical Co., Ltd.) whose solid content was adjusted to 1.0% by mass with ion-exchanged water Manufactured, "Methylene Blue") 1.200 g, ethanol 100.000 g, and ion-exchanged water 70.367 g were mixed and stirred to obtain an aqueous composition (F-12) having a solid content of 4.0% by mass. Obtained.
In the same manner as in Example 1, a test paper (G-12) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-12) and a test plate (I-12) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate was obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-12), the coating film and the test paper (G-12), and the coating film and the test plate (H-12, I-12).

Example 13
16.443 g of water-dispersed colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) and an inorganic oxide (C-1 ) 1.694 g (solid content 29% by mass), fluorocarbon surfactant (D-2) (AGC Seimi Chemical Co., Ltd., “Surflon S-232”; solid content 30% by mass) 0.667 g, mineral oil system Defoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”) 0.020 g, ethanol 10.000 g, and ion-exchanged water 71.176 g were mixed and stirred to obtain a solid content of 4.0% by mass. Obtained an aqueous composition (F-13).
In the same manner as in Example 1, a test paper (G-13) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-13) and a test plate (I-13) in which a coating film containing an antialgal and antifungal agent was formed on a substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-13), the coating film and the test paper (G-13), and the coating film and the test plate (H-13, I-13).

Example 14
15.908 g of water-dispersed colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) and an inorganic oxide (C-1) having photocatalytic activity 2.408 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol 000 g, mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”) 0.020 g, ethanol 10.000 g, and ion-exchanged water 70.664 g are mixed and stirred. An aqueous composition (F-14) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-14) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-14) and a test plate (I-14) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-14), the coating film and the test paper (G-14), and the coating film and the test plate (H-14, I-14).

Example 15
17.326 g of water-dispersed colloidal silica (B-2) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20 mass%) having a number average particle size of 8 nm is added to an inorganic oxide (C-1 ) 0.899 g (solid content 29% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 200 g, 0.030 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), and a fading dye (E) whose solid content is adjusted to 1.0% by mass with ion-exchanged water -2) By mixing and agitating 2.400 g (manufactured by Hodogaya Chemical Co., Ltd., “Acid Red”), ethanol 10.000 g, and ion-exchanged water 67.145 g, the solid content is 4.0. Yield% aqueous composition (F-15).
In the same manner as in Example 1, a test paper (G-15) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no antialgal and antifungal agent were formed on the substrate. Test plate (H-15) and a test plate (I-15) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-15), the coating film and the test paper (G-15), and the coating film and the test plate (H-15, I-15).

Example 16
Water-dispersed colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) is added to 15.046 g of an inorganic oxide (C-3 ) 42.438 g (solid content 2 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. 000 g, mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”) 0.030 g, and a fading dye (E-) whose solid content was adjusted to 1.0% by mass with ion-exchanged water 1) 1.200 g (manufactured by Kishida Chemical Co., Ltd., “methylene blue”), 100.00 g of ethanol, and 30.286 g of ion-exchanged water were mixed and stirred to obtain an aqueous group having a solid content of 4.0% by mass. To give an object (F-16).
In the same manner as in Example 1, a test paper (G-16) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-16) and the test plate (I-16) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-16), the coating film and the test paper (G-16), and the coating film and the test plate (H-16, I-16).

Example 17
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) was added to 14.507 g of an inorganic oxide (C-4 43.332 g (solid content 2% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 000 g, 0.020 g of mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), and a fading dye (E-) having a solid content adjusted to 1.0% by mass with ion-exchanged water 1) 1.200 g (manufactured by Kishida Chemical Co., Ltd., “methylene blue”), 10.000 g of ethanol, and 28.941 g of ion-exchanged water were mixed and stirred to obtain an aqueous group having a solid content of 4.0% by mass. To give an object (F-17).
In the same manner as in Example 1, a test paper (G-17) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-17) and a test plate (I-17) in which a coating film containing an anti-algal and anti-fungal agent was formed on a substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-17), the coating film and the test paper (G-17), and the coating film and the test plate (H-17, I-17).

Example 18
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries Ltd., “Snowtex NS”; solid content 20% by mass) is added to 14.765 g of an inorganic oxide (C-5 39.249 g (solid content 2% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 200 g, 0.030 g of a mineral oil-based antifoaming agent (A-3) (manufactured by San Nopco, “Nopco 8034L”), and a fading dye (E-) having a solid content adjusted to 1.0% by mass with ion-exchanged water 1) 1.200 g (manufactured by Kishida Chemical Co., “methylene blue”), 100.000 g of ethanol, and 32.556 g of ion-exchanged water were mixed and stirred to obtain an aqueous system having a solid content of 4.0 mass% To give an object (F-18).
In the same manner as in Example 1, a test paper (G-18) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-18) and the test plate (I-18) in which the coating film containing the antialgal and antifungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-18), the coating film and the test paper (G-18), and the coating film and the test plate (H-18, I-18).

Example 19
14.318 g of water-dispersed colloidal silica (B-2) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) having a number average particle size of 8 nm was added to an inorganic oxide (C-6) having photocatalytic activity. ) 45.216 g (solid content 2% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 000 g, 0.020 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), and a fading dye (E -1) Water having a solid content of 4.0% by mass was prepared by mixing and stirring 1.200 g (manufactured by Kishida Chemical Co., “methylene blue”), 10.000 g of ethanol, and 27.246 g of ion-exchanged water. To obtain a composition (F-19).
In the same manner as in Example 1, a test paper (G-19) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-19) and a test plate (I-19) on which a coating film containing an anti-algal and anti-fungal agent was formed were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-19), the coating film and the test paper (G-19), and the coating film and the test plate (H-19, I-19).

Example 20
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex NS”; solid content 20% by mass) 15.777 g of inorganic oxide (C-7) having photocatalytic activity 34.632 g (solid content 2 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, "Megafac F-444") whose solid content was adjusted to 10.0 mass% with ethanol. 000 g, 0.040 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), and a fading dye (E having a solid content adjusted to 1.0 mass% with ion-exchanged water) -1) Water having a solid content of 4.0% by mass was prepared by mixing and stirring 1.200 g (manufactured by Kishida Chemical Co., Ltd., “methylene blue”), 10.000 g of ethanol, and 37.351 g of ion-exchanged water. To obtain a composition (F-20).
In the same manner as in Example 1, a test paper (G-20) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. The test plate (H-20) and the test plate (I-20) in which the coating film containing the anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and characteristic evaluation results of the aqueous composition (F-20), the coating film and the test paper (G-20), and the coating film and the test plate (H-20, I-20).

Example 21
Water-dispersed colloidal silica (B-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, “Snowtex NS”; solid content 20 mass%) 15.826 g of inorganic oxide (C-1 ) 2.079 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. 000 g, 0.020 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), and a fading dye (E -1) 1.200 g (manufactured by Kishida Chemical Co., Ltd., “methylene blue”), 0.700 g of alcohol dispersion of copper oxide (CIK Nanotech Co., Ltd., “CUAP15WT% -G180”) (solid content) And 5.0 mass%), and ethanol 10.000 g, by stirring a mixture of ion-exchanged water 69.876G, to give a solid content 4.0% by weight of the aqueous composition (F-21).
In the same manner as in Example 1, a test paper (G-21) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-21) and a test plate (I-21) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-21), the coating film and the test paper (G-21), and the coating film and the test plate (H-21, I-21).

[Example 22]
14.815 g of water-dispersed colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass), and inorganic oxide (C-3) having photocatalytic activity ) 34.751 g (solid content 2% by mass) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0% by mass with ethanol. 000 g, 0.030 g of a mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”), and a fading dye (E -1) 1.200 g (manufactured by Kishida Chemical Co., Ltd., “methylene blue”), 0.700 g of alcohol dispersion of copper oxide (CIK Nanotech Co., Ltd., “CUAP15WT% -G180”) (solid content) And 5.0 mass%), and ethanol 10.000 g, by stirring a mixture of ion-exchanged water 37.204G, to give a solid content 4.0% by weight of the aqueous composition (F-22).
In the same manner as in Example 1, a test paper (G-22) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-22) and a test plate (I-22) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate was obtained.
Table 1 shows various physical properties and property evaluation results of the aqueous composition (F-22), the coating film and the test paper (G-22), and the coating film and the test plate (H-22, I-22).

[Comparative Example 1]
Water-dispersed colloidal silica (B-1) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries Ltd., “Snowtex OS”; solid content 20% by mass) is added to 14.550 g of an inorganic oxide (C-1 ) 3.345 g (solid content 29% by mass) and hydrocarbon surfactant (D-3) adjusted to 10.0% by mass with ethanol (manufactured by Nippon Emulsifier Co., Ltd., “New Coal 290-A”) Solid content 75% by mass) 1.000 g, mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN deformer VL”) 0.020 g, ethanol 10.000 g, and ion-exchanged water 71. By mixing and stirring 085 g, an aqueous composition (F-23) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-23) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-23) and a test plate (I-23) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained.
Table 2 shows various physical properties and property evaluation results of the aqueous composition (F-23), the coating film and the test paper (G-23), and the coating film and the test plate (H-23, I-23).

[Comparative Example 2]
14.832 g of water-dispersed colloidal silica (B-1) (manufactured by Nissan Chemical Industries, Ltd., “Snowtex OS”; solid content 20 mass%) having a number average particle size of 8 nm is added to an inorganic oxide (C-1 ) 2.885 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. By mixing and stirring 500 g, 0.047 g of silicone-based antifoaming agent (A-4) (manufactured by San Nopco, “SN Deformer 305”), 10.000 g of ethanol, and 70.636 g of ion-exchanged water, An aqueous composition (F-24) having an amount of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-24) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-24) and a test plate (I-24) in which a coating film containing an anti-algal and anti-fungal agent was formed on a substrate was obtained.
Table 2 shows various physical properties and property evaluation results of the aqueous composition (F-24), the coating film and the test paper (G-24), and the coating film and the test plate (H-24, I-24).

[Comparative Example 3]
14.223 g of water-dispersed colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass), and inorganic oxide (C-1) having photocatalytic activity ) 3.446 g (solid content 29 mass%) and fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) whose solid content was adjusted to 10.0 mass% with ethanol. By mixing and stirring 100 g, 0.046 g of a polyether antifoaming agent (A-5) (manufactured by San Nopco, “SN Deformer 170”), 10.000 g of ethanol, and 71.185 g of ion-exchanged water, An aqueous composition (F-25) having a solid content of 4.0% by mass was obtained.
In the same manner as in Example 1, a test paper (G-25) in which a coating film was formed on the black background portion of the concealment rate test paper and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-25) and a test plate (I-25) in which a coating film containing an anti-algal and anti-fungal agent was formed on the substrate were obtained. Table 2 shows various physical properties and characteristic evaluation results of the aqueous composition (F-25), the coating film and the test paper (G-25), and the coating film and the test plate (H-25, I-25).

[Comparative Example 4]
Water dispersion colloidal silica (B-2) having a number average particle diameter of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) to 16.475 g and ethanol to 10.0% by mass 7.000 g of adjusted fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) and mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN Deformer VL”) ) 0.005 g, ethanol 10.000 g, and ion-exchanged water 66.520 g were mixed and stirred to obtain an aqueous composition (F-26) having a solid content of 4.0% by mass.
In the same manner as in Example 1, a test paper (G-26) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-26) and a test plate (I-26) in which a coating film containing an anti-algal and anti-fungal agent was formed on a substrate was obtained.
Table 2 shows various physical properties and characteristic evaluation results of the aqueous composition (F-26), the coating film and the test paper (G-26), and the coating film and the test plate (H-26, I-26).

[Comparative Example 5]
Water dispersion colloidal silica (B-2) having a number average particle size of 8 nm (manufactured by Nissan Chemical Industries, Ltd., “Snowtex NS”; solid content 20% by mass) to 19.950 g, and ethanol to 10.0% by mass 0.060 g of prepared fluorocarbon surfactant (D-1) (manufactured by DIC, “Megafac F-444”) and mineral oil-based antifoaming agent (A-2) (manufactured by San Nopco, “SN deformer VL”) ) 0.004 g, ethanol 10.000 g, and ion-exchanged water 69.986 g were mixed and stirred to obtain an aqueous composition (F-27) having a solid content of 4.0% by mass.
In the same manner as in Example 1, a test paper (G-27) in which a coating film was formed on the black background portion of the concealment rate test paper, and a coating film containing no anti-algal and antifungal agent were formed on the substrate. Test plate (H-27) and a test plate (I-27) on which a coating film containing an anti-algal and anti-fungal agent was formed on a substrate were obtained.
Table 2 shows various physical properties and property evaluation results of the aqueous composition (F-27), the coating film and the test paper (G-27), and the coating film and the test plate (H-27, I-27).

  All of the aqueous compositions of the examples maintain high wettability and sprayability, do not impair the appearance even with a dark base material, and have a high appearance, stain resistance, and biofouling resistance over a long period of time. It was confirmed that a coating film that can be maintained at a level can be formed.

  The water-based composition, water-based paint, coating film, and coated product of the present invention are industrially applicable as various parts such as architectural exterior use, exterior display use, automotive parts, and optical parts such as displays and lenses. have.

Claims (9)

A fluorocarbon surfactant (D);
A mineral oil-based antifoaming agent (A),
Silicon dioxide (B),
Containing,
The mass ratio of the fluorocarbon surfactant (D) and the mineral oil-based antifoaming agent (A) is:
(Fluorocarbon surfactant (D) / mineral oil-based antifoaming agent (A)) = 2/1 to 100/1.   The aqueous composition according to claim 1, further comprising an inorganic oxide (C) having photocatalytic activity.   The aqueous composition according to claim 1 or 2, further comprising a fading dye (E).   A water-based paint containing the water-based composition according to any one of claims 1 to 3.   A coating film obtained from the water-based paint according to claim 4. A substrate;
The coating film according to claim 5 formed on at least a part of the surface of the substrate;
A coated product. A topcoat layer obtained from the coating film according to claim 5;
Having at least two subbing layers,
The undercoat layer contains a polymer and an algal and / or antifungal agent;
Composite coating. A substrate;
The composite coating film according to claim 7,
A coated product.   The coated product according to claim 6 or 8, wherein the substrate is an organic substrate.